TWI715652B - Film for forming protective film and composite sheet for forming protective film - Google Patents

Abstract

A film for forming a protective film which includes an energy ray curable compound (B) for forming the protective film having the following properties on the back surface of a semiconductor wafer or a semiconductor chip: when the film for forming the protective film is cured to form a cured product by irradiation with the energy ray, the cured product has no less than 500 MPa young's modulus and no less than 8% fracture elongation.

Description

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

The present invention relates to a protective film forming film for forming a protective film on the back surface of a semiconductor wafer or semiconductor wafer, and a composite sheet for forming a protective film provided with the protective film forming film.

This application claims priority based on Japanese Patent Application No. 2015-212845 for which an application was filed in Japan on October 29, 2015, and the content is cited herein.

In recent years, the industry has applied a mounting method called a so-called face down method to manufacture semiconductor devices. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used to bond the electrodes to the substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.

Sometimes a resin film made of an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, which is formed into a semiconductor chip with a protective film and then incorporated into a semiconductor device. The purpose of using protective film is to prevent The semiconductor wafer is cracked after the dicing step or packaging.

In order to form such a protective film, the composite sheet for protective film formation provided with the film for protective film formation on a support sheet is used, for example. Among the composite sheets for forming a protective film, the film for forming a protective film has the function of forming a protective film, and the support sheet can be used as a dicing sheet, and a composite sheet for forming a protective film can be formed in which the protective film forming film and the dicing sheet are integrated .

As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film including a film for forming a protective film that is cured by heating to form a protective film has been mainly used so far. For example, a semiconductor wafer is diced into a semiconductor wafer after attaching a composite sheet for forming a protective film to the back surface (a surface opposite to the electrode forming surface) of the protective film forming film. In addition, after the protective film is hardened by heating to form the protective film, the semiconductor chip is picked up with the protective film attached, or the semiconductor chip with the protective film forming film attached is picked up After that, the protective film forming film is cured by heating to form a protective film.

However, heat curing of the protective film forming film usually takes a long time of several hours, so it is expected that the curing time can be shortened. In response to this situation, the industry is studying films for forming protective films that can be cured by irradiating energy rays such as ultraviolet rays, and it has been revealed that the pencil hardness after curing is 5H or more, which can suppress chipping when cutting semiconductor wafers. Protective film (refer to Patent Document 1); can form laser mark recognition, hardness, and installation reliability An excellent protective film (refer to Patent Document 2); a protective film that can form a protective film with high hardness and excellent adhesion to semiconductor wafers (refer to Patent Document 3).

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2009-147277.

Patent Document 2: JP 2009-138026 A.

Patent Document 3: JP 2010-031183 A.

However, for the formation of a protective film, for example, it is required to form a protective film that has high protective effect on semiconductor wafers or semiconductor wafers, and maintains high protective effect even when exposed to large temperature changes, and has high reliability. , In order to suppress the generation of cracks or notches, for example, to suppress the generation of notches in the outer edge of the semiconductor wafer, that is, to suppress the so-called cracking. Therefore, based on the above point of view, there is still room for improvement in the conventional protective film formation film that can be cured by irradiation with energy rays.

The present invention is made in view of the above circumstances. The subject of the present invention is to provide a protective film forming film and a protective film forming composite sheet provided with the protective film forming film. The protective film forming film can be formed on a semiconductor wafer Or the backside of the semiconductor chip has high protection and high reliability Protective film.

In order to solve the above-mentioned problems, the present invention provides a protective film forming film containing an energy-ray curable compound (B) for forming a protective film on the back surface of a semiconductor wafer or semiconductor wafer, and irradiating energy to the protective film forming film The cured product obtained by the wire has a Young's modulus of 500 MPa or more, and an elongation at break of 8% or more.

The film for forming a protective film of the present invention is preferably composed of an energy ray curable compound (B1) having 2 to 4 energy ray polymerizable groups in one molecule relative to the total content of the aforementioned energy ray curable compound (B) The ratio of the total content is 90% by mass or more.

In addition, the present invention provides a composite sheet for forming a protective film, which is provided with the aforementioned film for forming a protective film on one surface of a support sheet.

That is, the present invention includes the following aspects.

[1] A film for forming a protective film for forming a protective film on the back surface of a semiconductor wafer or a semiconductor wafer, containing an energy ray curable compound (B), and having the following characteristics: by irradiating energy ray, the protective film When the formation film is cured to form a cured product, the Young's modulus of the cured product is 500 MPa or more, and the elongation at break is 8% or more.

[2] The film for forming a protective film as described in [1], wherein in the film for forming a protective film, the content of an energy ray curable compound (B1) having 2 to 4 energy ray polymerizable groups per molecule Compared with the aforementioned energy ray hardening The total mass of the compound (B) is 90% by mass or more.

[3] A composite sheet for forming a protective film comprising the film for forming a protective film as described in [1] or [2] on one surface of a support sheet.

According to the present invention, there is provided a film for forming a protective film and a composite sheet for forming a protective film provided with the film for forming the protective film. The film for forming a protective film can be formed to have a high protective effect on the back surface of a semiconductor wafer or a semiconductor wafer. And has a highly reliable protective film.

1A, 1B, 1C, 1D, 1E‧‧‧Composite sheet for forming protective film

10‧‧‧Support film

10a‧‧‧(supporting film) surface

11‧‧‧Substrate

11a‧‧‧(of the substrate) surface

12‧‧‧Adhesive layer

12a‧‧‧(adhesive layer) surface

13, 23‧‧‧Film for forming protective film

13a, 23a‧‧‧(The surface of the protective film forming film)

15‧‧‧Peeling film

16‧‧‧Adhesive layer for fixture

16a‧‧‧(adhesive layer for jig) surface

Fig. 1 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 4 is a cross-sectional view schematically showing yet another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.

"Film for forming protective film"

The film for forming a protective film of the present invention contains an energy-ray curable compound (B) for forming a protective film on the back of a semiconductor wafer or semiconductor wafer, and the cured product obtained by irradiating the film for forming a protective film with energy rays ( That is, the Young's modulus of the protective film is 500 MPa or more, and the elongation at break is 8% or more. That is, another aspect of the film for forming a protective film of the present invention contains an energy-ray curable compound (B), and has the following characteristics: the film for forming a protective film is cured by irradiating energy rays to form a cured product (protective film) ), the Young's modulus of the hardened product is 500 MPa or more, and the elongation at break is 8% or more.

The cured product, that is, the protective film, has a sufficiently high protective effect on the semiconductor wafer or the semiconductor wafer by setting the Young's modulus and the elongation at break to be higher than the aforementioned lower limit. For example, when dicing a semiconductor wafer provided with the aforementioned protective film forming film or protective film on the back side, the resulting semiconductor wafer is prevented from being cracked or chipped, for example, chipping is suppressed at the outer edge, that is, so-called chipping is suppressed . In addition, by making the Young's modulus and elongation at break of the protective film above the aforementioned lower limit value, even if exposed to a large temperature change, it can maintain the high protective effect as described above, and has high reliability. For example, although a semiconductor chip with a protective film is exposed to large temperature changes during mounting, the protective film can maintain a high protective effect even under such conditions.

In this way, the film for forming a protective film of the present invention can also form a protective film with high protective effect and high reliability by irradiating energy rays.

The aforementioned protective film formation film contains an energy ray curable compound (B), it can be cured by irradiating energy rays to form a protective film.

In this specification, the term "energy line" means that an electromagnetic wave or a charged particle beam has energy quantum, and examples thereof include ultraviolet rays, electron beams, and the like.

The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or a light emitting diode (LED) as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.

The irradiation amount of energy rays varies with the types of energy rays. For example, in the case of ultraviolet rays, the illuminance is preferably 50 mWcm ² to 500 mWcm ² , and the amount of light is preferably 200 mJ/cm ² to 800 mJ/cm ² .

The protective film formation film can be formed using a protective film formation composition containing the components used to form the protective film formation film. For example, the protective film formation composition can be applied to the surface of a support. Dry and form. The content ratio of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the content ratio of the aforementioned components of the protective film formation film. Furthermore, in this specification, the "normal temperature" refers to a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, etc.

The aforementioned support is not particularly limited as long as it can maintain the shape of the protective film forming film. For example, it may be a support used only for forming a protective film forming film, or it may be used to form a protective film forming film and then With the Bao It is a support for other purposes in the state where the film is laminated for forming a protective film. Examples of the support used only for forming the film for forming a protective film include a release film having a release treatment surface. In addition, as a support that is used for other purposes after forming the protective film forming film, for example, a support sheet or a base material such as a dicing sheet described later can be cited.

The thickness of the protective film formation film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. By making the thickness of the protective film forming film more than the aforementioned lower limit, the adhesive force to the semiconductor wafer or the semiconductor wafer as the adherend becomes greater. In addition, by setting the thickness of the protective film forming film to the aforementioned upper limit or less, when picking up the semiconductor wafer, the protective film as the cured product can be cut more easily by shear force.

In this specification, the term "thickness" means the average value obtained by measuring the thickness with a contact thickness meter at any 5 locations.

<Composition for forming protective film>

The composition for forming a protective film contains an energy ray curable compound (B), preferably contains a polymer component (A) and an energy ray curable compound (B), and more preferably contains a polymer component (A), Energy ray curable compound (B) and photopolymerization initiator (C).

Next, the components contained in the composition for forming a protective film and the film for forming a protective film will be described.

[Polymer component (A)]

The polymer component (A) can be regarded as a component formed by the polymerization reaction of a polymerizable compound, and the polymer component (A) is a polymer compound for imparting film-forming properties or flexibility to the protective film forming film . Furthermore, in the present invention, the polymerization reaction also includes a polycondensation reaction.

Furthermore, when there are components belonging to both the polymer component (A) and the energy ray curable compound (B) among the components contained in the protective film forming composition, such components are referred to as the energy ray curable compound (B) )deal with. As such a component, the acrylic polymer which has a hydroxyl group and has a polymerizable group in a side chain via a urethane bond is mentioned, for example.

A polymer component (A) may be used individually by 1 type, and may use 2 or more types together.

As the polymer component (A), for example, acrylic resin, polyester, polyurethane, urethane acrylate resin, silicone resin, rubber polymer, phenoxy resin, etc. can be cited. It is an acrylic resin.

As the aforementioned acrylic resin, a known acrylic polymer can be used.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. By making the weight average molecular weight of the acrylic resin more than the aforementioned lower limit, the adhesion between the support sheet and the protective film described later is suppressed, and the pick-up of the semiconductor wafer with the protective film is further improved. In addition, by averaging the weight of acrylic resin The molecular weight is below the above upper limit, the protective film forming film easily follows the uneven surface of the adherend (semiconductor wafer, semiconductor wafer), and the generation of gaps between the adherend and the protective film forming film is further suppressed.

In addition, in this specification, the "weight average molecular weight", unless otherwise specified, means a polystyrene conversion value measured by a gel permeation chromatography (Gel Permeation Chromatography; GPC) method.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. By making the Tg of the acrylic resin more than the aforementioned lower limit, the adhesive force between the support sheet and the protective film is suppressed, and the pick-up of the semiconductor wafer with the protective film is further improved. In addition, by setting the Tg of the acrylic resin to be equal to or lower than the aforementioned upper limit, the adhesive force between the adherend and the protective film forming film becomes greater.

Examples of monomers constituting acrylic resins include the following monomers: (meth)acrylic acid alkyl esters of which the alkyl group constituting the alkyl ester has a chain shape and the carbon number is 1 to 18, such as (meth)acrylic acid Methyl ester, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate Base) n-octyl acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, ten (meth)acrylate Dialkyl esters (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate) ), pentadecyl (meth)acrylate, cetyl (meth)acrylate (Also known as palm ester (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as stearyl (meth)acrylate), etc.; (Meth) acrylate of cyclic skeleton, such as cycloalkyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imine (meth)acrylate, etc.; (meth)acrylates containing hydroxyl groups, such as (meth) Hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; and (meth)acrylates containing glycidyl groups, such as glycidyl (meth)acrylate Wait.

Among the above, as the monomer constituting the acrylic resin, methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate are preferred. Ester etc.

In addition, in this specification, the term "(meth)acrylic acid" includes the concepts of both "acrylic acid" and "methacrylic acid". Terms similar to (meth)acrylic acid are also the same. For example, the so-called "(meth)acrylate" includes the concepts of both "acrylate" and "methacrylate". The so-called "(meth)acrylic acid ester" "Is a concept that includes both "acrylic acid base" and "methacrylic acid base".

As the monomer constituting the acrylic resin, monomers other than (meth)acrylate can also be cited, such as (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol Acrylic amide and so on.

The monomer constituting the acrylic resin may be only one type or two or more types.

Acrylic resins may also have functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional group may be bonded to other compounds via the crosslinking agent (G) described later, or may be directly bonded to other compounds without the crosslinking agent (G). By bonding the acrylic resin to another compound using the aforementioned functional group, there is a tendency that the packaging reliability of a semiconductor device obtained by using the protective film formation film is improved.

When the composition for forming a protective film contains acrylic resin as the polymer component (A), the content of the acrylic resin in the composition for forming a protective film is relative to all of the composition for forming a protective film except the solvent The total mass of the ingredients is preferably 5 to 50% by mass, and more preferably 10 to 45% by mass. By setting the aforementioned content of the acrylic resin within the above-mentioned range, the adhesive force between the support sheet and the protective film is suppressed, and the pick-up of the semiconductor wafer with the protective film is further improved.

When the protective film forming film contains acrylic resin as the polymer component (A), the content of the acrylic resin in the protective film forming film relative to the total mass of the protective film forming film is preferably 5% by mass To 50% by mass, more preferably 10% to 45% by mass.

In the present invention, by reducing the adhesion (peeling force) between the support sheet and the protective film, the pick-up of the semiconductor chip with the protective film is further improved, or the protective film forming film can easily follow the unevenness of the adherend In order to further suppress the generation of gaps between the adherend and the protective film forming film, in terms of the above aspects, as the polymer component (A), thermoplastic resins other than acrylic resins (hereinafter, sometimes (Referred to as "thermoplastic resin"), and the aforementioned thermoplastic resin may be used in combination with acrylic resin.

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

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

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

The said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

[Energy ray curable compound (B)]

The energy-ray curable compound (B) is a component that can undergo a curing (polymerization) reaction by irradiating energy rays. In addition, the energy ray curable compound (B) is used to harden the protective film forming film to form a hard protective film (also That is, the component of the cured product obtained by irradiating the film for forming a protective film with energy rays) may be any of monomers and oligomers.

The energy ray curable compound (B) may be used alone or in combination of two or more kinds.

The content of the energy ray curable compound (B) in the protective film forming composition is preferably 3% by mass to 30% by mass relative to the total mass of all components except the solvent in the protective film forming composition, and more Preferably, it is 5 mass% to 25 mass %.

The content of the energy ray curable compound (B) in the film for protective film formation is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 25% by mass relative to the total mass of the film for protective film formation.

Examples of the energy ray curable compound (B) include compounds having one or more energy ray polymerizable groups in one molecule.

The aforementioned energy ray polymerizable group is not particularly limited as long as it is a group that undergoes polymerization reaction by irradiation of energy rays. When one molecule of energy ray curable compound (B) has two or more energy ray polymerizable groups, the The iso-energy ray polymerizable groups may be the same or different from each other. That is, the two or more energy ray polymerizable groups possessed by one molecule of the energy ray curable compound (B) may all be the same, all may be different, or only a part may be the same.

As said energy ray polymerizable group, a vinyl group, a (meth)acryl group etc. are mentioned, for example, Preferably it is a (meth)acryl group.

The energy ray hardening compound (B) is preferably the energy contained in one molecule A polyfunctional compound in which the number of polymerizable groups is 2 or more. In addition, in the protective film forming composition and the protective film forming film, the content of the polyfunctional compound relative to the total mass of the energy ray curable compound (B) is preferably 90% by mass to 100% by mass, and more It is preferably 95% by mass or more and 100% by mass or less, more preferably 98% by mass or more and 100% by mass or less, or 100% by mass, that is, the energy contained in the protective film forming composition and the protective film forming film All the linear curable compounds (B) may be the aforementioned polyfunctional compounds.

The molecular weight of the energy ray curable compound (B) is preferably 1000 or less, more preferably 100 to 1000, still more preferably 150 to 800, particularly preferably 200 to 550. By setting the molecular weight of the energy ray curable compound (B) within the above range, the protective effect and reliability of the formed protective film become higher.

The energy ray curable compound (B) is preferably a (meth)acrylate compound, more preferably a multifunctional (meth)acrylate compound having two or more energy ray polymerizable groups in one molecule, and particularly preferably one molecule A polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in it. In addition, here, "(meth)acrylate compound" means (meth)acrylate or its derivative. In addition, in this specification, the term "derivative" means a compound in which at least one hydrogen atom of the original compound is substituted with a group (substituent) other than a hydrogen atom.

As the above-mentioned polyfunctional (methyl) group having two or more (meth)acrylic groups ) Acrylate compounds, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate , Polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di( Meth) acrylate (also known as tricyclodecane dimethanol diacrylate), caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth) phosphate Bifunctional (meth)acrylate compounds such as acrylate, bis(acryloxyethyl) isocyanurate, and allylated cyclohexyl di(meth)acrylate; trimethylolpropane tri( Meth) acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane three (Meth)acrylate, tris(acryloxyethyl) isocyanurate, bis(acryloxyethyl)hydroxyethyl isocyanurate, isocyanuric ethylene oxide Alkyl modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, ε-caprolactone modified tris(propylene oxyethyl) isocyanurate and other trifunctional (methyl ) Acrylate compounds; 4-functional (meth)acrylate compounds such as diglycerol tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate and propionic acid to modify dipentaerythritol 5-functional (meth)acrylate compounds such as penta(meth)acrylate; and 6-functional (meth) compounds such as dipentaerythritol hexa(meth)acrylate and caprolactone modified dipentaerythritol hexa(meth)acrylate Acrylate compounds, etc.

Among the above, tricyclodecane dimethylol diacrylate, ε-caprolactone modified tris(acryloxyethyl) isocyanurate, and the like are preferred.

The energy ray curable compound (B) preferably has 2 to 4 energy ray polymerizable groups in one molecule, and more preferably 2 to 3 energy ray polymerizable groups. By using such an energy ray curable compound (B), the protective effect and reliability of the formed protective film become higher. In this specification, the energy ray curable compound (B) may include a compound having 2 to 4 energy ray polymerizable groups in one molecule and a compound having at least 5 energy ray polymerizable groups in one molecule. The compound having 2 to 4 energy ray polymerizable groups in the above molecule is called "energy ray curable compound (B1)", and the compound having at least 5 energy ray polymerizable groups in the above molecule is called " Energy ray curable compound (B2)".

The energy ray curable compound (B1) is preferably a compound having 2 to 3 energy ray polymerizable groups in one molecule, for example, tricyclodecane dimethylol diacrylic acid Ester, ε-caprolactone modified tris(acryloyloxyethyl) isocyanurate, etc.

In the composition for forming a protective film and the film for forming a protective film, an energy ray curable compound (B) having 2 to 4 energy ray polymerizable groups in one molecule (ie, an energy ray curable compound (B1)) Relative to the total mass of the energy ray curable compound (B), the content is preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass, and particularly preferably from 98% by mass to 100% by mass Hereinafter, it may be 100% by mass, that is, the energy ray curable compound (B) contained in the protective film forming composition and the protective film forming film may all be energy ray curable compounds (B1)

In addition, in the protective film forming composition and the protective film forming film, the content of energy ray curable compounds having 2 to 3 energy ray polymerizable groups in one molecule is relative to the total energy ray curable compound (B) The mass is preferably 80% by mass or more and 100% by mass or less, more preferably 85% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less , It may be 100% by mass, that is, the energy ray curable compound (B) contained in the protective film forming composition and the protective film forming film may all have 2 to 3 energy rays per molecule Energy ray curable compound of polymerizable base.

The content of the energy ray curable compound (B) in the protective film forming composition and the protective film forming film is preferably 1 to 150 parts by mass when the content of the polymer component (A) is 100 parts by mass Parts, more preferably 5 parts by mass to 130 parts by mass, particularly preferably 10 parts by mass to 110 parts by mass. By making the aforementioned content of the energy ray curable compound (B) more than the aforementioned lower limit value, the formed protective film maintains a high protective effect even when exposed to a large temperature change, and the reliability becomes higher. In addition, by making the aforementioned content of the energy ray curable compound (B) below the aforementioned upper limit value, the adhesion between the support sheet and the protective film is suppressed, and the pick-up of the semiconductor wafer with the protective film is further improved.

[Photopolymerization initiator (C)]

The photopolymerization initiator (C) is a component that generates radicals by irradiating energy rays, and causes the energy ray curable compound (B) to start a hardening reaction by radical polymerization.

The photopolymerization initiator (C) may be a known photopolymerization initiator, specifically, for example, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone , Α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropane benzene, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4- (2-Hydroxy-2-methyl-propanyl)-benzyl)phenyl}-2-methyl-propan-1-one and other α-keto alcohol compounds; acetophenone, dimethylamino phenylethyl Ketone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-benzene Acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 and other acetophenone compounds; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, anisin methyl ether and other benzoin ether compounds; benzyl dimethyl ketal, acetophenone dimethyl Ketal compounds such as ketals; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1,1-propanedione-2-(O-ethoxycarbonyl)oxime, 1- [9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetoxime) and other photoactive oxime compounds; diphenyl Ketone, p-phenyl diphenyl ketone, benzoic acid, dichloro diphenyl ketone, 4,4'-diethylamino diphenyl ketone, 3,3'-dimethyl-4- Diphenyl ketone compounds such as methoxybenzophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone Ketone, 2-ethylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2 ,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone compounds; p-dimethylamino benzoate; camphor quinone; ketone halide (ketone) halide); diphenyl (2,4,6-trimethylbenzyl) phosphine oxide (phosphine oxide) and other phosphine oxides; phosphonate/ester, oligo[2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]acetone] and the like.

Among the above, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime) is preferred Wait.

The content of the photopolymerization initiator (C) in the composition for forming a protective film, when the content of the polymer component (A) is 100 parts by mass, is preferably 0.01 to 10 parts by mass, more preferably 0.1 Parts by mass to 7 parts by mass, particularly preferably 0.2 parts by mass to 5 parts by mass. By making the aforementioned content of the photopolymerization initiator (C) more than the aforementioned lower limit value, the curing reaction of the energy ray curable compound (B) proceeds more efficiently. In addition, by making the aforementioned content of the photopolymerization initiator (C) below the aforementioned upper limit, the protective effect and reliability of the formed protective film become higher.

In addition, the content of the photopolymerization initiator (C) in the protective film formation composition is preferably 0.1% by mass to 3% by mass relative to the total mass of the protective film formation composition or the protective film formation film.

[Filling material (D)]

The protective film forming composition and the protective film forming film may also contain filler Filling material (D). By containing the filler (D) in the protective film formation film, it becomes easy to adjust the thermal expansion coefficient. Therefore, by making the thermal expansion coefficient of the protective film after hardening of such a protective film formation film optimal for a semiconductor chip, it can improve package reliability.

In addition, generally, by using the protective film forming composition containing the filler (D), the moisture absorption rate of the cured protective film can be reduced, or the thermal conductivity of the cured protective film can be improved.

The filling material (D) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material.

As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; Beads; single crystal fibers such as silicon dioxide; glass fibers, etc.

Among them, the inorganic filler material is preferably silica filler or alumina filler.

The filler (D) may be used alone or in combination of two or more kinds.

In the case of using the filler (D), the content of the filler (D) relative to the total mass of the components other than the solvent in the protective film forming composition (that is, relative to the total mass of the protective film forming film The content of the mass filler (D)) is preferably 5 mass% to 80 mass%, more preferably 7 mass% to 65% by mass. By making the content of the filler (D) above the aforementioned lower limit , The effect of using filler (D) can be obtained more significantly. In addition, by making the content of the filler (D) below the aforementioned upper limit, the protective effect and reliability of the formed protective film become higher.

[Colorant (E)]

The composition for protective film formation and the film for protective film formation may contain a coloring agent (E).

As a coloring agent (E), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, an organic type dye, etc. are mentioned, for example.

Examples of the aforementioned organic pigments and organic dyes include: aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, and squaraine dyes. Squalium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalene Phthalocyanine pigments, naphtho lactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, Dioxane pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments , Metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indole phenol dyes, triallylmethane dyes, anthraquinone dyes (anthraquinone) pigments, naphthol-based pigments, azomethine-based pigments, benzimidazolone-based pigments, pyranthrone-based pigments, and threne-based pigments.

Examples of the aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO Indium tin oxide (indium tin oxide) type pigments, ATO (antimony tin oxide; antimony tin oxide) type pigments, etc.

Among the above, phthalocyanine dyes, isoindolinone dyes, anthraquinone dyes, etc. are preferred.

The coloring agent (E) may be used individually by 1 type, and may use 2 or more types together.

In the case of using the coloring agent (E), the content of the coloring agent (E) in the film for forming a protective film may be appropriately adjusted according to the purpose. For example, there is a case where the protective film is printed by laser irradiation. By adjusting the content of the coloring agent (E) in the protective film forming film, the light transmittance of the protective film can be adjusted, and the visibility of printing can be adjusted. In this case, the content of the colorant (E) relative to the total mass of the components other than the solvent in the protective film formation composition (that is, the colorant (E) relative to the total mass of the protective film formation film The content of) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass, and particularly preferably 0.8% by mass to 5% by mass. By making the aforementioned content of the coloring agent (E) more than the aforementioned lower limit, it is possible to obtain more significantly effect. In addition, by making the aforementioned content of the colorant (E) below the aforementioned upper limit value, it is possible to suppress the excessive use of the colorant (E).

[Coupling agent (F)]

The composition for forming a protective film and the film for forming a protective film may contain a coupling agent (F). The protective film formation film contains a coupling agent (F) having a functional group that can react with an inorganic compound or an organic compound as the coupling agent (F), thereby improving the adhesion and adhesion to the adherend. In addition, the protective film formed of the protective film forming film containing the coupling agent (F) improves the water resistance without impairing the heat resistance.

The coupling agent (F) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A), the energy ray curable compound (B), etc., and more preferably a silane coupling agent.

As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxy ring) Hexyl) ethyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-(2-aminoethyl amino) propyl trimethyl Oxysilane, 3-(2-aminoethylamino) propyl methyl diethoxy silane, 3-(phenylamino) propyl trimethoxy silane, (3-ureidopropyl) three Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfane (bis(3-ethoxysilylpropyl) )tetrasulfane), methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, Vinyl triacetoxysilane, imidazole silane, etc.

Among the above, 3-methacryloxypropyltrimethoxysilane and the like are preferred.

A coupling agent (F) may be used individually by 1 type, and may use 2 or more types together.

When the coupling agent (F) is used, the content of the coupling agent (F) in the protective film forming composition and the protective film forming film is based on the content of the polymer component (A) and the energy ray curable compound (B) When the total content is 100 parts by mass, it is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. By making the aforementioned content of the coupling agent (F) more than the aforementioned lower limit, the effect of using the coupling agent (F) can be obtained more significantly. In addition, by making the aforementioned content of the coupling agent (F) below the aforementioned upper limit value, the generation of outgassing can be further suppressed.

[Crosslinking agent (G)]

When using the above-mentioned acrylic resin with functional groups that can be bonded to other compounds, such as vinyl, (meth)acrylic, amino, hydroxyl, carboxyl, isocyanate and other functional groups as the polymer component (A) In order to bond the functional group with other compounds to cause crosslinking, a crosslinking agent (G) can be used. By using the crosslinking agent (G) to cause crosslinking, the initial adhesive force and cohesive force of the protective film formation film can be adjusted.

As the crosslinking agent (G), for example, organic polyisocyanate Compounds, organic polyimine compounds, etc.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and trimers, isocyanurate bodies, and adducts of these compounds ( Reaction products with low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, such as xylylene diisocyanate adducts of trimethylolpropane, etc.), Or a terminal isocyanate urethane prepolymer obtained by reacting an organic polyisocyanate compound and a polyol compound.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; Diphenylmethane-4,4'-Diisocyanate; Diphenylmethane-2,4'-Diisocyanate; 3-Methyldiphenylmethane Diisocyanate; Hexamethylene Diisocyanate; Isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of all or part of the hydroxyl groups of polyols such as trimethylolpropane toluene diisocyanate and hexamethylene A compound of either or both of methyl diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinemethamide), trimethylolpropane-trimethylolpropane -β-aziridinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinyl methamide ) Triethylene melamine, etc.

As the crosslinking agent (G), among the above, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are preferred.

When an isocyanate-based crosslinking agent is used as the crosslinking agent (G), it is preferable to use a hydroxyl-containing polymer as the aforementioned acrylic resin as the polymer component (A). When the crosslinking agent (G) has an isocyanate group and the acrylic resin has a hydroxyl group, the crosslinking structure can be easily introduced into the protective film formation film by the reaction between the crosslinking agent (G) and the acrylic resin .

When the crosslinking agent (G) is used, the content of the crosslinking agent (G) in the protective film forming composition or the protective film forming film is set to 100 parts by mass of the polymer component (A) At this time, it is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass.

[General additives (H)]

The composition for forming a protective film and the film for forming a protective film may contain a general-purpose additive (H) in addition to the above-mentioned components.

As a general-purpose additive (H), a well-known plasticizer, an antistatic agent, an antioxidant, a scavenger, a sensitizer, etc. are mentioned, for example.

[Solvent]

The composition for forming a protective film has improved operability by dilution, so it is preferable to further contain a solvent.

Although the solvent contained in the composition for forming a protective film is not particularly limited, preferred ones include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methyl Propan-1-ol), 1-butanol and other alcohols; ethyl acetate and other esters; acetone, methyl ethyl ketone and other ketones; tetrahydrofuran and other ethers; dimethylformamide, N-methylpyrrolidone and other alcohols Amines (compounds with amide bonds) and the like.

The solvent contained in the composition for forming a protective film may be only one type or two or more types.

When the composition for forming a protective film contains a solvent, the content of the solvent is preferably such that the solid content concentration of the composition is 35 to 75% by mass relative to the total mass of the composition.

The composition for forming a protective film can be obtained by blending the above-mentioned components to constitute the composition.

The order of addition when preparing each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, the solvent can be mixed with any compounding component other than the solvent, and the compounding component can be diluted before use, or the solvent can be mixed with the compounding component and used without pre-diluting anything other than the solvent. A blending ingredient.

The method of mixing the components during the preparation is not particularly limited, and can be appropriately selected from known methods, such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; and applying ultrasonic waves. Method of mixing.

As described above, the film for forming a protective film of the present invention can be formed, for example, by applying the composition for forming a protective film on the surface of a support and drying it.

The composition for forming a protective film may be applied to the surface of the support by a known method, for example, methods using various coating machines as follows: air knife coater, knife coater, bar coater Machine, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire bar coater, die lip coating Machine waiting.

When the composition for forming a protective film is dried, the drying temperature is preferably 80°C to 130°C, and the drying time is preferably 10 seconds to 10 minutes.

The Young's modulus of the protective film formed by curing the film for forming a protective film of the present invention by irradiating energy rays is 500 MPa or more, and the elongation at break is 8% or more.

By adjusting the components of the protective film forming film such as the energy ray curable compound (B), the Young's modulus of the protective film can preferably be set to 550 MPa or more, for example, it may be 1000 MPa or more, 1400 MPa or more, 1800 MPa or more.

On the other hand, although the upper limit of the Young's modulus of the aforementioned protective film is not particularly limited, it is preferably 10,000 MPa, and more preferably 5000 MPa in terms of cutting properties or packaging reliability.

That is, the Young's modulus of the protective film is 500 MPa or more and 10,000 MPa or less, preferably 550 MPa or more and 5,000 MPa or less, more preferably 1,000 MPa or more and 5,000 MPa or less, still more preferably 1,400 MPa or more and 5,000 MPa or less, particularly preferably 1800 MPa or more and 5,000 MPa or less.

Furthermore, in the present invention, the so-called "Young's modulus" means that when a test piece is stretched at a tensile speed of 200 mm/min (tensile test), it is determined from the slope of the stress-strain curve at the initial stage of the test The value. Young's modulus can be measured at the same time when measuring the "breaking elongation" described below.

By adjusting the content of the protective film forming film such as the energy ray curable compound (B), the elongation at break of the protective film can be preferably set to 10% or more, for example, 15% or more and 20% or more. , 30% or more, 40%, 50% or more, etc.

On the other hand, although the upper limit of the breaking elongation of the protective film is not particularly limited, it is preferably 100% in terms of easily obtaining the scission property during cutting.

That is, the elongation at break of the aforementioned protective film is 8% or more and 100% or less, and can be set to 10% or more and 100% or less, 15% or more and 100% or less, and 20% or less. Upper 100% or lower, 30% or higher and 100% or lower, 40% or higher and 100% or lower, 50% or higher and 100% or lower, particularly preferably 100%.

Furthermore, in the present invention, the tensile rupture strain in accordance with JIS K7161:1994 and JIS K7127:1999 is referred to as "elongation at break". The tensile rupture strain may be that when the test piece does not have a yield point. Tensile rupture strain, or tensile rupture with a yield point, is called strain.

The elongation at break is determined by the following method: use a test piece with a width of 15 mm and a length of 140 mm as the test piece, set the distance between the clamps to 100 mm, and stretch the test piece at a stretching speed of 200 mm/min. The elongation, and the elongation at break is determined using the measured value.

Another aspect of the film for forming a protective film of the present invention is a film for forming a protective film. By irradiating energy rays, a protective film having a Young's modulus of 590 MPa to 1960 MPa and a breaking elongation of 10.7% to 56.0% is formed. membrane.

"Composite sheet for protective film formation"

The composite sheet for forming a protective film of the present invention includes the film for forming a protective film of the present invention on one surface of the support sheet.

The composite sheet for forming a protective film of the present invention is used for forming a protective film on the back surface of a semiconductor wafer or a semiconductor wafer.

As the aforementioned support sheet, for example, a support sheet composed only of a base material, and a support sheet formed by laminating other layers on the base material.

Hereinafter, the composite sheet for forming a protective film of the present invention will be described in more detail.

Fig. 1 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention. In addition, in the drawings used in the following description, in order to facilitate understanding of the characteristics of the present invention, parts that become important parts may be enlarged for convenience, and the dimensional ratios of the components are not limited to the actual ones.

The composite sheet 1A for forming a protective film shown here includes an adhesive layer 12 on a base material 11 and a protective film forming film 13 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the protective film formation composite sheet 1A has a structure in which the protective film formation film 13 is laminated on one surface 10 a of the support sheet 10. In addition, the composite sheet 1A for forming a protective film further includes a release film 15 on the film 13 for forming a protective film. The film 13 for forming a protective film is the film for forming a protective film of the present invention described above.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and an adhesive layer 12 is laminated on the surface 12a of the adhesive layer 12 (that is, the adhesive layer 12 is in contact with the substrate 11). The protective film forming film 13 is laminated on the entire surface of the protective film forming film 13 (that is, the AND and the adhesive layer 12 in the protective film forming film 13 are The adhesive layer 16 for jigs is laminated on a part of the surface on the opposite side), and the jig adhesive layer 16 is not laminated on the surface 13a of the protective film forming film 13 The surface of the adhesive layer 16 and the surface 16a of the jig adhesive layer 16 (that is, the upper surface: the surface of the jig adhesive layer 16 that is in contact with the protective film forming film 13 is the opposite side Surface and side surface: the side surface located on the center side of the composite sheet 1A for forming a protective film in the adhesive layer 16 for jigs) has a release film 15 laminated thereon.

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing adhesive components, or a multiple-layer structure in which layers containing adhesive components are layered on both areas of a sheet that becomes a core material.

The composite sheet 1A for forming a protective film shown in FIG. 1 is a state in which the release film 15 is removed, and the back surface of a semiconductor wafer (not shown) is attached to the surface 13a of the protective film forming film 13, and then The upper surface of the surface 16a of the adhesive layer 16 for jigs is used by sticking to jigs, such as a ring frame.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In addition, in FIG. 2, the same components as those shown in FIG. 1 are assigned the same reference numerals as in FIG. 1, and detailed descriptions thereof are omitted. The same applies to the figures below Figure 3.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that it does not have the adhesive layer 16 for jigs. That is, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the adhesive layer 12 is The protective film forming film 13 is laminated on the entire surface 12a (that is, the surface of the adhesive layer 12 on the opposite side to the substrate 11), and the protective film forming film 13 is laminated on the surface 13a ( That is, the release film 15 is laminated on the entire surface of the protective film forming film 13 which is the surface on the opposite side to the adhesive layer 12. The film 13 for forming a protective film is the film for forming a protective film of the present invention described above.

The protective film forming composite sheet 1B shown in FIG. 2 is in the state where the release film 15 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the center of the surface 13a of the protective film forming film 13 A partial area on the side, and the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame for use.

Fig. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that it does not include the adhesive layer 12. That is, in the composite sheet 1C for forming a protective film, the support sheet is composed of only the base material 11. In addition, a protective film formation film 13 is laminated on one surface 11a of the base material 11, and a protective film formation film 13 is laminated on the surface 13a (the protective film formation film 13 is opposite to the surface in contact with the base material 11). A part of the side surface) is laminated with an adhesive layer 16 for jigs. On the surface 13a of the protective film forming film 13 where the adhesive layer 16 for jigs is not laminated, and the surface of the adhesive layer 16 for jigs 16a (that is, upper surface: one of the adhesive layer 16 for jig The surface in contact with the protective film forming film 13 is the opposite side and the side surface: that is, the side surface located on the center side of the protective film forming composite sheet 1C in the jig adhesive layer 16) is laminated with a release film 15 . The film 13 for forming a protective film is the film for forming a protective film of the present invention described above.

The composite sheet 1C for forming a protective film shown in FIG. 3 is the same as the composite sheet 1A for forming a protective film shown in FIG. 1. With the release film 15 removed, the semiconductor wafer (not shown) The back surface is attached to the surface 13a of the protective film forming film 13, and the upper surface of the surface 16a of the adhesive layer 16 for jigs is attached to jigs such as a ring frame for use.

Fig. 4 is a cross-sectional view schematically showing yet another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 3 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1D for forming a protective film, the protective film forming film 13 is laminated on one surface 11a of the base material 11, and the surface 13a of the protective film forming film 13 (the sum of the protective film forming film 13 The release film 15 is laminated on the entire surface of the surface in contact with the substrate 11 (the surface on the opposite side). The film 13 for forming a protective film is the film for forming a protective film of the present invention described above.

The composite sheet 1D for forming a protective film shown in FIG. 4 is the same as the composite sheet 1B for forming a protective film shown in FIG. 2. With the release film 15 removed, the semiconductor wafer (not shown) The back is attached to the protective film to form A part of the area on the central side of the surface 13a of the film 13, and the area near the periphery of the protective film forming film 13 is attached to a jig such as a ring frame for use.

Fig. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in FIG. 2 except that the shape of the film for forming a protective film is different. That is, the composite sheet 1E for forming a protective film is formed by including an adhesive layer 12 on a base material 11 and a protective film forming film 23 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the protective film forming composite sheet 1E has a layer on one surface 10a of the support sheet 10 (that is, the surface on the adhesive layer 12 side) The structure of the film 23 for forming a protective film. In addition, the composite sheet 1E for forming a protective film further includes a release film 15 on the film 23 for forming a protective film. The protective film forming film 23 is the protective film forming film of the present invention described above, and is the same as the protective film forming film 13 except for the difference in shape.

In the composite sheet 1E for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and an adhesive layer 12 is laminated on the surface 12a of the adhesive layer 12 (that is, the surface on the opposite side to the surface contacting the substrate 11a). The protective film forming film 23 is laminated on a part of the surface). In addition, on the surface 12a of the adhesive layer 12, the surface on which the protective film forming film 23 is not laminated, and the surface 23a of the protective film forming film 23 (upper and side surfaces: that is, one of the protective film forming films 23 Not sticky A release film 15 is laminated on the surface where the adhesive layer 12 contacts.

When the composite sheet 1E for protective film formation is viewed from above, the surface area of the protective film formation film 23 is smaller than that of the adhesive layer 12, and it has a shape, such as a circle, for example.

The protective film forming composite sheet 1E shown in FIG. 5 is in a state where the release film 15 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the protective film forming film 23, and then the The surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame for use.

The composite sheet for forming a protective film of the present invention is not limited to those shown in FIGS. 1 to 5, and may be a composite sheet for forming a protective film shown in FIGS. 1 to 5 within a range that does not impair the effects of the present invention. Part of the structure is changed or deleted, or another structure is added to the composite sheet for forming a protective film described above.

For example, in the composite sheet for forming a protective film shown in FIGS. 3 and 4, an intermediate layer may be provided between the base material 11 and the film 13 for forming a protective film.

As the intermediate layer, it can be arbitrarily selected according to the purpose.

In addition, in the composite sheet for forming a protective film shown in FIGS. 1, 2 and 5, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by sequentially laminating a base material, an intermediate layer, and an adhesive layer. Here, the so-called intermediate layer system and Figure 3 and The intermediate layer in the composite sheet for forming a protective film shown in FIG. 4 is the same.

In addition, the composite sheet for forming a protective film shown in FIGS. 1 to 5 may be provided with a layer other than the aforementioned intermediate layer at any position.

Next, the elements constituting the composite sheet for protective film formation other than the film for protective film formation will be described in more detail.

<Substrate>

The material of the base material is preferably various resins. As specific examples thereof, polyethylene (low density polyethylene (sometimes abbreviated as LDPE (low density polyethylene)), linear low-density polyethylene (sometimes abbreviated as LLDPE) (linear low density polyethylene)), high density polyethylene (sometimes referred to as HDPE (high density polyethylene)), etc., polypropylene, ethylene-propylene copolymer, polybutene, polybutadiene, polymethylpentene, Polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyamide Imine, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polystyrene, polycarbonate, fluororesin, etc. Any hydride, modified, cross-linked or copolymer of any resin.

The thickness of the substrate can be appropriately selected according to the purpose, and is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. By setting the thickness of the base material within the above range, the flexibility of the composite sheet for forming a protective film and the adhesion to the semiconductor wafer or the semiconductor wafer are further improved.

The substrate may be composed of one layer (single layer), or may be composed of two or more layers (for example, two to four layers). When the substrate is composed of multiple layers, the multiple layers may be the same or different from each other. That is, all the layers may be the same, all the layers may be different, or only a part of the layers may be the same. In addition, when the plural layers are different from each other, the combination of the plural layers is not particularly limited. Here, the term that the plural layers are different from each other means that at least one of the material and thickness of each layer is different from each other.

Furthermore, when the base material is composed of a plurality of layers, the total thickness of each layer may be the above-mentioned preferable base material thickness.

The surface of the substrate can also be subjected to the following treatments to improve the adhesion with other layers such as the adhesive layer provided on the substrate: concave-convex treatment by sandblasting, solvent treatment, etc.; corona discharge treatment, electronics Oxidation treatments such as beam irradiation treatment, plasma treatment, ozone, ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. In addition, the surface of the substrate may also be subjected to primer treatment.

<Adhesive layer>

The aforementioned adhesive layer can be appropriately composed of known components.

The adhesive layer can be formed using an adhesive composition containing various components for constituting the adhesive layer. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components of the adhesive layer.

In the case where the adhesive layer contains a component that is polymerized by irradiating energy rays, the adhesiveness is reduced by irradiating energy rays, and the semiconductor chip can be easily picked up. Such an adhesive layer can be formed using various adhesive compositions containing components polymerized by irradiation of energy rays, such as an energy-ray polymerizable acrylic polymer.

A preferable one among the adhesive composition is, for example, if it is an adhesive composition (energy-ray curable adhesive composition) containing a component polymerized by irradiation of energy rays, it may include: containing the aforementioned acrylic polymer Adhesive composition with energy-ray polymerizable compound (sometimes referred to as adhesive composition (i)); containing an acrylic polymer having a hydroxyl group and a polymerizable group in the side chain (for example, having a hydroxyl group and passing through an amine The adhesive composition (sometimes referred to as the adhesive composition (ii)) of an acrylic polymer having a polymerizable group on the side chain with an ethyl formate bond) and an isocyanate crosslinking agent, preferably further containing a solvent .

In addition to the above-mentioned components, the aforementioned adhesive composition may further contain any of various additives such as photopolymerization initiators, dyes, pigments, anti-deterioration agents, antistatic agents, flame retardants, silicone compounds, and chain transfer agents. One kind.

In addition, the adhesive composition is preferably, for example, if it is an adhesive composition (non-energy-ray curable adhesive composition) that does not contain a component that is polymerized by irradiation of energy rays, an acrylic-based Adhesive composition of resin and crosslinking agent (sometimes called adhesive composition (iii)), etc., It can also contain solvents and other components that are not solvents.

The thickness of the adhesive layer can be appropriately selected according to the purpose, and is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, particularly preferably 1 μm to 30 μm.

The adhesive composition can be obtained, for example, by blending acrylic polymers and other components for constituting the adhesive layer. For example, except for the difference in the blending components, the same as that of the protective film forming composition can be used. Method to obtain.

The adhesive layer can be formed by applying an adhesive composition to the target site and drying it.

At this time, if necessary, the applied adhesive composition can be heated to generate crosslinking. Although heating conditions can be set to 100 degreeC-130 degreeC for 1 minute to 5 minutes, for example, it is not limited to this.

Furthermore, when energy ray is irradiated to the target part through the support sheet, each layer such as the base material and the adhesive layer constituting the support sheet preferably has a high energy ray transmittance.

Hereinafter, the manufacturing method of the composite sheet for protective film formation is demonstrated in detail.

<Method for manufacturing composite sheet for forming protective film>

The composite sheet for forming a protective film of the present invention can be used on one of the supporting sheets It is manufactured by forming the protective film forming film of the present invention on the surface of the square.

For example, a composite sheet for forming a protective film having a support sheet composed of only a base material can be manufactured by applying a composition for forming a protective film on the surface of the base material and drying to form a protective film For the film, if necessary, another layer (film) such as an adhesive layer for jigs or a release film is provided on the film for forming a protective film. The formation conditions of the protective film formation film at this time are the same as the above-mentioned method.

Such a manufacturing method is suitable as a manufacturing method of the composite sheet for protective film formation shown in FIG. 3 and FIG. 4, for example.

In addition, for example, a composite sheet for forming a protective film having a support sheet formed by laminating an adhesive layer on a substrate can be manufactured by applying an adhesive composition on the surface of the substrate and drying to form an adhesive For the agent layer, a protective film forming film is further provided on the adhesive layer using the protective film forming composition, and other layers (films) such as a jig adhesive layer or a release film are provided on the protective film forming film as necessary.

In this case, for example, a protective film formation composition can be applied to the adhesive layer to provide a protective film formation film. However, in general, the laminated structure of the substrate, the adhesive layer, and the protective film forming film is preferably formed by separately forming the protective film forming film and bonding it to the surface of the adhesive layer, for example, by The protective film forming film formed by coating the protective film forming composition on the surface of the peeling layer of the peeling film and drying is attached to the surface of the adhesive layer, and the peeling film is removed if necessary.

In addition, the laminated structure of the substrate, the adhesive layer, and the protective film formation film can be formed by, for example, the following method: using an adhesive composition to form an adhesive layer on the release film, and using a protective film formation The composition forms a protective film forming film on another release film, and then overlaps the adhesive layer and the protective film forming film on the release film, and removes the release film laminated on the adhesive layer to expose the adhesive The layer surface (the surface of the adhesive layer on which the protective film formation film is not provided) is bonded to the base material.

Any of the above methods can be achieved by forming a layered structure of the substrate, adhesive layer, and protective film forming film, and then, if necessary, providing other layers such as a jig adhesive layer or a release film on the protective film forming film ( Film) to produce a composite sheet for forming a protective film having a support sheet formed by laminating an adhesive layer on a substrate. In either case, the formation conditions of the adhesive layer and the protective film formation film are the same as the above-mentioned method.

Such a manufacturing method is suitable as, for example, the manufacturing method of the composite sheet for forming a protective film shown in FIGS. 1, 2 and 5.

For example, when manufacturing a composite sheet for forming a protective film as shown in FIG. 5, when looking down from above and looking down on a composite sheet for forming a protective film, the surface area of the film for forming a protective film is smaller than that of the adhesive layer. In the method, the protective film forming film that has been cut into a predetermined size and shape in advance is only required to be placed on the adhesive layer.

<How to use the protective film formation film or the protective film formation composite sheet>

As a method of using the film for forming a protective film or a composite sheet for forming a protective film of the present invention, for example, use method 1 to use method 4 shown below can be cited.

[How to use 1]

In the use method 1, first, the protective film formation film of the protective film formation composite sheet is attached to the back surface of the semiconductor wafer, and the protective film formation composite sheet is fixed to the dicing device.

Then, by irradiating energy rays, the protective film forming film is cured to form a protective film. When the conventional protective film formation film is used, it takes a long time, for example, about several hours to harden the protective film formation film by heating. In contrast, the protective film formation film of the present invention is irradiated with energy The wire can be cured even in a short time of less than 1 minute, such as a few seconds or so, and a semiconductor chip with a protective film can be obtained in a much shorter time than the conventional technology.

Furthermore, when a back polishing tape is attached to the surface (electrode formation surface) of a semiconductor wafer, usually, the back polishing tape is removed from the semiconductor wafer, and then the protective film forming film is cured.

Then, the semiconductor wafer is cut to form a semiconductor wafer.

Then, the semiconductor chip together with the protective film attached to its back The self-supporting sheet is peeled off and picked up, thereby obtaining a semiconductor wafer with a protective film. When the support sheet is formed by laminating an adhesive layer on a base material, as the adhesive layer, a non-energy-ray-curable adhesive layer that does not contain components that are polymerized by irradiation with energy rays is used.

In the use method 1, it is also possible to irradiate the protective film formation film or the protective film with laser light through the support sheet at any time after the protective film formation film is attached to the semiconductor wafer to the dicing period. The protective film formation film or protective film is printed. In the case of printing the film for forming a protective film, by curing the film, a printed protective film is obtained.

In addition, when printing, gas is sometimes generated. Although this gas may cause the final peeling between the support sheet and the protective film, when printing on the protective film formation film, compared to the protective film In the case of printing, the frequency or degree of peeling can be reduced.

It is presumed that the reason is that the adhesiveness between the protective film forming film and the support sheet is higher than the adhesiveness between the protective film and the support sheet.

[How to use 2]

In the use method 2, first, the protective film formation film is attached to the back surface of the semiconductor wafer.

Then, by irradiating energy rays, the protective film forming film is cured to form a protective film. Thereby, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a much shorter time than the conventional technique. On the surface of the semiconductor wafer (electrode formation surface) is attached with a back polishing tape In this case, usually, after removing the back polishing tape from the semiconductor wafer, the protective film forming film is cured.

Then, a support sheet was attached to the exposed surface of the protective film. When the support sheet is formed by laminating an adhesive layer on a substrate, as the adhesive layer, an energy-ray curable adhesive layer containing a component polymerized by irradiation with energy rays, and the above-mentioned non-energy-ray curable adhesive can be used Any of the agent layers.

Then, the semiconductor wafer is cut to form a semiconductor wafer.

Then, the semiconductor chip is peeled from the support sheet together with the protective film attached to the back surface and picked up, thereby obtaining the semiconductor chip with the protective film. When the support sheet is formed by laminating an adhesive layer on the substrate, the semiconductor chip with the protective film can be picked up more easily by hardening the adhesive layer.

In the use method 2, it is also possible to directly irradiate the protective film formation film with laser light or to directly irradiate the protective film formation film to the protective film at any point during the dicing period after the protective film formation film is attached to the semiconductor wafer The laser light is irradiated to print the protective film forming film or protective film. In the case of printing the film for forming a protective film, by curing the film, a printed protective film is obtained.

[How to use 3]

In use method 3, first attach the protective film forming film to the semiconductor The back side of the wafer.

Then, a support sheet was attached to the exposed surface of the film for forming a protective film. When the support sheet is formed by laminating an adhesive layer on the base material, a non-energy ray-curable adhesive layer is used as the adhesive layer.

Then, by irradiating energy rays, the protective film forming film is cured to form a protective film. Thereby, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a much shorter time than the conventional technique. When a back polishing tape is attached to the surface (electrode formation surface) of a semiconductor wafer, normally, the back polishing tape is removed from the semiconductor wafer, and then the protective film forming film is cured.

Then, the semiconductor wafer is cut to form a semiconductor wafer.

Then, the semiconductor chip is peeled from the support sheet together with the protective film attached to the back surface and picked up, thereby obtaining the semiconductor chip with the protective film.

In use method 3, it is also possible to irradiate the protective film formation film with laser light directly or through a support sheet at any time between the time after the protective film formation film is attached to the semiconductor wafer and the dicing period to protect the The film for film formation is printed, or the protective film is irradiated with laser light through the support sheet to print the protective film. In the case of printing the film for forming a protective film, by curing the film, a printed protective film is obtained.

Furthermore, when printing the protective film forming film after attaching the support sheet, it is the same as the case of the above-mentioned use method 1, compared to the protective film When the film is printed, the frequency or degree of peeling between the support sheet and the protective film can be reduced.

[How to use 4]

In the use method 4, the protective film forming film is first attached to the back surface of the semiconductor wafer.

Then, a support sheet was attached to the exposed surface of the film for forming a protective film. When the support sheet is formed by laminating an adhesive layer on the base material, a non-energy ray-curable adhesive layer is used as the adhesive layer.

Then, the semiconductor wafer is cut to form a semiconductor wafer.

Then, by irradiating energy rays, the protective film forming film is cured to form a protective film. Thereby, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a much shorter time than the conventional technique.

Then, the semiconductor chip is peeled from the support sheet together with the protective film attached to the back surface and picked up, thereby obtaining the semiconductor chip with the protective film.

In use method 4, it is also possible to irradiate the protective film formation film with laser light directly or via a support sheet at any time between the time after the protective film formation film is attached to the semiconductor wafer and the dicing period to protect the The film for film formation is printed. The printed protective film is cured by curing the printed protective film.

Furthermore, in the use method 4, after attaching the support sheet, the protective film In the case of printing on the formed film, as in the case of the above-mentioned use method 1, compared to the case of printing the protective film in other use methods, the frequency or degree of peeling between the support sheet and the protective film can be reduced.

By using the protective film forming film or the protective film forming composite sheet of the present invention, the protective film has a sufficiently high protective effect until the semiconductor chip with the protective film is obtained. Therefore, the generation of cracks or chipping in the semiconductor wafer is suppressed, for example, cracking is suppressed. In addition, even if the aforementioned protective film is exposed to a large temperature change, it can maintain such a high protective effect and has high reliability.

One aspect of the protective film formation film of one embodiment of the present invention includes the following protective film formation film: used to form a protective film on the back surface of a semiconductor wafer or semiconductor wafer; the protective film formation film contains an energy ray curable compound (B), and optionally selected from polymer component (A), photopolymerization initiator (C), filler (D), coloring agent (E), coupling agent (F), crosslinking agent (G) and At least one component in the group consisting of general additives (H); the aforementioned component (B) includes energy ray hardening that is a (meth)acrylate compound and has 2 to 4 energy ray polymerizable groups in one molecule Compound (B1), the aforementioned component (A) is an acrylic resin with a weight average molecular weight (Mw) of 10,000 to 2,000,000 and a glass transition temperature of -60°C to 70°C, and the aforementioned component (C) is composed of 1-[9- Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime) is composed; the content of the aforementioned (B) component is relative The total mass of the aforementioned protective film formation film is 3% by mass or more and 30% by mass or less Next; In the aforementioned (B) component, the content of the aforementioned (B1) component relative to the total mass of the aforementioned (B) component is 90% by mass to 100% by mass, preferably 95% by mass to 100% by mass, more preferably 98% by mass or more and 100% by mass or less, particularly preferably 100% by mass; when the aforementioned (A) component is included, the content of the aforementioned (A) component relative to the total mass of the protective film forming film is 5 mass% to 50% by mass, preferably 10% to 45% by mass. When the component (C) is included, the content of the component (C) is 0.1% to 3% by mass relative to the total mass of the protective film forming film %; The total content of the components constituting the protective film forming film does not exceed 100% by mass; further, the protective film forming film having the following characteristics can be cited.

When the protective film forming film is cured by irradiating energy rays to form a cured product (protective film), the Young's modulus of the cured product is 500 MPa or more and 10,000 MPa or less, preferably 550 MPa or more and 5,000 MPa or less, and elongation at break It is 8% or more and 100% or less, preferably 10% or more and 100% or less.

The Young's modulus of the aforementioned hardened product may be 590 MPa or more and 1960 MPa or less, and the elongation at break may be 10.7% or more and 56% or less.

Another aspect of the film for forming a protective film of an embodiment of the present invention includes the following film for forming a protective film: a film for forming a protective film on the back of a semiconductor wafer or a semiconductor wafer; At least one energy ray curable compound (B) in the group consisting of decane dimethanol diacrylate and ε-caprolactone modified tris(acryloxyethyl) isocyanurate; Free methyl (meth)acrylate, (meth)acrylic acid Polymer component (A) formed by polymerization of at least one monomer in the group consisting of butyl ester, 2-hydroxyethyl (meth)acrylate and glycidyl (meth)acrylate; 1-[9-乙Group-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(0-acetyloxime) (C); and selected from filler materials (D), At least one component in the group consisting of coloring agent (E), coupling agent (F), crosslinking agent (G) and general additive (H); and relative to the total mass of the aforementioned protective film forming film, the aforementioned The content of component (B) is 10% by mass to 20% by mass, the content of component (A) is 20% to 32% by mass, and the content of component (C) is 0.6% by mass or more; When the protective film forming film is cured to form a cured product (protective film), the Young's modulus of the cured product is 590 MPa to 1960 MPa, and the elongation at break is 10.7% to 56.0%.

[Example]

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

The raw materials used to manufacture the protective film forming composition are shown below.

‧Polymer composition (A)

(A)-1: Acrylic resin obtained by copolymerizing 10 parts by mass of butyl acrylate, 70 parts by mass of methyl acrylate, 15 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of glycidyl methacrylate ( The weight average molecular weight is 800,000, and the glass transition temperature is -1°C).

‧Energy ray hardening compound (B)

(B1)-1: Tricyclodecane dimethanol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., a bifunctional ultraviolet curable compound, molecular weight 304).

(B1)-2: ε-caprolactone modified tris(2-propenoxyethyl) isocyanurate ("A-9300-1CL" manufactured by Shinnakamura Chemical Industry Co., Ltd., 3 functional UV curing Sexual compound, molecular weight 537).

(B2)-1: Mixture of dipentaerythritol hexaacrylate (6-functional ultraviolet curable compound, molecular weight 578) and dipentaerythritol pentaacrylate (5-functional ultraviolet curable compound, molecular weight 525) (manufactured by Nippon Kayaku Corporation "KAYARAD DPHA”).

˙Photopolymerization initiator (C)

(C)-1: 1-[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime)( "Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).

‧Filling material (D)

(D)-1: Silica filler (fused silica filler, average particle size 8μm).

‧Colorant (E)

(E)-1: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and anthraquinone-based red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass, and pigmenting so that the total amount of the aforementioned 3 kinds of pigments/amount of styrene acrylic resin=1/3 (mass ratio).

‧Coupling agent (F)

(F)-1: 3-Methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)

[Example 1]

<Production of protective film forming film>

(Manufacturing of protective film forming composition)

Polymer component (A)-1 (32 parts by mass), energy ray curable compound (B)-1 (10 parts by mass), photopolymerization initiator (C)-1 (0.3 parts by mass), photopolymerization Starting agent (C)-2 (0.3 parts by mass), filler (D)-1 (56 parts by mass), coloring agent (E)-1 (2 parts by mass), and coupling agent (F)-1 (0.4 parts by mass) ) Are mixed to obtain a composition for forming a protective film. Table 1 shows the types of blended components and their blended amounts. In addition, all the blending amounts shown in Table 1 are solid content amounts. In addition, in Table 1, each component is shown only by the end symbol, for example, the polymer component (A) is abbreviated as "(A)".

(Manufacture of protective film forming film)

The peeling treatment of the peeling film ("SP-PET381031" made by Lintec Corporation, thickness 38μm) made by peeling off one side of the polyethylene terephthalate film by silicone treatment On the surface, the protective film forming composition obtained above was applied using a knife coater, and dried at 120°C to obtain a protective film forming film (thickness 25 μm). Furthermore, the same release film as above was attached to the exposed surface of the obtained protective film formation film so that the release treatment surface was in contact with the protective film formation film, and the two sides of the protective film formation film were provided with the aforementioned Laminated body of peeling film. The obtained laminate was wound into a roll shape and stored.

<Evaluation of protective film forming film>

(Evaluation of Young's modulus and elongation at break of protective film)

The laminate obtained above was rolled out, and ultraviolet rays were irradiated under conditions of an illuminance of 230 mW/cm ² and a light quantity of 170 mJ/cm ² to harden the protective film forming film to form a protective film.

Then, the protective film with the release film was cut into a size of 15 mm in width and 140 mm in length, and the release film was removed from both sides and used as a test piece. According to JIS K7161: 1994 and JIS K7127: 1999, the test glue board (label) is attached from the two ends of the test piece to the 20mm part in the length direction, and the universal testing machine (manufactured by Shimadzu Corporation) "Autograph AG-IS 500N"), the part is fixed with clamps so that the distance between the clamps becomes 100mm, and the tensile test is performed at a tensile speed of 200mm/min.

In addition, the stress-strain curve at this time was prepared, the Young's modulus was calculated from the slope of the stress-strain curve at the initial stage of the test, and the elongation at break was calculated from the elongation of the test piece at the time of breaking. The results are shown in Table 1.

(Evaluation of the reliability of the protective film)

The laminate obtained above was rolled out, one of the aforementioned release films was removed from one side of the protective film forming film, and a tape mounter ("Adwill RAD-3600F/12 manufactured by Lintec Corporation) was used to remove The exposed surface of the protective film formation film with the release film on one side was heated to 70°C and attached to the polished surface of a #2000 silicon wafer (diameter 200mm, thickness 280μm) polished. Then, the illuminance was 230mW/cm ^2. Irradiate ultraviolet rays under the condition of a light quantity of 170mJ/cm ² to harden the protective film forming film and form a protective film on the polished surface of the silicon wafer.

Then, after removing another release film from the aforementioned protective film, a dicing sheet ("Adwill G-562" manufactured by Lintec Corporation) was attached, and a cutting device ("DFD651" manufactured by Disco Corporation) was used to remove the above-mentioned protective film. The silicon wafer is cut into a size of 3mm×3mm to obtain a semiconductor chip with a protective film.

Then, the semiconductor chip with the protective film obtained above is placed under the preconditions shown below that mimic the process of mounting the semiconductor chip. That is, after baking the semiconductor wafer with the protective film at 125°C for 20 hours, it absorbs moisture for 168 hours under the conditions of 85°C and 85% relative humidity, and then makes the protective film attached just after being taken out from the hygroscopic environment The semiconductor wafers are passed 3 times in an IR (infrared) reflow oven with a preheating of 160°C and a peak temperature of 260°C. In addition, the 25 semiconductor wafers with protective films that have undergone the above operations are placed in a thermal shock device ("TSE-11-A" manufactured by ESPEC Corporation), repeated 1,000 times and kept at -65°C for 10 minutes. Keep at 150°C for 10 minutes of heat and cold cycle.

Then, the semiconductor chip with the protective film was taken out from the thermal shock device, and the scanning ultrasonic flaw detection device ("D9600 ^TM CSAM" manufactured by Sonoscan) was used to observe the cross-section of the semiconductor chip with the protective film. Check whether the junction between the semiconductor wafer and the protective film is raised or peeled, and whether there are cracks in the semiconductor wafer. In addition, count the number of semiconductor wafers with a protective film that produced at least one of the above-mentioned bumps, peeling, and cracks, and judge the reliability as acceptable when the number (NG number) is 2 or less (A) , It will be judged as reliability failure (B) for 3 or more cases. The results are shown in Table 1.

<Production and Evaluation of Film for Forming Protective Film>

[Example 2 to Example 4, Comparative Example 1 to Comparative Example 6]

Except that the types and the amounts of the components to be blended when manufacturing the protective film forming composition were as shown in Table 1, the same method as in Example 1 was used to manufacture and evaluate the protective film forming film.

The results are shown in Table 1.

※1: Cracks occurred during cutting, and the semiconductor chip with protective film could not be obtained.

From the above results, it is clear that the protective film formed from the protective film forming film of Example 1 and Example 4 has high Young's modulus and elongation at break, has sufficient protective effect, and has high reliability.

In contrast, the protective film formed from the protective film forming film of Comparative Example 1, Comparative Example 2, Comparative Example 4, and Comparative Example 6 had low elongation at break, insufficient protective effect, and low reliability. The reasons are presumed to be that the energy ray curable compound (B2)-1 was used in Comparative Examples 1 to 2, and the energy ray curable compound (B1)-1 was used in an excessive amount in Comparative Example 4. In Comparative Example 6, there are these two reasons.

In addition, the protective film formed from the protective film forming film of Comparative Example 3 and Comparative Example 5 had a low Young's modulus and cracked during dicing. The semiconductor wafer with the protective film could not be obtained, and the reliability of the protective film could not be evaluated. . It is presumed that the reason is that the usage amount of the energy ray curable compound (B1)-1 in Comparative Example 3 is too small, and the usage amount of the energy ray curable compound (B2)-1 in Comparative Example 5 is too small.

(Industrial availability)

The invention can be used to manufacture semiconductor chips whose backside is protected by a protective film And so on, so it is extremely useful in industry.

1A‧‧‧Composite sheet for forming protective film

10‧‧‧Support film

10a‧‧‧(supporting film) surface

11‧‧‧Substrate

11a‧‧‧(of the substrate) surface

12‧‧‧Adhesive layer

12a‧‧‧(adhesive layer) surface

13‧‧‧Film for forming protective film

13a‧‧‧(The surface of the protective film forming film)

15‧‧‧Peeling film

16‧‧‧Adhesive layer for fixture

16a‧‧‧(adhesive layer for jig) surface

Claims (6)

A film for forming a protective film, used to form a protective film on the back of a semiconductor wafer or a semiconductor wafer, containing selected from acrylic resin, polyester, polyurethane, urethane acrylate resin, silicone resin, The polymer component (A) of rubber-based polymer, phenoxy resin, and energy-ray curable compound (B), wherein the film for forming a protective film does not contain polyimide, and has the following characteristics: When the protective film forming film is cured to form a cured product, the Young's modulus of the cured product is from 1080 MPa to 10,000 MPa, and the elongation at break is 8% or more. A film for forming a protective film, used to form a protective film on the back of a semiconductor wafer or a semiconductor wafer, containing selected from acrylic resin, polyester, polyurethane, urethane acrylate resin, silicone resin, The polymer component (A) of rubber-based polymer, phenoxy resin, and energy-ray curable compound (B), wherein the film for forming a protective film does not contain polyimide, and has the following characteristics: When the protective film forming film is cured to form a cured product, the Young's modulus of the cured product is 500 MPa or more, and the elongation at break is 8% or more to 56.0% or less. A film for forming a protective film, used to form a protective film on the back of a semiconductor wafer or a semiconductor wafer, containing selected from acrylic resin, polyester, polyurethane, urethane acrylate resin, silicone resin, Rubber-based polymer, polymer component (A) of phenoxy resin, energy ray curable compound (B) and filler (D); the aforementioned filler (D) Relative to the total mass of the protective film forming film is 5 mass% to 80 mass%; wherein the protective film forming film does not contain polyimide, and has the following characteristics: by irradiating energy rays, the aforementioned protection When the film for film formation is cured to form a cured product, the Young's modulus of the cured product is 500 MPa or more, and the elongation at break is 8% or more. The film for forming a protective film as described in any one of claims 1 to 3, wherein the content of the energy ray curable compound (B) is 5 to 25% by mass relative to the total mass of the film for forming the protective film . The film for forming a protective film according to any one of claims 1 to 3, wherein in the film for forming a protective film, an energy ray curable compound (B1) having 2 to 4 energy ray polymerizable groups in one molecule The content of) is 90% by mass or more with respect to the total mass of the energy ray curable compound (B). A composite sheet for forming a protective film is provided with the film for forming a protective film as described in any one of claims 1 to 5 on one surface of a support sheet.

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