Protective film-forming film and protective film-coated chip manufacturing method

Abstract

To provide an energy ray-curable protective film-forming film that has excellent punching processability and can effectively suppress generation of suction marks caused by conveying means, and a method for manufacturing a protective film-coated chip.SOLUTION: A protective film-forming film 13 is energy ray-curable, and has a Young's modulus of 2.6 MPa or more and a breaking elongation of 80% or more and 900% or less, as determined by the following measurement method. [Measurement method] The protective film-forming film 13 is cut into a test piece measuring 15 mm wide and 30 mm long, and a tensile test is performed with a chuck distance of 20 mm and a pulling speed of 200 mm / min to measure the tensile load and elongation. The Young's modulus [MPa] is calculated from the slope of the stress-strain curve at the beginning of the test, and the breaking elongation [%] is determined from the elongation of the test piece at break.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a protective film-forming film and a method for manufacturing a chip with a protective film. [Background technology]

[0002] Some wafers, such as semiconductor wafers and insulator wafers, have circuits formed on one surface (circuit surface) and also have protruding electrodes such as bumps on that surface (circuit surface). Such wafers are divided into chips, and are mounted on a circuit board by connecting the protruding electrodes to connection pads on the circuit board using the so-called face-down method. In such wafers and chips, the surface opposite to the circuit surface (back surface) may be protected with a protective film to prevent damage such as cracks.

[0003] To form such a protective film, a protective film-forming film for forming the protective film is attached to the back surface of the wafer. The protective film-forming film is laminated on a support sheet for supporting it, and the protective film-forming film may be attached to the back surface of the wafer in the form of a composite sheet for forming a protective film, or the protective film-forming film may be attached to the back surface of the wafer without being laminated on a support sheet. After laser marking on the protective film-forming film, the semiconductor wafer is divided into chips by dicing and picked up, if necessary, after curing with heat or energy rays to enhance the protective performance of the protective film-forming layer. Alternatively, the protective film formed by curing the protective film-forming film with heat or energy rays is laser marked, and the semiconductor wafer is divided into chips by dicing and picked up. Next, the picked-up semiconductor chip with the protective film is flip-chip connected to connection pads on a circuit board such as a motherboard, and the circuit board is heated to melt the protruding electrodes on the chip with the protective film (hereinafter referred to as the reflow process), strengthening the electrical connection between the protruding electrodes and the connection pads on the circuit board, and the chip is then mounted on the circuit board.

[0004] When a thermosetting protective film-forming film that is cured by heating or an energy ray-curable protective film-forming film that is cured by irradiation with energy rays is used, the cured product serves as the protective film, which has the advantage of providing higher protection for wafers and chips than when a non-curable protective film-forming film is used. While a thermosetting protective film-forming film requires a relatively long heating time for curing, an energy ray-curable protective film-forming film has the advantage of requiring only a short energy ray irradiation time for curing. Accordingly, various efforts have been made to develop energy ray-curable protective film-forming films (see Patent Documents 1 to 3, etc.). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 068042 [Patent Document 2] International Publication No. 2017 / 188197 [Patent Document 3] International Publication No. 2019 / 082977 Summary of the Invention [Problem to be solved by the invention]

[0006] When a protective film-forming film is not laminated on a support sheet but is attached to the back surface of a semiconductor wafer to manufacture a semiconductor chip with a protective film, a transport step is performed in which a transport means is brought into contact with the exposed surface of the protective film-forming film opposite the semiconductor wafer side, and the semiconductor wafer with the protective film-forming film is transported in a fixed state by the transport means. When a workpiece with an energy ray-curable protective film-forming film is transported using such a transport means, contact marks of the transport means (the fixing portion) may be formed at the fixing portion of the energy ray-curable protective film by the transport means, more specifically, at the contact portion of the fixing portion in the transport means. For example, if the fixing portion is a suction cup with a circular planar shape, a circular suction mark may be formed on the exposed surface of the protective film-forming film. On the other hand, if the composition of the energy ray-curable protective film-forming film is designed to be relatively hard in an attempt to suppress the occurrence of suction marks, the protective film-forming film with a release film may be cut into a circular shape, and the unnecessary circular outer periphery of the protective film-forming film may be torn off when it is wound up.

[0007] The present invention has been made in consideration of the above circumstances, and provides an energy ray-curable protective film-forming film that has excellent punching processability from a protective film-forming film with a release film and can effectively suppress the occurrence of suction marks caused by a semiconductor wafer transport means with a protective film-forming film, and a method for manufacturing a chip with a protective film. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] An energy ray-curable protective film-forming film, A protective film-forming film having a Young's modulus of 2.6 MPa or more and a breaking elongation of 80% or more and 900% or less, as determined by the following measurement method. [Measurement method] The protective film-forming film is cut into test pieces measuring 15 mm in width and 30 mm in length, and a tensile test is performed with a chuck distance of 20 mm and a tensile speed of 200 mm / min. The tensile load and elongation are measured, and the Young's modulus [MPa] is calculated from the slope of the stress-strain curve at the beginning of the test, and the breaking elongation [%] is determined from the elongation of the test piece at the time of break. [2] The protective film-forming film according to [1], wherein the Young's modulus determined by the above measurement method is 45 MPa or less. [3] The protective film-forming film according to [1] or [2], which has a near-infrared transmittance at a wavelength of 1300 nm of 10% or less. [4] The protective film-forming film according to any one of [1] to [3], wherein the protective film-forming film contains a component (a2) having an energy ray-curable group and a weight average molecular weight of 100 or more and less than 80,000, and the component (a2) contains a multifunctional acrylate compound having two (meth)acryloyl groups in one molecule and a multifunctional acrylate compound having three (meth)acryloyl groups in one molecule. [5] A method for manufacturing a chip with a protective film, the method comprising: A punching process for punching the protective film-forming film according to any one of [1] to [4]; a bonding step of bonding a punched protective film-forming film to the back surface of the wafer to produce a semiconductor wafer with a protective film-forming film; a conveying step of bringing a conveying means into contact with an exposed surface of the semiconductor wafer with the protective film-forming film on the side opposite to the semiconductor wafer side, and conveying the semiconductor wafer with the protective film-forming film in a fixed state by the conveying means; a curing step of curing the protective film-forming film with energy rays to form the protective film; a dividing step of dividing the wafer and cutting the protective film to produce a plurality of chips with the protective film; A method for manufacturing a chip with a protective film having the above structure. [Effects of the Invention]

[0009] According to the present invention, there is provided an energy ray curable protective film-forming film and a method for manufacturing a chip with a protective film, which has excellent processability for cutting a protective film-forming film from a protective film-forming film with a release film and can effectively suppress the occurrence of suction marks caused by a semiconductor wafer transport means with a protective film-forming film. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a protective film-forming film according to an embodiment of the present invention. [Figure 2] 1A to 1C are cross-sectional views for schematically illustrating an example of a punching process in a method for manufacturing a chip with a protective film according to an embodiment of the present invention. [Figure 3] 1A to 1C are cross-sectional views for schematically illustrating examples of a bonding step, a transport step, and a curing step in a method for manufacturing a chip with a protective film according to one embodiment of the present invention. [Figure 4] 1A to 1C are cross-sectional views for schematically illustrating an example of a dividing step in the method for manufacturing a chip with a protective film according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] ◇Protective film forming film The protective film-forming film according to one embodiment of the present invention is an energy ray-curable protective film-forming film, and has a Young's modulus of 2.6 MPa or more and a breaking elongation of 80% or more and 900% or less, as determined by the following measurement method.

[0012] [Measurement method] The protective film-forming film is cut into test pieces measuring 15 mm in width and 30 mm in length, and a tensile test is performed with a chuck distance of 20 mm and a tensile speed of 200 mm / min. The tensile load and elongation are measured, and the Young's modulus [MPa] is calculated from the slope of the stress-strain curve at the beginning of the test, and the breaking elongation [%] is determined from the elongation of the test piece at the time of break.

[0013] As used herein, "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radioactive rays, and electron beams. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet light source. Electron beams can be irradiated using those generated by an electron beam accelerator or the like. In this specification, "energy ray curable" means a property of being cured by irradiation with energy rays, and "non-energy ray curable" means a property of not being cured even when irradiated with energy rays.

[0014] The protective film-forming film of this embodiment has a Young's modulus determined by the above-mentioned measurement method of 2.6 MPa or more, preferably 2.7 MPa or more, and more preferably 2.8 MPa or more. When the Young's modulus is equal to or greater than the above-mentioned lower limit, when the protective film-forming film is transported in a state where the transport means is in contact with the exposed surface of the protective film-forming film, the generation of suction marks by the transport means can be more effectively suppressed.

[0015] The protective film-forming film of this embodiment has a breaking elongation of 80% or more, preferably 90% or more, more preferably 100% or more, and even more preferably 120% or more. When the breaking elongation is equal to or more than the lower limit, the protective film-forming film can be more effectively prevented from breaking when it is attached to a semiconductor wafer. The protective film-forming film of the present embodiment has a breaking elongation of 900% or less, preferably 800% or less, more preferably 750% or less, and even more preferably 700% or less. When the breaking elongation is equal to or less than the upper limit, the protective film-forming film has better punching processability.

[0016] The protective film-forming film of this embodiment has a Young's modulus determined by the above-mentioned measurement method of preferably 45 MPa or less, more preferably 40 MPa or less, and even more preferably 38 MPa or less. When the Young's modulus is equal to or less than the above-mentioned upper limit, the punching processability of the protective film-forming film is superior, and the adhesion of the protective film-forming film to a wafer is improved.

[0017] In order to provide an excellent near-infrared shielding effect, the protective film-forming film of the present embodiment preferably has a near-infrared transmittance at a wavelength of 1300 nm of 10% or less. The near-infrared transmittance at a wavelength of 1300 nm can be measured, for example, using a commercially available ultraviolet-visible-near-infrared spectrophotometer.

[0018] In order to ensure excellent near-infrared shielding effect, the near-infrared transmittance of the protective film-forming film at a wavelength of 1300 nm is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and particularly 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.

[0019] The near-infrared transmittance of the protective film-forming film at a wavelength of 1300 nm can be adjusted by the components contained in the protective film-forming composition described below, the energy ray-curable component (a), the polymer (b) not having an energy ray-curable group, the type and content of the inorganic filler (d) and / or the colorant (g), particularly the type and content of the inorganic filler (d) and the colorant (g).

[0020] By using the protective film-forming film of this embodiment, a chip with a protective film can be manufactured, which includes a chip and a protective film provided on the back surface of the chip. The chip with the protective film can be manufactured, for example, by attaching a protective film-forming film to the back surface of a wafer, forming a protective film by hardening the protective film-forming film, dividing the wafer into chips, and cutting the protective film along the outer periphery of the chip.

[0021] In this specification, the term "wafer" refers to a semiconductor wafer made of an elemental semiconductor such as silicon, germanium, or selenium, or a compound semiconductor such as GaAs, GaP, InP, CdTe, ZnSe, or SiC; or an insulating wafer made of an insulating material such as sapphire, glass, lithium niobate, or lithium tantalate. A circuit is formed on one surface of each of these wafers, and in this specification, the surface of the wafer on which the circuit is formed is referred to as the "circuit side," and the surface of the wafer opposite the circuit side is referred to as the "back side." The wafer is divided into chips by dicing or other means. In this specification, as with the wafer, the surface of the chip on which the circuit is formed is referred to as the "circuit side," and the surface of the chip opposite the circuit side is referred to as the "back side." Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps, pillars, etc. The protruding electrodes are preferably made of solder.

[0022] Furthermore, by using the chip with the protective film, a substrate device can be manufactured. In this specification, the term "substrate device" refers to a device in which a chip with a protective film is flip-chip connected to connection pads on a circuit board at protruding electrodes on the circuit surface of the chip. For example, if a semiconductor wafer is used as the wafer, the substrate device may be a semiconductor device.

[0023] The protective film-forming film of the present embodiment is energy ray curable.

[0024] As used herein, "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radioactive rays, and electron beams. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet light source. Electron beams can be irradiated using those generated by an electron beam accelerator or the like. In this specification, "energy ray curable" means a property of being cured by irradiation with energy rays, and "non-energy ray curable" means a property of not being cured even when irradiated with energy rays. Moreover, "non-curable" means a property that does not cure by any means such as heating or irradiation with energy rays.

[0025] The curing conditions when the protective film-forming film is cured with energy rays to form a protective film are not particularly limited as long as the degree of curing is such that the protective film can fully perform its function, and may be selected appropriately depending on the type of protective film-forming film. For example, the irradiance of the energy ray when the energy ray curable protective film forming film is cured with the energy ray is 60 to 320 mW / cm 2 The amount of energy rays during the curing is preferably 100 to 1000 mJ / cm. 2 It is preferable that:

[0026] Examples of the protective film-forming film include one containing an energy ray-curable component (a), one containing an energy ray-curable component (a) and a polymer (b) having no energy ray-curable group, and one containing an energy ray-curable component (a), a polymer (b) having no energy ray-curable group, and an inorganic filler (d). The components contained in the protective film-forming film will be described in detail later.

[0027] The protective film-forming film may be composed of one layer (single layer) or two or more layers. When the protective film-forming film is 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.

[0028] In this specification, not only in the case of a protective film-forming film, "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same," and further, "multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other."

[0029] The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 3 to 60 μm. When the thickness of the protective film-forming film is equal to or greater than the lower limit, a protective film with higher protective ability can be formed. When the thickness of the protective film-forming film is equal to or less than the upper limit, the thickness of the protective film-coated chip can be prevented from becoming excessive, which is suitable for miniaturizing and thinning semiconductor devices. Here, "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film, and for example, the thickness of a protective film-forming film consisting of multiple layers means the total thickness of all layers that make up the protective film-forming film. The "thickness" in this specification can be determined by the method specified in JIS K 7130:1999 (ISO 4593:1993).

[0030] <<Composition for forming protective film>> The protective film-forming film can be formed using an energy ray-curable protective film-forming composition (sometimes simply referred to as "protective film-forming composition" in this specification) containing its constituent materials. For example, the protective film-forming film can be formed by applying the protective film-forming composition to the surface to be formed and drying it as necessary. The ratio of the contents of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the ratio of the contents of the components in the protective film-forming film. In this specification, "room temperature" means a temperature that is not particularly cooled or heated, i.e., an ordinary temperature, and examples thereof include a temperature of 18 to 28°C.

[0031] The protective film-forming composition may be applied by a known method, such as a method using various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Mayer bar coater, or kiss coater.

[0032] The drying conditions for the composition for forming a protective film are not particularly limited. However, when the composition for forming a protective film contains a solvent described below, it is preferable to heat-dry it. The composition for forming a protective film containing a solvent is preferably heat-dried, for example, at 70 to 130°C for 10 seconds to 5 minutes.

[0033] <Energy ray-curable protective film-forming composition (IV-1)> A preferred example of the energy ray-curable protective film-forming composition is energy ray-curable protective film-forming composition (IV-1) (sometimes abbreviated herein simply as "composition (IV-1)") containing the energy ray-curable component (a).

[0034] [Energy ray curable component (a)] The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and it imparts film-forming properties, flexibility, etc. to the energy ray-curable protective film-forming film, and is also a component that forms a hard protective film after curing. 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 or more and 2,000,000 or less, and a component (a2) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 80,000. The polymer (a1) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked. In this specification, unless otherwise specified, the "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC). When the chromatogram of the energy ray-curable component (a) obtained by GPC has peaks separated into both weight-average molecular weight regions of 100 or more and less than 80,000 and 80,000 or more and 2,000,000 or less, the energy ray-curable component (a) can be considered to contain both the polymer (a1) and the component (a2).

[0035] (Polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80,000 or more and 2,000,000 or less) Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 or more and 2,000,000 or less include 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 a group reactive with the functional group and an energy ray-curable group such as an energy ray-curable double bond.

[0036] Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom), an epoxy group, etc. However, from the viewpoint of preventing corrosion of circuits of a workpiece or a processed workpiece, etc., it is preferable that the functional group be a group other than a carboxy group. Among these, the functional group is preferably a hydroxyl group.

[0037] Acrylic polymer having functional groups (a11) The acrylic polymer (a11) having a functional group may be, for example, a polymer obtained by copolymerizing an acrylic monomer having the functional group with an acrylic monomer not having the functional group. In addition to these monomers, the acrylic polymer may also be a polymer obtained by copolymerizing a monomer other than the acrylic monomer (a non-acrylic monomer). The acrylic polymer (a11) may be a random copolymer or a block copolymer, and known methods can be used for the polymerization method.

[0038] Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

[0039] 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 not having a (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol.

[0040] Examples of the carboxy 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 and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; and (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

[0041] The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.

[0042] The acrylic monomer having a functional group that constitutes the acrylic polymer (a11) may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0043] Examples of the acrylic monomer not having a 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, and isopropyl (meth)acrylate. Examples of alkyl (meth)acrylate esters include those in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as sononyl, 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, and octadecyl (meth)acrylate (stearyl (meth)acrylate).

[0044] Examples of the acrylic monomer not having a functional group include alkoxyalkyl group-containing (meth)acrylic acid esters such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and derivatives thereof; and non-crosslinkable tertiary amino group-containing (meth)acrylic acid esters such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

[0045] The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be selected arbitrarily.

[0046] Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene. The non-acrylic monomer constituting the acrylic polymer (a11) may be of one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be selected arbitrarily.

[0047] In the acrylic polymer (a11), the proportion (content) of the structural units derived from the acrylic monomer having the functional group relative to the total amount of structural units constituting the acrylic polymer (a11) is preferably 0.1 to 50 mass%, more preferably 1 to 40 mass%, and particularly preferably 3 to 30 mass%. When the proportion is within this 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) can easily adjust the degree of curing of the protective film within a preferred range.

[0048] The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be selected arbitrarily.

[0049] In the composition (IV-1), the proportion of the content of the acrylic resin (a1-1) relative to the total content of components other than the solvent (i.e., the proportion of the content of the acrylic resin (a1-1) relative to the total mass of the energy ray-curable protective film-forming film) is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, and particularly preferably 10 to 50 mass%.

[0050] Energy ray curable compounds (a12) The energy ray-curable compound (a12) preferably has one or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group reactive with the functional group of the acrylic polymer (a11), and more preferably has an isocyanate group as the group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.

[0051] The number of energy ray-curable groups that the energy ray-curable compound (a12) has in one molecule is not particularly limited and can be appropriately selected in consideration of, for example, the physical properties required for the target protective film, such as the shrinkage rate. For example, the energy ray-curable compound (a12) preferably has 1 to 5, and more preferably 1 to 3, energy ray-curable groups in one molecule.

[0052] Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate; Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate. Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

[0053] The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof can be selected arbitrarily.

[0054] In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable groups derived from the energy ray-curable compound (a12) to the content of the functional groups derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is within this range, the adhesive strength of the cured product of the energy ray-curable protective film-forming film is increased. When the energy ray-curable compound (a12) is a monofunctional compound (having one such group per molecule), the upper limit of the content ratio is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having two or more such groups per molecule), the upper limit of the content ratio may exceed 100 mol%.

[0055] The weight average molecular weight (Mw) of the polymer (a1) is 80,000 or more and 2,000,000 or less, preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000. Here, the "weight average molecular weight" is as explained above.

[0056] When the polymer (a1) is at least partially crosslinked with a crosslinking agent, the polymer (a1) may be crosslinked at the group reactive with the crosslinking agent by polymerization of a monomer that does not correspond to any of the above-mentioned monomers described as constituting the acrylic polymer (a11) and has a group reactive with the crosslinking agent, or may be crosslinked at a group reactive with the functional group derived from the energy ray-curable compound (a12).

[0057] The polymer (a1) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0058] (Component (a2) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 80,000) The energy ray-curable group in component (a2) having an energy ray-curable group and a weight average molecular weight of 100 or more and less than 80,000 includes a group containing an energy ray-curable double bond, and preferred examples thereof include a (meth)acryloyl group and a vinyl group.

[0059] The component (a2) can be classified into a component (a2-1) having an energy ray-curable group and a weight average molecular weight of 100 or more and less than 5000, and a component (a2-2) having an energy ray-curable group and a weight average molecular weight of 5000 or more and less than 80000. When the chromatogram of the component (a2) obtained by GPC has peaks separated into both weight-average molecular weight regions of 100 or more and less than 5,000 and 5,000 or more and less than 80,000, the component (a2) can be considered to contain both the component (a2-1) and the component (a2-2).

[0060] The component (a2-1) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 5000, and the component (a2-2) having an energy ray-curable group and a weight-average molecular weight of 5000 or more and less than 80000, are not particularly limited as long as they satisfy the above conditions, and examples thereof include low-molecular-weight compounds having energy ray-curable groups, polyfunctional oligomers, acrylate oligomers having (meth)acryloyl groups, epoxy resins having energy ray-curable groups, and phenolic resins having energy ray-curable groups.

[0061] Among the components (a2-1) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 5000, examples of low-molecular-weight compounds having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth)acryloyl group are preferred. Examples of the acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1,10-decanediol ... Bifunctional (meth)acrylates such as 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane; polyfunctional (meth)acrylates such as tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Examples include polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers.

[0062] Among the components (a2-1) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 5,000, and the components (a2-2) having an energy ray-curable group and a weight-average molecular weight of 5,000 or more and less than 80,000, examples of polyfunctional oligomers and acrylate oligomers having a (meth)acryloyl group include polyfunctional oligomers and urethane (meth)acrylate oligomers sold by Mitsubishi Chemical Corporation under the trade name "Shiko (registered trademark)" and urethane (meth)acrylate oligomers sold by KJ Chemicals Corporation under the trade name "Quick cure (registered trademark)."

[0063] Among the component (a2-1) having an energy ray-curable group and a weight-average molecular weight of 100 or more but less than 5000 and the component (a2-2) having an energy ray-curable group and a weight-average molecular weight of 5000 or more but less than 80000, examples of the epoxy resin having an energy ray-curable group and the phenolic resin having an energy ray-curable group that can be used include those described in paragraph 0043 of JP 2013-194102 A. Such resins also fall under the category of resins constituting the thermosetting component described below, but in the present invention, if the component has an energy ray-curable group and a weight-average molecular weight of 100 or more but less than 5000, it is treated as the component (a2-1), and if the component has an energy ray-curable group and a weight-average molecular weight of 5000 or more but less than 80000, it is treated as the component (a2-2).

[0064] In the composition (IV-1) and the protective film-forming film, when the energy ray-curable component (a) contains the component (a2), the component (a2) preferably contains a polyfunctional acrylate compound having two (meth)acryloyl groups per molecule and a polyfunctional acrylate compound having three (meth)acryloyl groups per molecule. This improves adhesion to the wafer when the protective film-forming film is cured with energy rays to form a protective film. Furthermore, the component (a2) preferably contains a component (a2-2-1) having two (meth)acryloyl groups per molecule and a weight-average molecular weight of 5,000 or more and less than 80,000, and a component (a2-1-1) having three (meth)acryloyl groups per molecule and a weight-average molecular weight of 100 or more and less than 5,000.

[0065] The weight average molecular weight of the component (a2-1) is 100 or more and less than 5,000, preferably 200 to 3,000, and more preferably 300 to 2,000.

[0066] The component (a2-1) contained in the composition (IV-1) and the energy ray-curable film for forming a protective film may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0067] The weight average molecular weight of the component (a2-2) is 5,000 or more and less than 80,000, preferably 5,600 to 30,000, more preferably 5,700 to 20,000, and even more preferably 5,700 to 10,000.

[0068] The component (a2-2) contained in the composition (IV-1) and the energy ray-curable film for forming a protective film may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0069] When the protective film-forming film contains the component (a2-1) as the energy ray-curable component (a), it preferably contains a polyfunctional acrylate compound having two or three or more (meth)acryloyl groups in one molecule, more preferably a polyfunctional acrylate compound having three or more (meth)acryloyl groups in one molecule, and even more preferably a polyfunctional urethane (meth)acrylate oligomer. The cured product (protective film) of the protective film-forming film containing such energy ray-curable component (a) by energy ray irradiation has good protective ability and flexibility, and has particularly excellent properties.

[0070] When the composition (IV-1) and the protective film-forming film contain the energy ray-curable component (a), the content of the energy ray-curable component (a) in the composition (IV-1) and the protective film-forming film is preferably 60 to 200 parts by mass, more preferably 80 to 180 parts by mass, relative to 100 parts by mass of the content of the polymer (b) that does not have an energy ray-curable group, and may be, for example, 100 to 160 parts by mass or 120 to 150 parts by mass.

[0071] In composition (IV-1), the content ratio of the energy ray-curable component (a) relative to the total content of all components other than the solvent (i.e., the content ratio of the energy ray-curable component (a) in the protective film relative to the total mass of the protective film) is preferably 12 to 31 mass%, more preferably 14 to 28 mass%, and even more preferably 16 to 25 mass%. When the content ratio of the energy ray-curable component (a) (i.e., the content ratio of the energy ray-curable component (a)) is not less than the lower limit, the energy ray curability of the protective film-forming film becomes better. When the content ratio of the energy ray-curable component (a) (i.e., the content ratio of the energy ray-curable component (a)) is not more than the upper limit, it is easy to prepare a desired protective film-forming film.

[0072] The component (a2-2) contained in the composition (IV-1) and the energy ray-curable film for forming a protective film may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0073] When the protective film-forming film contains the component (a2-1) as the energy ray-curable component (a), it preferably contains a polyfunctional acrylate compound having two or three or more (meth)acryloyl groups in one molecule, more preferably a polyfunctional acrylate compound having three or more (meth)acryloyl groups in one molecule, and even more preferably a polyfunctional urethane (meth)acrylate oligomer. The cured product (protective film) of the protective film-forming film containing such energy ray-curable component (a) by energy ray irradiation has good protective ability and flexibility, and has particularly excellent properties.

[0074] When the composition (IV-1) and the protective film-forming film contain the energy ray-curable component (a), the content of the energy ray-curable component (a) in the composition (IV-1) and the protective film-forming film is preferably 60 to 200 parts by mass, more preferably 80 to 180 parts by mass, relative to 100 parts by mass of the content of the polymer (b) that does not have an energy ray-curable group, and may be, for example, 100 to 160 parts by mass or 120 to 150 parts by mass.

[0075] In composition (IV-1), the content ratio of the energy ray-curable component (a) relative to the total content of all components other than the solvent (i.e., the content ratio of the energy ray-curable component (a) in the protective film relative to the total mass of the protective film) is preferably 12 to 31 mass%, more preferably 14 to 28 mass%, and even more preferably 16 to 25 mass%. When the content ratio of the energy ray-curable component (a) (i.e., the content ratio of the energy ray-curable component (a)) is not less than the lower limit, the energy ray curability of the protective film-forming film becomes better. When the content ratio of the energy ray-curable component (a) (i.e., the content ratio of the energy ray-curable component (a)) is not more than the upper limit, it is easy to prepare a desired protective film-forming film.

[0076] [Polymer (b) having no energy ray-curable group] When the composition (IV-1) and the energy ray-curable protective film-forming film contain either or both of the component (a2-1) and the component (a2-2) as the energy ray-curable component (a), they preferably further contain a polymer (b) that does not have an energy ray-curable group. The polymer (b) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.

[0077] Examples of the polymer (b) having no energy ray-curable group include acrylic resins, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Among these, the polymer (b) is preferably an acrylic resin (hereinafter sometimes abbreviated as "acrylic resin (b-1)").

[0078] The acrylic resin (b-1) may be a known one, and may be, for example, a homopolymer of one kind of acrylic monomer, a copolymer of two or more kinds of acrylic monomers, or a copolymer of one or more kinds of acrylic monomers and one or more kinds of monomers other than the acrylic monomers (non-acrylic monomers).

[0079] Examples of the acrylic monomer constituting the acrylic resin (b-1) include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid esters, hydroxyl group-containing (meth)acrylic acid esters, substituted amino group-containing (meth)acrylic acid esters, etc. Here, the "substituted amino group" is as explained above.

[0080] Examples of the (meth)acrylic acid alkyl ester include the same as the acrylic monomer not having a functional group (e.g., a (meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has a chain structure containing 1 to 18 carbon atoms) that constitutes the acrylic resin (a11) described above.

[0081] Examples of the (meth)acrylic acid ester having no functional group and having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; (Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester; (Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester are included.

[0082] Examples of the glycidyl group-containing (meth)acrylic acid ester include glycidyl (meth)acrylate. Examples of the hydroxyl group-containing (meth)acrylic acid ester include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylate.

[0083] The acrylic resin (b-1) preferably has a structural unit derived from 4-(meth)acryloylmorpholine and other structural units, i.e., the acrylic resin (b-1) is preferably a copolymer of 4-(meth)acryloylmorpholine and other monomers or oligomers.

[0084] In the acrylic resin (b-1), the proportion of the amount of structural units derived from 4-(meth)acryloylmorpholine relative to the total amount of structural units is preferably 10 to 30 mass%, more preferably 13 to 30 mass%, and may be any of 18 to 30 mass%, and 23 to 30 mass%.

[0085] Examples of the non-acrylic monomer that constitutes the acrylic resin (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0086] The polymer (b) having no energy ray-curable group and at least a portion of which is crosslinked with a crosslinking agent may be, for example, a polymer in which a reactive functional group in the polymer (b) has reacted with a crosslinking agent. The reactive functional group may be appropriately selected depending on the type of crosslinking agent, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, etc., and among these, a hydroxyl group, which has high reactivity with an isocyanate group, is preferred. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, etc., and among these, a carboxyl group, which has high reactivity with an epoxy group, is preferred. However, from the viewpoint of preventing corrosion of the circuit of the workpiece or the processed workpiece, it is preferable that the reactive functional group be a group other than a carboxyl group.

[0087] Examples of the polymer (b) having a reactive functional group but not having an energy ray-curable group include those obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic resin (b-1), one or both of the acrylic monomers and non-acrylic monomers listed as the monomers constituting the acrylic resin (b-1) may be those having the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester, and also those obtained by polymerizing a monomer in which one or more hydrogen atoms in the acrylic monomers or non-acrylic monomers listed above are substituted with the reactive functional group.

[0088] In the polymer (b) having a reactive functional group, the proportion (content) of the amount of the structural units derived from the monomer having a reactive functional group relative to the total amount of the structural units constituting the polymer (b) is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 18% by mass or less, and even more preferably 3% by mass or more and 16% by mass or less. When the proportion is in this range, the degree of crosslinking in the polymer (b) becomes a more preferable range.

[0089] The weight-average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, in order to improve the film-forming properties of the composition (IV-1). Here, the "weight-average molecular weight" is as explained above.

[0090] The polymer (b) not having an energy ray-curable group contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0091] The energy ray-curable component (a) contained in the composition (IV-1) and the energy ray-curable protective film-forming film preferably contains either one or both of the components (a2-1) and (a2-2) as the component (a2). When the composition (IV-1) contains either one or both of the components (a2-1) and (a2-2), it preferably also contains a polymer (b) having no energy ray-curable groups, and in this case, it may further contain the (a1). The composition (IV-1) and the energy ray-curable protective film-forming film may not contain the polymer (a1), but may contain both the component (a2) and the polymer (b) having no energy ray-curable groups. The composition (IV-1) and the energy ray-curable protective film-forming film may also not contain the components (a2-1) and (a2-2), but may contain both the polymer (a1) and the polymer (b) having no energy ray-curable groups.

[0092] When composition (IV-1) contains the component (a2) (i.e., the component (a2-1) and / or the component (a2-2)), the total content of the components (a2-1) and (a2-2) is preferably 80 to 250 parts by mass, and more preferably 120 to 200 parts by mass, per 100 parts by mass of the polymer (b) that does not have an energy ray-curable group. Furthermore, the content of the component (a2-2) is preferably 50 to 250 parts by mass, and more preferably 70 to 180 parts by mass, per 100 parts by mass of the polymer (b) that does not have an energy ray-curable group.

[0093] When the composition (IV-1) contains the component (a2) and the polymer (b) having no energy ray-curable groups, the content of the component (a2) in the composition (IV-1) is preferably 8% by mass or more and 400% by mass or less, and more preferably 10% by mass or more and 350% by mass or less, relative to 100% by mass of the total content of the component (a2) and the polymer (b) having no energy ray-curable groups.

[0094] In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the protective film-forming film) is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and particularly preferably 20% by mass or more and 70% by mass or less. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray curability of the protective film-forming film becomes better.

[0095] [Other ingredients] The composition (IV-1) and the protective film-forming film may contain other components that do not fall into either the energy ray-curable component (a) or the polymer (b) that does not have an energy ray-curable group, within a range that does not impair the effects of the present invention. Examples of the other components include a photopolymerization initiator (c); an inorganic filler (d); a coupling agent (e); a crosslinking agent (f); a colorant (g); a thermosetting component (h); an ultraviolet absorber (m); and a general-purpose additive (z).

[0096] (Photopolymerization initiator (c)) When the composition (IV-1) and the protective film-forming film contain a photopolymerization initiator (c), the polymerization (curing) reaction of the energy ray-curable component (a) can be efficiently promoted.

[0097] Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as 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-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. Examples of suitable acylphosphine oxide compounds include acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone. Examples of the photopolymerization initiator include photosensitizers such as amines.

[0098] The photopolymerization initiator (c) contained in the composition (IV-1) and the protective film-forming film may be one type or two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily. For example, a highly reactive photopolymerization initiator that is liquid at room temperature, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, can be used alone to efficiently crosslink the protective film-forming film and increase the gel fraction. A less reactive photopolymerization initiator, such as 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one or 1-hydroxycyclohexyl-phenyl ketone, can be used in combination with a more reactive photopolymerization initiator, such as 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, to efficiently crosslink the protective film-forming film and increase the gel fraction.

[0099] When a photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition (IV-1) 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, per 100 parts by mass of the energy ray-curable component (a).

[0100] (Inorganic filler (d)) When the composition (IV-1) 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., a protective film) can be more easily adjusted by adjusting the amount of the inorganic filler (d) in the composition (IV-1) 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. In addition, by using a protective film-forming film containing an inorganic filler (d), it is also possible to reduce the moisture absorption rate of the cured product of the protective film-forming film (e.g., a protective film) and improve heat dissipation properties.

[0101] Examples of the inorganic filler (d) include powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads made by spheronizing these inorganic materials; surface-modified products of these inorganic materials; single-crystal fibers of these inorganic materials; and glass fibers. Among these, the inorganic filler (d) is preferably silica or alumina.

[0102] The inorganic filler (d) contained in the composition (IV-1) and the protective film-forming film may be one type or two or more types, and if there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0103] The average particle size of the inorganic filler (d) is preferably 15 μm or less, more preferably 12 μm or less, and even more preferably 10 μm or less. The average particle size of the inorganic filler (d) may be 0.1 μm or more, 0.2 μm or more, or 0.4 μm or more.

[0104] In composition (IV-1), the ratio of the content of inorganic filler (d) to the total content of all components other than the solvent (i.e., the ratio of the content of inorganic filler (d) in the protective film-forming film to the total mass of the protective film-forming film) is preferably 35 to 75 mass%, and may be, for example, 45 to 70 mass%, or 50 to 65 mass%. When the ratio is in this range, the effect of using inorganic filler (d) is further enhanced without impairing the properties of the protective film-forming film.

[0105] (Coupling agent (e)) When the composition (IV-1) 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 adhesiveness and adhesion of the protective film-forming film to an adherend are improved. In addition, the cured product of the protective film-forming film (e.g., a protective film) has improved water resistance without impairing heat resistance.

[0106] The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group possessed by the acrylic resin (b-1), the energy ray-curable component (a), etc., and is more preferably a silane coupling agent. Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2- Examples of such silanes include (aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazole silane.

[0107] The coupling agent (e) contained in the composition (IV-1) and the protective film-forming film may be one type only or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0108] When a coupling agent (e) is used, the content of the coupling agent (e) in the composition (IV-1) 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-1). When the content of the coupling agent (e) is equal to or greater than the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the inorganic filler (d) in the resin and improved adhesion of the protective film-forming film to the adherend, are more significantly obtained. When the content of the coupling agent (e) is equal to or less than the upper limit, the generation of outgassing is further suppressed.

[0109] (Crosslinking agent (f)) When the acrylic resin (b-1) has a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxy group, or isocyanate group that can bond with other compounds, the composition (IV-1) and the protective film-forming film may contain a crosslinking agent (f). The crosslinking agent (f) is a component that bonds the functional group in the acrylic resin (b-1) with other compounds to form a crosslink, and by crosslinking in this manner, the initial adhesive strength and cohesive strength of the protective film-forming film can be adjusted.

[0110] Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridinyl group).

[0111] 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."); trimers, isocyanurates, and adducts of the aromatic polyisocyanate compounds, etc.; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compounds, etc. with polyol compounds. The "adduct" refers to a reaction product of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound with a low-molecular-weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. Examples of the adduct include the xylylene diisocyanate adduct of trimethylolpropane, as described below. Furthermore, the term "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

[0112] More specific examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound in which one or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or some of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, and the like.

[0113] Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine.

[0114] When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the acrylic resin (b-1). When the crosslinking agent (f) has an isocyanate group and the acrylic resin (b-1) has a hydroxyl group, a crosslinked structure can be easily introduced into the protective film-forming film by the reaction between the crosslinking agent (f) and the acrylic resin (b-1).

[0115] The crosslinking agent (f) contained in the composition (IV-1) and the protective film-forming film may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0116] When a crosslinking agent (f) is used, the content of the crosslinking agent (f) in the composition (IV-1) is preferably 0.01 to 20 parts by mass per 100 parts by mass of the acrylic resin (b-1). When the content of the crosslinking agent (f) is equal to or greater than the lower limit, the effect of using the crosslinking agent (f) is more pronounced. When the content of the crosslinking agent (f) is equal to or less than the upper limit, excessive use of the crosslinking agent (f) is suppressed.

[0117] (Colorant (g)) When a colorant (g) is used, the colorant (g) is preferably an inorganic pigment, such as carbon black, 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)-based pigments, and ATO (antimony tin oxide)-based pigments, with carbon black being preferred.

[0118] The content of the colorant (g) in the composition (IV-1) and the protective film-forming film may be adjusted as appropriate. For example, in the composition (IV-1), the ratio of the content of the colorant (g) to the total content of all components other than the solvent (i.e., the ratio of the content of the colorant (g) in the protective film-forming film to the total mass of the protective film-forming film) is preferably 0.05% by mass or more and less than 1% by mass, more preferably 0.05 to 0.8% by mass, and particularly preferably 0.1 to 0.5% by mass. When the ratio is equal to or greater than the lower limit, the effect of using the colorant (g) can be more significantly obtained. When the ratio is equal to or less than the upper limit, poor curing due to energy rays can be suppressed.

[0119] The colorant (g) may contain, in addition to inorganic pigments, known materials such as organic pigments and organic dyes.

[0120] The colorant (g) contained in the composition (IV-1) and the protective film-forming film may be one type only, or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0121] (Thermosetting component (h)) When the composition (IV-1) and the protective film-forming film contain an energy ray-curable component (a) and a thermosetting component (h), the adhesive strength of the protective film-forming film to the substrate is improved by heating, and the strength of the cured product of this protective film-forming film (e.g., a protective film) is also improved.

[0122] Examples of the thermosetting component (h) include epoxy-based thermosetting resins, polyimide resins, unsaturated polyester resins, etc., with epoxy-based thermosetting resins being preferred.

[0123] The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2). The epoxy-based thermosetting resin contained in the composition (IV-1) and the protective film-forming film may be one type only or two or more types, and if there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0124] (Ultraviolet absorber (m)) The composition (IV-1) and the protective film-forming film preferably contain an ultraviolet absorber. By using the composition (IV-1) containing an ultraviolet absorber, the protective film-forming film formed has excellent stability under fluorescent light. Examples of the ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole; 2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; ,2'-Dihydroxybenzophenone-based UV absorbers; 2-hydroxybenzophenone-based UV absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; salicylic acid ester-based UV absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate; cyanoacrylate-based UV absorbers such as 2-ethyl-hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, and octyl-2-cyano-3,3-diphenylacrylate; 2-( Examples of such ultraviolet absorbers include triazine-based ultraviolet absorbers such as 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl, 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3-5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, and tris(hydroxyphenyl)triazine; and reactive ultraviolet absorbers in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton.

[0125] In composition (IV-1), the ratio of the content of the ultraviolet absorber to the total content of all components other than the solvent (i.e., the ratio of the content of the ultraviolet absorber in the protective film-forming film to the total mass of the protective film-forming film) is preferably 0.1 to 5.0 mass%, more preferably 0.2 to 4.5 mass%, and even more preferably 0.4 to 4.0 mass%. When the ratio is equal to or greater than the lower limit, the effect of using the ultraviolet absorber is more pronounced. When the ratio is equal to or less than the upper limit, excessive use of the ultraviolet absorber is suppressed.

[0126] (General-purpose additive (z)) The general-purpose additive (z) may be a known one and may be selected arbitrarily depending on the purpose, and is not particularly limited. Preferred general-purpose additives (z) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, etc.

[0127] The general-purpose additive (z) contained in the composition (IV-1) and the protective film-forming film may be one type only, or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0128] When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the composition (IV-1) and the protective film-forming film is not particularly limited and may be appropriately selected depending on the purpose.

[0129] <<Method for producing an energy ray-curable protective film-forming composition>> The energy ray-curable protective film-forming composition such as composition (IV-1) can be obtained by blending the components that constitute it. The order of addition of the components when blending is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any of the ingredients other than the solvent to pre-dilute the ingredients, or the solvent may be mixed with any of the ingredients other than the solvent without pre-diluting these ingredients. The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound. The temperature and time for adding and mixing each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately, but the temperature is preferably 15°C or higher and 30°C or lower.

[0130] [solvent] The composition (IV-1) preferably further contains a solvent, and the composition (IV-1) containing a solvent has good handleability. The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The composition (IV-1) may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0131] A more preferred example of the solvent contained in composition (IV-1) is methyl ethyl ketone, etc., from the viewpoint of enabling the components contained in composition (IV-1) to be mixed more uniformly.

[0132] The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on, for example, the types of components other than the solvent.

[0133] <<Method for producing an energy ray-curable protective film-forming composition>> The energy ray-curable protective film-forming composition such as composition (IV-1) can be obtained by blending the components that constitute it. The order of addition of the components when blending is not particularly limited, and two or more components may be added simultaneously. The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound. The temperature and time for adding and mixing each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. A temperature of 15 to 30°C is preferred.

[0134] 1 is a cross-sectional view schematically showing an example of a protective film-forming film of the present embodiment. In the drawings used in the following description, for the sake of convenience, in order to make the features of the present invention easier to understand, essential parts may be shown enlarged, and the dimensional ratios of each component may not necessarily be the same as in reality.

[0135] The protective film-forming film 13 shown here has a first release film 151 on one of its surfaces (sometimes referred to as the "first surface" in this specification) 13a, and a second release film 152 on the other surface (sometimes referred to as the "second surface" in this specification) 13b opposite the first surface 13a. Such a protective film-forming film 13 is suitable for storage in the form of a roll, for example.

[0136] The protective film-forming film 13 has the above-mentioned properties. The protective film-forming film 13 can be formed using the above-mentioned composition (IV-1).

[0137] The first release film 151 and the second release film 152 may both be known 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, in that the peeling force required to peel them from the protective film-forming film 13 is different from each other.

[0138] 1, one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the surface to be attached to the back surface of a wafer (not shown). Then, the other remaining one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the surface to be attached to a dicing sheet, which will be described later.

[0139] Figure 1 shows an example in which a release film is provided on both sides (first side 13a, second side 13b) of the protective film-forming film 13, but the release film may be provided on only one side of the protective film-forming film 13, i.e., only the first side 13a or only the second side 13b.

[0140] The protective film-forming film of this embodiment can be attached to the back surface of the wafer without using a dicing sheet described later. In this case, a release film may be provided on the surface of the protective film-forming film opposite to the surface attached to the wafer, and this release film may be removed at an appropriate time.

[0141] ◇Manufacturing method for chips with protective film (How to use protective film forming film) The method for manufacturing a chip with a protective film according to this embodiment is a method for manufacturing a chip with a protective film, the method comprising: A punching process for punching the protective film-forming film according to one embodiment of the present invention; a bonding step of bonding a punched protective film-forming film to the back surface of the wafer to form a semiconductor wafer with a protective film-forming film; a conveying step of bringing a conveying means into contact with an exposed surface of the semiconductor wafer with the protective film-forming film on the side opposite to the semiconductor wafer side, and conveying the semiconductor wafer with the protective film-forming film in a fixed state by the conveying means; a curing step of curing the protective film-forming film with energy rays to form the protective film; a dividing step of dividing the wafer and cutting the protective film to produce a plurality of chips with the protective film; It has.

[0142] The protective film-forming film can be suitably used in the manufacture of the chip with a protective film when the protective film-forming film is attached to the back surface of a wafer without forming a composite sheet for protective film formation in which the protective film-forming film is laminated on a support sheet.

[0143] Hereinafter, an example of a method for manufacturing a chip with a protective film according to this embodiment will be described in order with reference to the drawings.

[0144] FIG. 2 is a cross-sectional outline view that schematically shows an example of a punching process for punching the protective film-forming film in the method for producing a protective film-equipped chip according to this embodiment. A circular punching blade 70 is applied to the protective film-forming film 5 with a release film (Figure 2(a)) from the side of the first release film 151, which is the light-surface release film (Figure 2(b)), to peel off the first release film 151 and remove the circular outer periphery of the protective film-forming film 13 (Figure 2(c)).

[0145] In the method for manufacturing a chip with a protective film according to this embodiment, the protective film-forming film according to one embodiment of the present invention is used, and therefore the protective film-forming film has excellent punching processability.

[0146] 3A to 3C are cross-sectional views for schematically explaining examples of the bonding step, the transporting step, and the curing step in the method for producing a chip with a protective film according to this embodiment. In the bonding step, as shown in Fig. 3(a), the first surface 13a of the protective film-forming film 13 that has been punched as described above is bonded to the back surface 9b of the wafer 9. The arrow in Fig. 3(a) indicates the bonding direction of the protective film-forming film 13 to the wafer 9. At this time, it is preferable that the wafer 9 is placed on a table 8 that can adjust its own temperature as shown here, and the wafer 9 is heated by heating the table 8, and the protective film-forming film 13 is bonded to the wafer 9 in this heated state. In order to attach the protective film-forming film 13 to the back surface 9b of the wafer 9, the wafer 9 is placed on the table 8 with the circuit surface 9a having the protruding electrodes 91 facing the table 8. Note that the circuit of the wafer 9 is not shown here.

[0147] This produces a semiconductor wafer with a protective film-forming film, in which the protective film-forming film 13 and the wafer 9 are laminated in the thickness direction. A second release film 152 is provided on the second surface 13b of the protective film-forming film 13. 3(a) shows a case where the first release 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 back surface 9b of the wafer 9. In FIG.

[0148] Next, as shown in Figure 3(b), the second release film 152 is removed from the protective film-forming film 13 to produce a first laminated film 901 in which the protective film-forming film 13 and the wafer 9 are laminated in their thickness direction.

[0149] Next, in the transporting process, the transporting means 7 is brought into contact with the exposed surface 13b of the first laminated film 901 opposite the wafer 9 side, and the first laminated film 901 is transported to an energy ray irradiation device while being fixed by the transporting means 7.

[0150] Next, in the curing step, the protective film-forming film 13 in the first laminate film 901 is cured with energy rays to form a protective film 13', thereby producing a second laminate film 902 in which the protective film 13' and the wafer 9 are laminated in their thickness direction, as shown in Figure 3(d). Reference numeral 13a' denotes 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). Reference numeral 13b' denotes 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).

[0151] In the curing step, the protective film 13 is irradiated with energy rays from the outside of the first laminated film 901 on the protective film-forming film 13 side, thereby forming a protective film 13'.

[0152] The conditions for irradiation with energy rays in the curing step are as described above.

[0153] The back surface 9b of the wafer 9 in Figure 3(a) may be laser-marked by irradiating it with a laser, or the back surface 9b of the wafer 9 shown in Figure 3(b) may be laser-marked by irradiating it with a laser through the protective film-forming film 13 (through the protective film-forming film 13), or the back surface 9b of the wafer 9 shown in Figure 3(d) may be laser-marked by irradiating it with a laser through the protective film 13' (through the protective film 13').

[0154] 4 is a cross-sectional view for schematically illustrating an example of the dividing step in the method for manufacturing a chip with a protective film according to this embodiment. Note that protruding electrodes of wafer 9 are not shown here.

[0155] Next, one side 80a (sometimes referred to as the "first side" in this specification) of the dicing sheet 80 is attached to the second side 13b' of the protective film 13' to produce a third laminated film 903, which is constructed by stacking the dicing sheet 80, the protective film 13', and the wafer 9 in their thickness direction, as shown in Figure 4(a). The dicing sheet 80 shown here is configured to include a base material 81 and an adhesive layer 82 provided on one surface 81a of the base material 81, and the adhesive layer 82 in the dicing sheet 80 is attached to the protective film 13'. The surface 82a of the adhesive layer 82 facing the protective film 13' (sometimes referred to as the "first surface" in this specification) is the same as the first surface 80a of the dicing sheet 80.

[0156] The dicing sheet 80 may be a known one.

[0157] Here, a case is shown in which a dicing sheet 80 having a base material 81 and an adhesive layer 82 is used, but in the dividing process, a dicing sheet other than this, for example, a dicing sheet consisting of only a base material, may also be used.

[0158] 4(a) and 4(b), in a state where a dicing sheet 80 is provided on the protective film 13′ side of the third laminate film 903, the wafer 9 in the third laminate film 903 is divided and the protective film 13′ is cut. The wafer 9 is divided into individual pieces into a plurality of chips 90.

[0159] Dividing the wafer 9 and cutting the protective film 13′ may be performed by a known method. For example, dividing the wafer 9 and cutting the protective film 13′ can be performed consecutively by dicing such as blade dicing, laser dicing using laser irradiation, or water dicing using water containing an abrasive. The protective film 13' is cut along the outer periphery of the chip 90 regardless of the cutting method.

[0160] In this manner, by dividing the wafer 9 and cutting the protective film 13′, a plurality of protective film-coated chips 913′ are obtained, each chip including a chip 90 and a protective film (sometimes simply referred to as a “protective film” in this specification) 130′ after cutting provided on the back surface 90b of the chip 90. Reference numeral 130b′ denotes the surface of the protective film 130′ after cutting that was the second surface 13b′ of the protective film 13′ (sometimes referred to as the “second surface” in this specification).

[0161] In the dividing step, a fourth laminated film 904 is produced in which a plurality of chips 913' with protective film are fixed on the dicing sheet 80 as described above.

[0162] Next, in the pick-up step, as shown in FIG. 4(c), the protective film-coated chip 913' in the fourth laminated film 904 is picked up by being pulled away from the dicing sheet 80. In the pick-up step, peeling occurs between the second surface 130b' of the protective film 130' in the protective film-coated chip 913' and the first surface 82a of the adhesive layer 82 in the dicing sheet 80.

[0163] Here, a case is shown in which a separating means 7 such as a vacuum collet is used to separate the protective film-coated chip 913' in the direction of arrow P. Note that a cross-sectional view of the separating means 7 is omitted here. The chip 913' with the protective film can be picked up by a known method.

[0164] If the adhesive layer 82 is energy ray-curable, it is preferable in the pick-up step to irradiate the adhesive layer 82 with energy rays to cure the adhesive layer 82 and form a cured product (not shown), and then peel the protective film-equipped chip 913′ from the dicing sheet 80. In this case, peeling occurs between the protective film 130′ in the protective film-equipped chip 913′ and the cured product of the adhesive layer 82 in the dicing sheet 80 in the pick-up step. In this case, the cured product of the adhesive layer 82 is less likely to deform than before curing, making it easier to pick up the protective film-equipped chip 913'.

[0165] The conditions for irradiating the pressure-sensitive adhesive layer 82 with energy rays in the pick-up step may be the same as the conditions for irradiating the protective film-forming film 13 with energy rays in the curing step, for example.

[0166] In this specification, even after the energy ray-curable pressure-sensitive adhesive layer is cured with energy rays, as long as the laminated structure of the substrate and the cured product of the energy ray-curable pressure-sensitive adhesive layer is maintained, this laminated structure is referred to as a "dicing sheet."

[0167] On the other hand, if the adhesive layer 82 is non-energy ray curable, the protective film-equipped chip 913' can be simply pulled away from the adhesive layer 82, and since there is no need to harden the adhesive layer 82, the protective film-equipped chip 913' can be picked up in a simplified process. Even if the adhesive layer 82 is energy ray curable, by picking up the protective film-attached chip 913' without curing the adhesive layer 82, the protective film-attached chip 913' can be picked up in a simplified process.

[0168] In the pick-up step, such pick-up of the protective film-coated chips 913' is carried out for all of the desired protective film-coated chips 913'.

[0169] By carrying out the above steps up to the pick-up step, the desired chip 913' with a protective film is obtained.

[0170] ◇ Manufacturing method of substrate device (method of using chip with protective film) After the chip with the protective film is obtained by the above-described manufacturing method, a substrate device can be manufactured by the same method as the conventional method for manufacturing a substrate device.

[0171] An example of a method for manufacturing such a substrate device is a manufacturing method that includes a flip-chip connection step in which the protruding electrodes of a chip with a protective film obtained using the protective film-forming film are brought into contact with the connection pads on a circuit board, thereby electrically connecting the protruding electrodes and the connection pads on the circuit board. [Example]

[0172] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the examples shown below.

[0173] <Raw materials for resin production> The full names of the raw materials for producing the resins, which are abbreviated in the examples and comparative examples, are shown below. BA: n-butyl acrylate MA: methyl acrylate ACrMO: 4-acryloylmorpholine HEA: 2-hydroxyethyl acrylate

[0174] <Raw materials for producing the energy ray-curable protective film-forming composition (IV-1)> The raw materials used in the production of composition (IV-1) are shown below.

[0175] [Energy ray curable component (a)] (Component (a2-1) having an energy ray-curable group and a weight-average molecular weight of 100 or more and less than 5,000) (a2-1)-1: ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 728, trifunctional UV-curable compound) (a2-1)-2: urethane acrylate ("Shiko (registered trademark) UV-6630B" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1936, bifunctional ultraviolet-curable compound) (a2-1)-3: Ethoxylated bisphenol A diacrylate ("ABE-300" manufactured by Shin-Nakamura Chemical Co., Ltd., weight average molecular weight: 468, bifunctional UV-curable compound)

[0176] (Component (a2-2) having an energy ray-curable group and a weight-average molecular weight of 5,000 or more and less than 80,000) (a2-2)-1: urethane acrylate ("Shiko (registered trademark) UV-3310B" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 5804, bifunctional ultraviolet-curable compound) (a2-2)-2: Urethane acrylate (KJ Chemicals Corporation's "Quick Cure (registered trademark) 8100EA70", weight average molecular weight: 10231, bifunctional UV-curable compound)

[0177] [Polymer (b) having no energy ray-curable group] (b)-1: Acrylic resin (manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 800,000, glass transition temperature: 2°C) which is a copolymer of BA (33 parts by mass), MA (27 parts by mass), ACrMO (25 parts by mass), and HEA (15 parts by mass).

[0178] [Photopolymerization initiator (c)] (c)-1: 1-[4-(phenylthio)-2-(O-benzoyloxime)]1,2-octanedione (trade name IRGACURE® OXE01, manufactured by BASF Japan Ltd.)

[0179] [Inorganic filler (d)] (d)-1: Silica filler ("5SP-CM1" manufactured by Admatechs Co., Ltd., spherical silica filler surface-modified with phenyl groups, average particle diameter 0.5 μm)

[0180] [Colorant (g)] (g)-1: Carbon black (manufactured by Mitsubishi Carbon Black Co., Ltd., "#20, particle size 50 nm")

[0181] <<Protective Film Forming Film Manufacturing>> [Example 1] <Production of Energy Ray-Curable Protective Film-Forming Composition (IV-1)-1> Energy ray curable component (a2-1)-1 (22 parts by mass), polymer (b)-1 (15.5 parts by mass) not having energy ray curable group, photopolymerization initiator (c)-1 (1.0 part by mass), inorganic filler (d)-1 (60 parts by mass), and colorant (g)-1 (1.5 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to obtain composition (IV-1)-1, in which the total concentration of all components other than the solvent was 55% by mass. Note that the blending amounts of all components other than the solvent shown here are the blending amounts of the target material excluding the solvent, and this is the same in the following composition (IV-1).

[0182] <Production of protective film-forming film> A release film (second release film, "SP-PET382150" manufactured by Lintec Corporation, thickness 38 μm) made of polyethylene terephthalate film, one side of which had been treated for release by silicone treatment, was used. Composition (IV-1)-1 obtained above was applied to the release-treated surface, and the coating was dried at 100°C for 2 minutes to produce an energy ray-curable protective film-forming film having a thickness of 25 μm.

[0183] Furthermore, by bonding the release-treated surface of a release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) to the exposed surface of the obtained protective film-forming film that did not have the second release film, a protective film-forming film with a release film was obtained, which was composed of 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.

[0184] [Examples 2 to 4, Comparative Examples 1 to 3] Composition (IV-1) was obtained in the same manner as in Example 1, using the blending ratios (solid content) in Tables 1 and 2. Using each composition (IV-1), protective film-forming films of Examples 2 to 4 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1.

[0185] <<Evaluation of protective film forming films>> <Measurement of Young's modulus and breaking elongation of protective film-forming film> The protective film-forming film with release film was cut into a size of 15 mm wide and 30 mm long, and the first and second release films on both sides were removed to obtain a test piece. This test piece was left to stand for 24 hours in an environment of 23 ° C and 50% RH, and then a tensile test was performed using a universal testing machine (Shimadzu Corporation, Autograph AG-IS 500N) with clamping tools so that the chuck distance was 20 mm, and a tensile test was performed at a tensile speed of 200 mm / min to measure the tensile load and elongation. A stress-strain curve was created, and the Young's modulus [Pa] was calculated from the slope of the stress-strain curve at the beginning of the test. Furthermore, the breaking elongation [%] was calculated from the elongation of the test piece at break.

[0186] <Evaluation of laminating processability of protective film with release film> Using a 300 mm fully automatic LC tape laminator (Rintec Corporation, RAD-3600F / 12) with specifications for 12-inch (300 mm) wafers, the protective film-forming film with release film was cut into a wafer shape with a diameter of 300 mm from the side of the first release film (light release film) by punching with a cutting blade, and the first release film and the protective film-forming film on the periphery of the cut area were unwound and removed. Of the 10 protective film-forming films punched, the number of protective film-forming films that could not be unwound (number of films that could not be punched) was counted.

[0187] For each of the 10 protective film-formed films on the first release film, the punching processability with a laminator was evaluated according to the following criteria. A: The punching process for all 10 protective film formation films was carried out properly. B: Of the 10 protective film-forming films punched, 1 to 3 could not be fed. C: Of the 10 protective film-forming films punched, 4 to 6 could not be fed. D: Of the 10 protective film-forming films punched, 7 to 10 could not be fed.

[0188] <Evaluation of the effect of suppressing suction marks caused by the transport means on silicon wafers with protective films> For the protective film-forming films with release film of Examples 1 to 4 and Comparative Examples 1 to 3, a 300 mm fully automatic LC tape laminator (Lintec Corporation, RAD-3600F / 12) was used with specifications for 12-inch (300 mm) wafers, and the protective film-forming films with release film were cut into wafer shapes with a diameter of 300 mm from the side of the first release film (light release film) by punching with a cutting blade, and the first release film and the protective film-forming film on the periphery of the cut area were unwound and removed. Next, using 10 protective film-forming films that could be unwound without any problems in the punching process, the surface (exposed surface) of the protective film-forming film that was not provided with the second release film was attached to one side of a 12-inch silicon wafer (diameter 300 mm, thickness 350 μm, no bumps). At this time, the protective film-forming film was attached while the silicon wafer was heated to 70°C using a heating table. In this way, a silicon wafer with a protective film-forming film and a second release film was produced, which included the protective film-forming film, a silicon wafer 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.

[0189] Next, the second release film was removed from the silicon wafer with the protective film-forming film, and the resulting silicon wafer with the protective film-forming film was transported in the LC tape laminator using a suction arm as a transport means and stored in a wafer cassette. At this time, the transport means was in contact with the exposed surface of the protective film-forming film in the silicon wafer with the protective film-forming film. The process from removing the first release film from the laminated film to storing the silicon wafer with the protective film-forming film in the wafer cassette was repeated 10 times with different silicon wafers, thereby storing 10 silicon wafers with the protective film-forming film in the wafer cassette. After transportation, an ultraviolet ray irradiator (Rintec Corporation, RAD-2010m / 12) was used to irradiate the sample at 220 mW / cm 2 UV light with an illuminance of 500mJ / cm 2 The silicon wafer with the protective film was obtained by irradiating the silicon wafer with the protective film so that the exposure amount was 1000 ppm.

[0190] The protective film surfaces of 10 silicon wafers each having a protective film were visually inspected, and the effect of suppressing suction marks caused by the conveying means was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. A: No traces of the suction arms were found on the protective film surface of 10 sheets. B: Traces of suction arms were observed on 1 to 3 of the 10 protective film surfaces. C: Traces of the suction arms were observed on 4 to 10 of the 10 protective film surfaces.

[0191] <Cross-cut test evaluation of silicon wafers with protective film> For the protective film-forming films of Examples 1 to 4 and Comparative Examples 1 to 3, a cutter knife was used to make a cut in the exposed surface of the protective film in the protective film-coated silicon wafer obtained in the above <Evaluation of the effect of suppressing suction marks caused by the transport means on the protective film-coated silicon wafer> only in the protective film in the protective film-coated silicon wafer, and the protective film was divided into 100 squares with a size of 1 mm x 1 mm per square. Next, adhesive tape (Nichiban Co., Ltd.'s "Cellotape (registered trademark)") was applied to the protective film side of each of the 100 squares of silicon wafers with protective film in an environment of 23°C and 50% RH, and the wafer was left standing at 25°C for 20 minutes to ensure that the adhesive tape was firmly attached to the protective film. After that, the edge of the adhesive tape was quickly peeled off from each of the 100 squares of silicon wafers with protective film, and the state of the grid was observed to visually check whether the protective film had peeled off.

[0192] The cross-cut test results of the protective film were evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. A: Of the 100 protective films, 80% or more of the protective films were in good contact. B: Of the 100 squares of protective film, 60 to 80% of the protective film was in close contact. C: Of the 100 protective films, less than 60% were in tight contact. Tables 1 and 2 show the results of the loss-cut test on the protective film.

[0193] <Temperature cycle reliability evaluation of silicon chips with protective film> For the protective film-forming films of Examples 1 to 4 and Comparative Examples 1 to 3, the adhesive layer side of a dicing tape (Adwill (registered trademark) D-686H, manufactured by Lintec Corporation) was attached to the protective film in the protective film-coated silicon wafer obtained in the above <Evaluation of the effect of suppressing suction marks caused by conveying means on protective film-coated silicon wafers>. The attachment conditions were an attachment speed of 30 mm / s, a roller temperature of 23°C, a table temperature of 23°C, and an attachment pressure of 0.25 MPa. Next, the silicon wafer with the protective film was diced using a dicing saw (DISCO Corporation, DFD6362) to divide the silicon wafer into silicon chips measuring 3 mm × 3 mm, and the protective film was cut to the same size as the silicon chips to produce a large number of silicon chips with the protective film. At this time, the moving speed of the dicing blade (DISCO Corporation, Z05-SD2000-N1-90 CC) was set to 50 mm / s, the rotation speed to 45,000 rpm, and the height to 60 μm. The individual silicon chips with protective film were heated at 125°C for 24 hours, then treated in a constant temperature and humidity chamber at 85°C and 85% RH for 168 hours, and then passed through an IR reflow furnace three times with a preheat of 160°C and a peak temperature of 260°C.

[0194] Then, using a small thermal shock device (manufactured by Espec Corporation, "TSE-11-A"), the silicon chip with the protective film was placed in an environment of 150°C for 15 minutes, then immediately placed in an environment of -65°C for 15 minutes, and then immediately returned to the environment of 150°C.A temperature cycle test was performed by exposing the silicon chip with the protective film to this temperature cycle of 15 minutes of heating at 150°C and 15 minutes of cooling at -65°C a total of 1,000 times. The obtained silicon chips with the protective film were then observed using a high-precision ultrasonic microscope (manufactured by Sonoscan, "D9600 C-SAM") to check for peeling between the silicon chip and the protective film.

[0195] The temperature cycle reliability of each of the 25 silicon chips with protective film was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. A: Of the 25 silicon chips with protective film, no peeling occurred at the interface between the protective film and the silicon chip. B: Peeling occurred at the interface between the protective film and the silicon chip in 1 to 5 of the 25 protective film-coated silicon chips. C: Of the 25 silicon chips with protective film, 6 to 25 silicon chips with protective film had peeling at the interface between the protective film and the silicon chip.

[0196] <Transmittance measurement of protective film> For the protective film-forming films of Examples 1 to 4 and Comparative Examples 1 to 3, the first release film and the second release film on both sides were removed, and then the transmittance of each protective film-forming film was measured using a spectrophotometer (Shimadzu Corporation, UV-VIS-NIR SPECTROPHOTOMETER UV-3600) under the transmittance measurement conditions below. The measurement results of light transmittance [%] at a wavelength of 1300 nm are shown in Tables 1 and 2.

[0197] (Transmittance measurement conditions) Wavelength range: 190-2000nm Scan speed: Fast Slit width: 8.0 mm Detector unit: Direct light reception

[0198] [Table 1]

[0199] [Table 2]

[0200] As is clear from the above results, the protective film-forming films of Examples 1 to 4 have a Young's modulus of 2.6 MPa or more and a breaking elongation of 80% or more and 900% or less, and therefore the protective film-forming films with a release film have excellent punching processability with a laminator, and the protective film-coated silicon wafers have excellent punching processability with a laminator. The occurrence of suction marks caused by the transport means can be suppressed.

[0201] On the other hand, the protective film-forming films of Comparative Examples 1 and 2 had Young's moduli of less than 2.6 MPa, and thus did not sufficiently suppress suction marks caused by the transport means of the protective film-coated silicon wafer. Furthermore, the protective film-forming film of Comparative Example 2 had a breaking elongation of more than 900%, and thus the protective film-coated film with a release film had insufficient punching processability in a laminator. The protective film-coated film of Comparative Example 3 had a breaking elongation of less than 80%, and thus broke during punching process in a laminator.

[0202] The results of the cross-cut test of the silicon wafers with protective films showed that the protective film-forming films of Examples 2 to 4 were good, and the protective film-forming film of Example 4 was particularly excellent.

[0203] The protective film-forming films of Examples 1 to 4 also had excellent temperature cycle reliability for the protective film-attached silicon chip.

[0204] Furthermore, as is clear from the above results, the protective film-forming films of Examples 1 to 4 and Comparative Examples 1 to 3 all had a low near-infrared transmittance of 10% or less at a wavelength of 1300 nm, which indicated that they also had excellent near-infrared shielding properties. [Industrial Applicability]

[0205] The present invention can be used in the manufacture of semiconductor devices, including chips with protective films, and various substrate devices. [Explanation of symbols]

[0206] 13... Energy ray curable protective film forming film, 901...first laminate film, 902...second laminate film, 903...third laminate film, 904...fourth laminate film, 80... dicing sheet, 81... substrate, 82... adhesive layer, 9...wafer, 9b...backside of wafer, 90...chip, 913'...chip with protective film

Claims

1. An energy ray-curable protective film-forming film, A protective film-forming film having a Young's modulus of 2.6 MPa or more and a breaking elongation of 80% or more and 900% or less, as determined by the following measurement method. [Measurement method] The protective film-forming film is cut into a test piece having a width of 15 mm and a length of 30 mm, and a tensile test is performed at a chuck distance of 20 mm and a tensile speed of 200 mm / min. The tensile load and elongation are measured, and the Young's modulus [MPa] is calculated from the slope of the stress-strain curve at the beginning of the test, and the breaking elongation [%] is determined from the elongation of the test piece at the time of break.

2. The protective film-forming film according to claim 1 , wherein the Young's modulus determined by the measurement method is 45 MPa or less.

3. The protective film-forming film according to claim 1 or 2, wherein the transmittance of near-infrared rays at a wavelength of 1,300 nm is 10% or less.

4. The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film contains a component (a2) having an energy ray-curable group and a weight average molecular weight of 100 or more and less than 80,000, and the component (a2) contains a polyfunctional acrylate compound having two (meth)acryloyl groups in one molecule and a polyfunctional acrylate compound having three (meth)acryloyl groups in one molecule.

5. A method for manufacturing a chip with a protective film, the method comprising: A punching process for punching the protective film-forming film according to claim 1 or 2; a bonding step of bonding a punched protective film-forming film to the back surface of the wafer to produce a semiconductor wafer with a protective film-forming film; a conveying step of bringing a conveying means into contact with an exposed surface of the semiconductor wafer with the protective film-forming film on the side opposite to the semiconductor wafer side, and conveying the semiconductor wafer with the protective film-forming film in a fixed state by the conveying means; a curing step of curing the protective film-forming film with energy rays to form the protective film; a dividing step of dividing the wafer and cutting the protective film to produce a plurality of chips with the protective film; A method for manufacturing a chip with a protective film having the above structure.

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