KR20200080237A - Method for manufacturing a film for forming a protective film, a composite sheet for forming a protective film, and a semiconductor chip - Google Patents

Abstract

The present invention relates to a film 13 for forming an energy ray curable protective film, the protective film forming film 13 is adhered to a semiconductor wafer, and for the gloss value (G1) measured after irradiating energy rays, the protective film is formed The deterioration rate (G1-G2)/G1×100 of the gloss value (G2) measured after attaching the molten film 13 to a semiconductor wafer, irradiating energy rays, and further heating at 260° C. for 5 minutes is 30% or less to be.

Description

Method for manufacturing a film for forming a protective film, a composite sheet for forming a protective film, and a semiconductor chip

The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, and a method for manufacturing a semiconductor chip.

This application claims priority based on Japanese Patent Application No. 2017-208437 for which it applied to Japan on October 27, 2017, and uses the content here.

In recent years, manufacture of a semiconductor device to which a mounting method called a so-called face down method is applied has been performed. In the face down method, a semiconductor chip having an electrode such as a bump is used on the circuit surface, and the electrode is joined to the substrate. For this reason, the back surface on the opposite side to the circuit surface of the semiconductor chip can be exposed.

A resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and can be introduced into a semiconductor device as a semiconductor chip on which the protective film is formed.

The protective film is used to prevent cracking in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film comprising a film for forming a protective film for forming a protective film on a support sheet is used. The protective film-forming film can form a protective film by curing. The support sheet can be used to fix a semiconductor wafer when a semiconductor wafer having a protective film forming film or a protective film on the back surface is divided into semiconductor chips. Further, the support sheet can be used as a dicing sheet, and the composite sheet for forming a protective film can also be used as an integrated film for forming a protective film and a dicing sheet.

As such a composite sheet for forming a protective film, a film having a thermosetting protective film forming film that forms a protective film by curing by heating, for example, has been mainly used so far. However, since the heat curing of the film for forming a thermosetting protective film usually requires a long time of about several hours, shortening of the curing time is required. On the other hand, it has been studied to use a film for forming a protective film (energy-ray-curable) that can be cured by irradiation with energy rays such as ultraviolet rays to form a protective film.

Patent Document 1 discloses a film for protecting an energy ray-curable chip attached to a back surface of a wafer circuit forming surface. This energy ray-curable chip protective film has a release film and an energy ray-curable protective film-forming layer formed on the release film. The energy ray-curable protective film-forming layer contains a non-energy ray curing component as a binder polymer component in addition to the energy ray curable component.

Japanese Patent Application Publication No. 2010-056328

The semiconductor chip on which the protective film is formed using the energy ray-curable chip protective film described in Patent Document 1 is bonded to a desired device by heating. By this heating, among the non-energy-ray-cured components included in the protective film, a relatively low molecular weight component (so-called brid-out component) is segregated on the surface of the protective film, and the surface gloss of the protective film can be significantly reduced. Thereby, the fall of the designability of a protective film and the visibility fall when printing on the surface of a protective film.

Therefore, in the present invention, even when a semiconductor chip having a protective film as a cured product of a film for forming a protective film on the back surface is heated for the purpose of bonding or the like, the film for forming a protective film capable of suppressing a decrease in surface gloss of the protective film, forming the protective film An object of the present invention is to provide a composite sheet for forming a protective film provided with a film for use and a method for manufacturing a semiconductor chip using the film for forming a protective film or the composite sheet for forming a protective film.

In order to solve the above-mentioned problems, the present invention is a film for forming an energy ray-curable protective film. The film for forming a protective film for the gloss value measured after affixing the film for forming a protective film to a semiconductor wafer and irradiating energy rays. A film for forming a protective film having a decrease rate of a gloss value of 30% or less after attaching to a semiconductor wafer, irradiating with energy rays, and heating at 260°C for 5 minutes is also provided.

The present invention provides a composite sheet for forming a protective film provided with a support sheet and provided with the film for forming a protective film on the support sheet.

The present invention provides a process for attaching a film for forming a protective film or a film for forming a protective film in a composite sheet for forming a protective film to a semiconductor wafer, and irradiating ultraviolet rays on the film for forming a protective film after being attached to the semiconductor wafer to form a protective film. There is provided a method of manufacturing a semiconductor chip having a process and a step of dividing the semiconductor wafer by cutting the semiconductor wafer together with the protective film or a film for forming a protective film to obtain a plurality of semiconductor chips.

The film for forming a protective film of the present invention can suppress a decrease in surface gloss of the protective film even when a semiconductor chip having a protective film as a cured product of the film for forming a protective film is heated on the back surface for the purpose of bonding or the like. Further, according to the present invention, a method for manufacturing a semiconductor chip using the composite sheet for forming a protective film and the protective film forming film or the composite sheet for forming a protective film provided with the film for forming a protective film is provided.

1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
7 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a film for forming a protective film is used.
8 is a cross-sectional view schematically illustrating one embodiment of a method for manufacturing a semiconductor chip when a composite sheet for forming a protective film is used.

◇Film for forming protective film

The film for forming a protective film according to one embodiment of the present invention is a film for forming an energy ray-curable protective film, and the film for forming a protective film is adhered to a semiconductor wafer, and for the gloss value measured after irradiation with energy rays, the protective film is formed After attaching the film to the semiconductor wafer, irradiating with energy rays, and further heating at 260° C. for 5 minutes, the decrease rate of the measured gloss value is 30% or less, preferably 25% or less, more preferably 20% or less Do.

When the rate of decrease of the gloss value is equal to or less than the above upper limit, even when the semiconductor chip provided with the protective film as a cured product of the film for forming a protective film on the back surface is heated for the purpose of bonding or the like, the decrease in the surface gloss of the protective film can be suppressed.

It is most preferable that the rate of decrease of the gloss value is 0%, but even when a semiconductor chip provided with a protective film, which is a cured product of a film for forming a protective film, is heated for the purpose of bonding or the like, the reduction in surface gloss of the protective film can be sufficiently suppressed. It may be as low as possible. From this viewpoint, the rate of decrease of the gloss value may be 1% or more, or 2% or more.

As a combination of an upper limit and a lower limit, 0% or more and 30% or less, 1% or more and 25% or less, 2% or more and 20% or less are mentioned.

The gloss value can be measured under a condition where the angle of incidence is 60° by means of a glossimeter (for example, "VG7000" manufactured by Nippon Electric Industries, Ltd.).

In this specification, "the rate of decrease in the gloss value" can be obtained by dividing the difference between the gloss value before heating and the gloss value after heating by the gloss value before heating.

As will be described later, a composite sheet for forming a protective film can be formed by forming the film for forming a protective film on a support sheet.

The film for forming a protective film is cured by irradiation with energy rays to form a protective film. This protective film protects the back surface of the semiconductor wafer or semiconductor chip (a surface opposite to the electrode formation surface). The film for forming a protective film is soft and can be easily attached to an object to be attached.

Since the film for forming a protective film is energy ray curable, a protective film can be formed by curing in a shorter time than a film for forming a thermosetting protective film.

In the present specification, "the film for forming a protective film" means before curing, and the "protecting film" means that a film for forming a protective film is cured.

The film for forming a protective film contains at least an energy ray-curable component. As the energy ray curable component, an energy ray polymerizable acrylic polymer obtained by reacting a non-energy ray curable acrylic polymer with a compound containing an energy ray polymerizable group and an energy ray curable group introduced into an acrylic polymer (hereinafter referred to as "adduct type") It is preferable to contain).

The energy ray-curable component is preferably uncured, preferably has tackiness, and more preferably uncured also has tackiness.

In the present invention, "energy beam" means having both energy in an electromagnetic wave or charged particle beam, and examples thereof include ultraviolet rays, radiation, and electron beams.

Ultraviolet rays can be irradiated, for example, by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. The electron beam generated by an electron beam accelerator or the like can be irradiated.

In the present invention, "energy ray curable" means a property that is cured by irradiating energy rays, and "non-energy ray curability" means a property that is not cured even when irradiated with energy rays.

The film for forming a protective film may be a single layer (single layer), a plurality of layers of two or more layers, and in the case of a plurality of layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

In this specification, it is not limited to the case of the film for forming a protective film, and "the plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some of the layers may be the same". It means that it is, and also, "a plurality of layers differ from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. Since the thickness of the film for forming a protective film is greater than or equal to the above lower limit, a protective film with a higher protective ability can be formed. Since the thickness of the film for forming a protective film is equal to or less than the above upper limit, it is suppressed that the protective film becomes an excessive thickness.

Here, the "thickness of the film for forming a protective film" means the entire thickness of the film for forming a protective film. For example, the thickness of the film for forming a protective film composed of multiple layers is the sum of all layers constituting the film for forming a protective film. It means thickness.

The curing conditions when the protective film forming film is cured to form a protective film are not particularly limited as long as the protective film is sufficiently hard to exhibit its function, and may be appropriately selected depending on the type of the protective film forming film.

For example, it is preferable that the illuminance of the energy ray at the time of curing of the film for forming a protective film is 4 to 280 mW/cm 2. In addition, it is preferable that the amount of light of the energy ray during the curing is 3 to 1000 mJ/cm 2.

1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention. The drawings used in the following description may, for convenience, be enlarged to show a portion that becomes a main part for convenience of understanding, and the dimensional ratio of each component is not limited to the same as actual.

The film 13 for protective film formation shown here is provided with the 1st peeling film 151 on the one surface (it may be called "the first surface" in this specification) 13a, and the said agent The 2nd peeling film 152 is provided on the other surface (it may be called "the 2nd surface" in this specification) on the other side opposite to the 1st surface 13a.

The film 13 for forming such a protective film is suitable for storage in a roll shape, for example.

The film 13 for forming a protective film can be formed using a composition for forming a protective film described later.

The film 13 for forming a protective film is energy ray curable.

Both the first release film 151 and the second release film 152 may be known.

The first peeling film 151 and the second peeling film 152 may be the same as each other, for example, the peeling force required for peeling from the film 13 for forming a protective film is different from each other, such as being different from each other. You can do it.

In the film 13 for forming a protective film shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed to an exposed surface formed by removing one of the first release film 151 and the second release film 152. In addition, the exposed surface formed by removing the other of the rest of the first release film 151 and the second release film 152 becomes the abutment surface of the support sheet.

<<Composition for forming a protective film>>

The film for forming a protective film can be formed using a composition for forming a protective film containing the constituent material. For example, a film for forming a protective film can be formed on a target site by coating a composition for forming a protective film on a surface to be formed of the film for forming a protective film and drying as necessary.

In the composition for forming a protective film, the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the film for forming a protective film. In the present specification, "normal temperature" means a temperature not specifically cooled or heated, that is, a normal temperature, and for example, a temperature of 15 to 25°C.

Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater , Meyer bar coater, kiss coater, and the like.

The conditions for drying the protective film-forming composition are not particularly limited, but when the protective film-forming composition contains a solvent to be described later, heating and drying are preferable. The composition for forming a protective film containing a solvent is desirably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

<Composition for forming a protective film (IV-1)>

As a composition for forming a protective film, a composition for forming a protective film (IV-1) containing at least the energy ray-curable component (a) may be mentioned.

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film forming properties, flexibility, and the like to the film for forming a protective film.

Examples of the energy ray-curable component (a) include a polymer (a1) having a weight average molecular weight of 80000 to 2000000 having an energy ray-curable group and a compound (a2) having a molecular weight of 100 to 80000 having an energy ray-curable group. . The polymer (a1) may be at least partially crosslinked with a crosslinking agent (f) described later, or may be uncrosslinked.

In this specification, a weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method, unless otherwise specified.

(Polymer having an energy ray-curable group having a weight average molecular weight of 80000 to 2000000 (a1))

As the polymer (a1) having a weight average molecular weight of 80000 to 2000000 having an energy ray-curable group, the above-mentioned adduct-type acrylic polymer (a1-1) can be exemplified. The adduct-type acrylic polymer (a1-1) is an energy ray-curable compound having an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound and an energy ray-curable group such as a group reacting with the functional group and an energy ray-curable double bond. It can be obtained by reacting (a12).

Examples of the functional group capable of reacting with a group of another compound include, for example, a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (hereinafter referred to as "substituted amino group") wherein one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Means), epoxy groups, and the like. However, from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip, the functional group is preferably a group other than a carboxy group.

Among these, it is preferable that the said functional group is a hydroxyl group.

・Acrylic polymer having a functional group (a11)

Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing an acrylic monomer having the functional group with an acrylic monomer having no functional group, and in addition to these monomers, monomers other than the acrylic monomer ( The non-acrylic monomer) may be copolymerized.

The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, and (meth) (Meth)acrylic acid hydroxyalkyl, such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; And non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton).

In this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid (monocarboxylic acids having ethylenically unsaturated bonds); Ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); Anhydride of the ethylenically unsaturated dicarboxylic acid; And (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

As for the acrylic monomer which has the said functional group which comprises the said acrylic polymer (a11), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the acrylic monomer having no functional group include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)isopropyl acrylate, (meth)n-butyl acrylate, (meth) )Isobutyl acrylate, sec-butyl acrylate, (tert-butyl acrylate), pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl methacrylate, (meth) )Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (Meta) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)) Alkyl groups constituting alkyl esters such as palmityl acrylate), (meth)acrylic acid heptadecyl, and (meth)acrylic acid octadecyl (also referred to as (meth)acrylic acid stearyl) are chain structures having 1 to 18 carbon atoms ( And meta) acrylic acid alkyl esters.

Examples of the acrylic monomer having no functional group include an alkoxyalkyl group such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate ( Meta) acrylic acid esters; (Meth)acrylic acid ester having an aromatic group including (meth)acrylic acid aryl ester such as (meth)acrylate phenyl; Non-crosslinkable (meth)acrylamide and derivatives thereof; And (meth)acrylic acid esters having non-crosslinkable tertiary amino groups such as (meth)acrylic acid N,N-dimethylaminoethyl and (meth)acrylic acid N,N-dimethylaminopropyl.

As for the acrylic monomer which does not have the said functional group which comprises the said acrylic polymer (a11), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; Vinyl acetate; Styrene and the like.

As for the said non-acrylic-type monomer which comprises the said acrylic polymer (a11), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting it is preferably 0.1 to 50% by mass, 1 It is more preferable that it is-40 mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is within this range, the content of the energy ray-curable group in the adduct-type acrylic polymer (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) is cured of the protective film. The degree of can be easily adjusted to a desired range.

As for the said acrylic polymer (a11) which comprises the said adduct type acrylic polymer (a1-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the composition for forming a protective film (IV-1), the content of the adduct-type acrylic polymer (a1-1) is preferably 1 to 50% by mass relative to the total mass of the composition for forming a protective film (IV-1). , It is more preferably 5 to 40% by mass, and particularly preferably 10 to 35% by mass.

・Energy ray curable compound (a12)

The energy ray-curable compound (a12) is a group capable of reacting with a functional group of the acrylic polymer (a11), and preferably has one or two or more selected from the group consisting of isocyanate groups, epoxy groups and carboxy groups, and as the groups It is more preferable to have an isocyanate group. The energy ray-curable compound (a12), for example, when having an isocyanate group as the group, readily reacts with this hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.

The energy ray-curable compound (a12) preferably has 1 to 5 of the energy ray-curable groups in one molecule, and more preferably 1 to 3 particles.

As the energy ray-curable compound (a12), for example, 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (Bisacryloyloxymethyl) ethyl isocyanate;

An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate;

And an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate.

Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the adduct-type acrylic polymer (a1-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the adduct-type acrylic polymer (a1-1), the content ratio of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 1 It is preferably -90 mol%, more preferably 5-80 mol%, more preferably 10-70 mol%, and particularly preferably 20-40 mol%. When the content ratio is within this range, the adhesive force of the protective film formed by curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional (having one of the above groups in one molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is polyfunctional ( In the case of a compound having two or more of the above groups in one molecule, the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 150,000.

When at least a part of the polymer (a1) is crosslinked by a crosslinking agent (f), the polymer (a1) does not correspond to any of the monomers described above as constituting the acrylic polymer (a11), Further, a monomer having a group reacting with a crosslinking agent (f) may be polymerized to be crosslinked in a group reacting with a crosslinking agent (f), or a crosslinked group in a group reacting with the functional group derived from the energy ray-curable compound (a12). You can do it.

The composition (IV-1) for forming a protective film and the polymer (a1) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

(A compound having an energy ray-curable group having a molecular weight of 100 or more and less than 80000 (a2))

Among the compounds (a2) having an energy ray-curable group having a molecular weight of 100 or more and less than 80,000, the energy ray-curable group includes a group containing an energy ray-curable double bond, and preferably (meth)acryloyl group, vinyl group, etc. Can be lifted.

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

Among the compound (a2), examples of the low molecular weight compound having an energy ray-curable group include a polyfunctional monomer or oligomer, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylated bisphenol A di(meth) Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy Diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy )Phenyl]propane, tricyclodecanedimethanoldi(meth)acrylate (tricyclodecanedimethyloldi(meth)acrylate), 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi( Meta)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetra Methylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)) 2 such as acryloxyethoxy)phenyl]propane, neopentyl glycoldi(meth)acrylate, ethoxylated polypropylene glycoldi(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, etc. Functional (meth)acrylate;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tree (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritoltetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol Polyfunctional (meth)acrylates such as poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

And polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers.

Among the compounds (a2), epoxy resins having an energy ray-curable group and phenolic resins having an energy ray-curable group can be used, for example, those described in paragraph 0043 of JP 2013-194102 A. . These resins also apply to the resins constituting the thermosetting component (h) described later, but are treated as the compound (a2) in the present invention.

The molecular weight of the compound (a2) is preferably 100 to 30000, and more preferably 300 to 10000.

When the compound (a2) is a monomer, the molecular weight can be calculated from the food. On the other hand, when the compound (a2) is an oligomer, its molecular weight means a weight average molecular weight.

The composition (IV-1) for forming a protective film and the compound (a2) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the film for forming a protective film (the composition for forming a protective film) contains the energy ray-curable component (a), the energy ray-curable component (a) is polymerized by an energy ray-curable group by ultraviolet irradiation to make the film for protective film as a protective film. , As a result, the low-molecular-weight polymer is hardly contained in the protective film. As a result, even when the protective film is heated, it is difficult for the low-molecular-weight polymer to segregate on the surface of the protective film.

The film for protective film formation (the composition for forming a protective film) contains the energy ray-curable component (a), so that the film for protective film formation is adhered to a semiconductor wafer, and for the gloss value measured after irradiation with energy rays, the protective film is formed The film is adhered to a semiconductor wafer, irradiated with energy rays, and further heated at 260° C. for 5 minutes, so that the decrease rate of the measured gloss value is 30% or less.

[Polymer (b) having no energy ray-curable groups]

The composition for forming a protective film (IV-1) and the film for forming a protective film may contain a polymer (b) having no energy ray-curable group.

The said polymer (b) may be the thing bridge|crosslinked by the crosslinking agent (f) mentioned later at least one part may be sufficient as the thing which is not crosslinked.

As the polymer (b) having no energy ray-curable group, for example, acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, acrylic urethane resin, polyvinyl alcohol (PVA), butyral resin, polyester urethane resin And the like.

Among these, it is preferable that the said polymer (b) is an acryl-type polymer (it may abbreviate as "acrylic-type polymer (b-1) hereafter.").

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid ester, and hydroxyl group ( And meta) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) )Isobutyl acrylate, sec-butyl acrylate, (tert-butyl acrylate), pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl methacrylate, (meth) )Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (Meta) acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)) Alkyl groups constituting alkyl esters such as palmityl acrylate), (meth)acrylic acid heptadecyl, and (meth)acrylic acid octadecyl (also referred to as (meth)acrylic acid stearyl) are chain structures having 1 to 18 carbon atoms ( And meta) acrylic acid alkyl esters.

Examples of the (meth)acrylic acid ester having the cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;

And (meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester.

As said glycidyl group containing (meth)acrylic acid ester, (meth)acrylic acid glycidyl etc. are mentioned, for example.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxy Propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

As said substituted amino group containing (meth)acrylic acid ester, (meth)acrylic acid N-methylaminoethyl etc. are mentioned, for example.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; Vinyl acetate; Styrene and the like.

As the polymer (b) having at least a part of the energy ray-curable group crosslinked by a crosslinking agent (f), for example, a reactive functional group in the polymer (b) reacted with a crosslinking agent (f).

The reactive functional group may be appropriately selected depending on the type of the crosslinking agent (f) or the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned as the reactive functional group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among these, a carboxyl group having high reactivity with an epoxy group is preferable. However, from the viewpoint of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip, the reactive functional group is preferably a group other than a carboxy group.

As a polymer (b) which does not have an energy ray-curable group which has the said reactive functional group, what was obtained by superposing|polymerizing the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer may be used as monomers constituting the monomer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include, for example, those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester, and in addition, in the aforementioned acrylic monomer or non-acrylic monomer, one or two What was obtained by superposing|polymerizing the monomer formed by the substitution of the reactive functional group with one or more hydrogen atoms is mentioned.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting it is preferably 1 to 25% by mass , It is more preferably 2 to 20% by mass. When the ratio is such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.

When the content of the polymer (b) which does not have a low-molecular-weight energy ray-curable group in the film for forming a protective film is large, when the semiconductor chip provided with the protective film as a cured product of the film for forming a protective film is heated for the purpose of bonding or the like, the protective film The surface gloss decreases.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 200000 or more, more preferably 250000 or more, and even more preferably 300000 or more. When the weight average molecular weight of the polymer (b) having no energy ray-curable group is greater than or equal to the above lower limit, the glossiness of the surface of the protective film is obtained even when the semiconductor chip provided with the protective film as a cured product of the film for forming a protective film on the back surface is heated by bonding or the like. It is hard to fall. The upper limit of the weight average molecular weight of the polymer (b) having no energy ray-curable group is not particularly limited, but from the viewpoint of easy production of a composite sheet for forming a protective film, the weight average molecular weight of the polymer (b) having no energy ray curable group is It is preferably 2000000 or less. When the weight average molecular weight of the polymer (b) having no energy ray-curable group is 2000000 or less, dispersibility in the protective film-forming composition (IV-1) becomes good.

Examples of the combination of the upper limit and the lower limit include 200000 or more and 2000000 or less, 250000 or more and 2000000 or less, and 300000 or more and 2000000 or less.

When the weight average molecular weight (Mw) of the polymer (b) which does not have an energy ray-curable group is less than the above lower limit, an energy ray-curable group such as an energy ray-curable double bond is formed by using the polymer (b) without an energy ray-curable group as an adduct. It is desirable to introduce.

Specifically, the adduct of the polymer (b) that does not have an energy ray-curable group has a polymer (b) that does not have an energy ray-curable group having a functional group capable of reacting with a group of another compound, and a group that reacts with the functional group and energy ray-curable. It can be obtained by reacting an energy ray-curable compound having an energy ray-curable group such as a double bond.

When the polymer (b) having no energy ray-curable group is an acrylic polymer, the adduct can be obtained in the same manner as the above-mentioned adduct-type acrylic polymer (a1-1).

When the polymer (b) having no energy ray-curable group is used as an adduct, and an energy ray-curable group such as an energy-ray-curable double bond is introduced, polymerization is performed by the energy-ray-curable group by ultraviolet irradiation for forming a protective film-forming film as a protective film. As a result, the low-molecular-weight polymer is hardly contained in the protective film, and even when the protective film is heated, the low-molecular-weight polymer becomes difficult to segregate on the surface of the protective film.

When a polymer (b) having no energy ray-curable group is used as an adduct and an energy ray-curable group such as an energy ray-curable double bond is introduced, the film for forming the protective film is adhered to a semiconductor wafer, and the gloss measured after irradiation with energy rays With respect to the value, the film for forming a protective film is adhered to a semiconductor wafer, irradiated with energy rays, and further heated at 260° C. for 5 minutes, so that the decrease rate of the measured gloss value is 30% or less.

The composition (IV-1) for forming a protective film and the polymer (b) having no energy ray-curable groups contained in the film for forming a protective film may be one type, two or more types, and when two or more types, combinations and ratios thereof You can choose arbitrarily.

It is preferable to contain the said compound (a2) and the said polymer (a1) as composition (IV-1) for protective film formation. It is also preferable that the composition (IV-1) for forming a protective film contains the polymer (a1) and the compound (a2) and does not contain a polymer (b) having no energy ray-curable groups. The composition (IV-1) for forming a protective film does not contain the compound (a2), and may contain the polymer (a1).

The polymer (a1) is preferably an adduct-type acrylic polymer (a1-1).

When the composition (IV-1) for forming a protective film contains the polymer (a1) and the compound (a2), in the composition for forming a protective film (IV-1), the content of the compound (a2) is the polymer (a1) It is preferable that it is 10-400 mass parts with respect to 100 mass parts of total content of ), and it is more preferable that it is 30-350 mass parts.

In the composition for forming a protective film (IV-1), the content of the energy ray-curable component (a) relative to the total content of components other than the solvent is preferably 12 to 90 mass%, more preferably 15 to 80 mass% It is preferable, and it is particularly preferably 20 to 70% by mass, for example, any of 25 to 60% by mass and 30 to 50% by mass. When the said content is such a range, the energy ray curability of a film for protective film formation becomes more favorable.

When the composition for forming a protective film (IV-1) contains the adduct-type acrylic polymer (a1-1), in the composition for forming a protective film (IV-1) and the film for forming a protective film, the polymer (a1-1) The content of is preferably 30 to 100 parts by mass, more preferably 50 to 95 parts by mass, and particularly preferably 70 to 90 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable component (a). When the content of the polymer (a1-1) is within this range, the energy ray curability of the film for forming a protective film becomes better.

The composition for forming a protective film (IV-1) is a photopolymerization initiator (c), a filler (d), a coupling agent (e) other than the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, depending on the purpose. , A crosslinking agent (f), a coloring agent (g), a thermosetting component (h), a curing accelerator (i), and a general-purpose additive (z).

For example, by using the composition for forming a protective film (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed film for forming a protective film has an adhesive strength to an adherend by heating. The strength of the protective film formed from the film for forming a protective film is also improved.

[Photopolymerization initiator (c)]

As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoate, methyl benzoin dimethyl ketal, etc. Benzoin compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenylketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H Benzophenone compounds such as -carbazol-3-yl]-,1-(O-acetyloxime); Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone, etc. are mentioned.

Examples of the photopolymerization initiator (c) include quinone compounds such as 1-chloroanthraquinone; It is also possible to use photosensitizers such as amines.

As for the photopolymerization initiator (c) contained in the composition for forming a protective film (IV-1), only one type may be used, or two or more types may be used. In the case of two or more types, combinations and ratios of these may be arbitrarily selected.

When the photopolymerization initiator (c) is used, in the composition for forming a protective film (IV-1), the content of the photopolymerization initiator (c) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound (a). It is preferable, it is more preferably 0.03 to 15 parts by mass, and particularly preferably 0.05 to 10 parts by mass.

[Filling material (d)]

When the film for forming a protective film contains a filler (d), the protective film obtained by curing the film for forming a protective film can easily adjust the thermal expansion coefficient. Then, by optimizing the coefficient of thermal expansion for the object to be formed of the protective film, the reliability of the package obtained using the composite sheet for forming the protective film is further improved. When the film for forming a protective film contains a filler (d), the moisture absorption rate of the protective film can be reduced or the heat dissipation property can be improved.

As a filler (d), what consists of a heat conductive material is mentioned, for example.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; Beads in which these inorganic fillers are spheroidized; Surface modified products of these inorganic fillers; Single crystal fibers of these inorganic fillers; And glass fibers.

Among these, it is preferable that the inorganic filler is silica or alumina.

The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. When the average particle diameter of the filler (d) is in this range, a decrease in the light transmittance of the protective film can be suppressed while maintaining adhesion to the object to be formed.

In the present specification, "average particle diameter" means the value of the particle diameter (D ₅₀ ) at an integrated value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method, unless otherwise specified.

The composition (IV-1) for forming a protective film and the filler (d) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the filler (d) is used, in the composition for forming a protective film (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the filler (d) of the film for forming a protective film) The content of) is preferably 10 to 85 mass%, more preferably 20 to 80 mass%, particularly preferably 30 to 75 mass%, for example, 40 to 70 mass% and 45 to 65 mass% % May be used. When the content of the filler (d) is within this range, adjustment of the thermal expansion coefficient becomes easier.

[Coupling agent (e)]

By using what has a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (e), the adhesiveness and adhesion to the adherend of the film for forming a protective film can be improved. By using the coupling agent (e), the protective film obtained by curing the film for forming a protective film does not impair heat resistance and improves water resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), a polymer (b) having no energy ray-curable group, and more preferably a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycyl Cydyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-( 2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltri Ethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

The composition (IV-1) for forming a protective film and the coupling agent (e) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the coupling agent (e) is used, in the composition for forming a protective film (IV-1) and the film for forming a protective film, the content of the coupling agent (e) is 100 parts by mass of the content of the energy ray-curable component (a), It is preferable that it is 0.03-20 mass parts, it is more preferable that it is 0.05-10 mass parts, and it is especially preferable that it is 0.1-5 mass parts.

Since the content of the coupling agent (e) is greater than or equal to the above lower limit, the use of the coupling agent (e), such as improving the dispersibility of the filler (d) with respect to the resin or improving the adhesion of the protective film-forming film to the adherend The effect by is obtained more remarkably. Moreover, generation|occurrence|production of outgas is suppressed more because the said content of the coupling agent (e) is below the said upper limit.

[Crosslinking system (f)]

By crosslinking the above-mentioned energy ray-curable component (a) or the polymer (b) having no energy ray-curable group using the crosslinking agent (f), the initial adhesive strength and cohesive strength of the film for forming a protective film can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate-based crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine-based crosslinking agent (a crosslinking agent having an aziridinyl group), and the like.

As said organic polyvalent isocyanate compound, For example, aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound, and alicyclic polyvalent isocyanate compound (Hereinafter, these compounds may be abbreviated as "aromatic polyvalent isocyanate compound, etc."); Trimers, isocyanurates and adducts such as the aromatic polyvalent isocyanate compounds; And a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound with a polyol compound. The "adduct" is a mixture of the aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Means reactants. Examples of the adducts include xylylenediisocyanate adducts of trimethylolpropane as described later. "Terminal isocyanate urethane prepolymer" means a prepolymer having an urethane bond and an isocyanate group at the terminal end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylenediisocyanate; 1,4-xylenediisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to hydroxyl groups of all or part of a polyol such as trimethylolpropane; And lysine diisocyanate.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, And tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) without an energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable component (a) or the energy ray-curable group By the reaction of the polymer (b) not having, a crosslinked structure can be easily introduced into the film for forming a protective film.

As for the composition (IV-1) for forming a protective film and the crosslinking agent (f) contained in the film for forming a protective film, only 1 type may be sufficient, or 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

When the crosslinking agent (f) is used, in the composition for forming a protective film (IV-1), the content of the crosslinking agent (f) is the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group 100 It is preferable that it is 0.01-20 mass parts with respect to mass part, it is more preferable that it is 0.1-10 mass parts, and it is especially preferable that it is 0.5-5 mass parts. Since the said content of crosslinking agent (f) is more than the said lower limit, the effect by using crosslinking agent (f) is obtained more remarkably. Since the content of the crosslinking agent (f) is less than or equal to the above upper limit, excessive use of the crosslinking agent (f) is suppressed.

[Colorant (g)]

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

Examples of the organic pigments and organic dyes include, for example, aluminum-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squarylium-based dyes, azurenium-based dyes, polymethine-based dyes, and naphthoquinone-based dyes. , Pyryllium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment, Isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indolphenol pigment, triarylmethane pigment, anthra And quinone-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazole-based dyes, pyrantrone-based dyes, and styrene-based dyes.

Examples of the inorganic pigment include carbon black, cobalt pigment, iron pigment, chromium pigment, titanium pigment, vanadium pigment, zirconium pigment, molybdenum pigment, ruthenium pigment, platinum pigment, and ITO (Indium Tin oxide) pigments, ATO (antimony tin oxide) pigments, and the like.

The composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When the coloring agent (g) is used, the content of the protective film forming composition (IV-1) and the coloring agent (g) of the protective film forming film may be appropriately adjusted according to the purpose. For example, by controlling the content of the colorant (g) to control the light transmittance of the protective film to control printing visibility, in the composition for forming a protective film (IV-1), the total content of all components other than the solvent The content ratio of the colorant (g) (that is, the content of the colorant (g) in the film for forming a protective film) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and 0.8 to 5% by mass It is particularly preferred. Since the said content of the coloring agent (g) is more than the said lower limit, the effect by using the coloring agent (g) is obtained more remarkably. Since the content of the colorant (g) is equal to or less than the above upper limit, excessive use of the colorant (g) is suppressed.

[Thermosetting component (h)]

The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

Examples of the thermosetting component (h) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy-based thermosetting resins are preferred.

(Epoxy watch thermosetting resin)

The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).

The composition for forming a protective film (IV-1) and the epoxy-based thermosetting resin contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

·Epoxy resin (h1)

A well-known thing is mentioned as an epoxy resin (h1), For example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its additive, orthocresol novolac epoxy resin, dicyclopentadiene And bifunctional or higher epoxy compounds such as a type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenylene skeleton type epoxy resin.

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

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of the epoxy group of a polyfunctional epoxy resin into a group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained by, for example, addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple|bonded with the aromatic ring which comprises an epoxy resin etc. are mentioned, for example.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also called a vinyl group), a 2-propenyl group (also called an allyl group), a (meth)acryloyl group, and a (meth)acrylamide group. And an acryloyl group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably from 300 to 30000, more preferably from 400 to 10000, and from 500 to 10000, in view of the curability of the film for forming a protective film and the strength and heat resistance of the protective film. It is particularly preferable that it is 3000.

In the present specification, "number average molecular weight" means a number average molecular weight expressed in terms of standard polystyrene conversion measured by gel permeation chromatography (GPC), unless otherwise specified. The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g/eq, and more preferably 150 to 800 g/eq.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of the epoxy compound containing 1 gram equivalent of epoxy group, and can be measured according to the method of JIS K 7236:2001.

Epoxy resin (h1) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and proportion thereof may be arbitrarily selected.

·Heat curing agent (h2)

The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).

The thermosetting agent (h2) includes, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydride, and the like, and a phenolic hydroxyl group, an amino group, or an acid group in an anhydride group is preferred, and is phenolic. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. Can.

Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of the phenol resin, and the like. Can.

The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the aforementioned unsaturated hydrocarbon group.

When a phenolic curing agent is used as the heat curing agent (h2), it is preferable that the heat curing agent (h2) has a high softening point or a glass transition temperature, since the peelability from the support sheet of the protective film is improved.

In the present specification, "glass transition temperature" refers to the temperature of the inflection point of the obtained DSC curve by measuring the DSC curve of the sample using a differential scanning calorimeter.

Among the thermosetting agents (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resins, novolac type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins is preferably 300 to 30000, It is more preferable that it is 400-10000, and it is particularly preferable that it is 500-3000.

Among the thermosetting agents (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

As the thermosetting agent (h2), one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and proportion thereof may be arbitrarily selected.

When the thermosetting component (h) is used, in the protective film-forming composition (IV-1) and the protective film-forming film, the content of the thermosetting agent (h2) is 0.01 to 100 parts by mass of the epoxy resin (h1) content. It is preferably 20 parts by mass.

When the thermosetting component (h) is used, in the composition for forming a protective film (IV-1) and the film for forming a protective film, the content of the thermosetting component (h) (for example, epoxy resin (h1) and thermosetting agent (h2) It is preferable that it is 1-500 mass parts with respect to 100 mass parts of content of polymer (b) which does not have an energy ray curable group).

[Hardening accelerator (i)]

The curing accelerator (i) is a component for adjusting the curing rate of the film for forming a protective film.

Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethyl imidazole; Organic phosphine such as tributylphosphine, diphenylphosphine, and triphenylphosphine; And tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate.

The curing accelerator (i) may be used alone, or two or more may be used in combination, and when two or more are used in combination, the combination and proportion thereof may be arbitrarily selected.

When using the curing accelerator (i), the content of the curing accelerator (i) in the protective film forming composition (IV-1) and the film for forming a protective film is not particularly limited, and may be appropriately selected depending on the components used in combination.

[Universal additive (z)]

The general-purpose additive (z) may be any known one, and may be arbitrarily selected according to the purpose, and is not particularly limited, and preferred examples thereof include plasticizers, antistatic agents, antioxidants, gettering agents, and the like.

The composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

When using the general purpose additive (z), the content of the general purpose additive (z) in the protective film forming composition (IV-1) and the protective film forming film is not particularly limited, and may be appropriately selected according to the purpose.

[menstruum]

It is preferable that the composition for forming a protective film (IV-1) further contains a solvent. The composition (IV-1) for forming a protective film containing a solvent has good handleability.

The solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (also called 2-methylpropan-1-ol), and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; And amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone.

As for the solvent contained in the composition for forming a protective film (IV-1), only one type may be used, or two or more types may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone, toluene, ethyl acetate, or the like, because the components contained in the protective film-forming composition (IV-1) can be more uniformly mixed. .

One aspect of the present invention is a polymer for forming a protective film (a1) having an energy ray-curable group, the adduct type acrylic polymer (a1-1) is 25 to 35% by mass relative to the total mass of the film for forming a protective film, energy beam As a compound (a2) having a curable group, ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate is 5 to 15% by mass relative to the total mass of the film for forming a protective film, and 2-(as a photopolymerization initiator (c). Dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone is 0.3 to 0.9% by mass relative to the total mass of the film for forming a protective film, and a silica filler as a filler (d) for forming a protective film It is a film for protective film formation which contains 52-62 mass% with respect to the total mass of a film and 0.1-0.7 mass% of 3-methacryloxypropyl trimethoxysilane as a coupling agent (e) with respect to the total mass of a film for protective film formation. .

On the other hand, the adduct-type acrylic polymer (a1-1) is a 2-methacryloyloxyethyl isocyanate as an acrylic polymer (a11) formed by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate and an energy-curable compound (a12). It is preferably obtained by reacting.

The content ratio of the energy ray-curable group derived from the energy-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 5 to 50 mol%, and 20 to 40 mol % Is more preferable. Moreover, the said ratio may be 2-15 mol%.

In addition, it is preferable that the film for forming a protective film does not contain a polymer (b) having no energy ray-curable groups.

Another aspect of the present invention further comprises 25 to 40 parts by mass of a phthalocyanine blue pigment, 10 to 25 parts by mass of an isoindolinone yellow pigment, and 40 to 60 parts by mass of anthraquinone red pigment as a colorant (g), It is preferable that it is a film for forming a protective film containing 1 to 5% by mass of the pigment obtained by pigmentation so that the total amount of the above three dyes/amount of styrene acrylic resin = 1/3 (mass ratio). .

<<Production method of protective film forming composition>>

The composition for forming a protective film, such as the composition for forming a protective film (IV-1), is obtained by blending each component for constituting it.

The order of addition when mixing each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any other blending component other than the solvent to dilute the blending component in advance, or may be used without diluting any blending component other than the solvent in advance, and the solvent mixed with these blending components. You may use it by doing.

The method of mixing each component when compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; A method of mixing using a mixer; You may select suitably from well-known methods, such as the method of adding and mixing ultrasonic waves.

The temperature and time during addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Method of manufacturing a film for forming a protective film

The film for forming a protective film can be produced by coating a composition for forming a protective film on a release film (preferably, its release treatment surface) and drying as necessary. The manufacturing method at this time is as described above.

The film for forming a protective film is usually stored in a state where a release film is pasted on both sides, as shown in FIG. 1. To this end, a peeling film (preferably, the peeling treatment surface) may be added to the exposed surface of the film for forming a protective film formed on the release film as described above (the side opposite to the side having the peeling film). .

◇How to use the film for forming a protective film

As described above, the film for forming a protective film can be formed on a support sheet to form a composite sheet for forming a protective film. The composite sheet for forming a protective film is affixed to the back surface (a surface opposite to the electrode forming surface) of the semiconductor wafer by the film for forming a protective film. Thereafter, in this state, a target semiconductor chip and a semiconductor device can be manufactured by a manufacturing method described later.

On the other hand, the film for forming a protective film may be formed first on the back surface of the semiconductor wafer, not the support sheet. For example, first, a film for forming a protective film is affixed to the back surface of a semiconductor wafer, and a support sheet is affixed to the exposed surface (a surface opposite to the side affixed to the semiconductor wafer) of the film for forming a protective film, or this film is attached. After the energy ray is irradiated to the film for forming a protective film in one state, cured to form a protective film, a support sheet is bonded to the exposed surface of the protective film (the side opposite to the side affixed to the semiconductor wafer) to form a protective film composite Sheet. Thereafter, in this state, a target semiconductor chip and a semiconductor device can be manufactured by a manufacturing method described later.

◇Composite sheet for protective film formation

The composite sheet for forming a protective film according to one embodiment of the present invention includes a support sheet, and is provided with the film for forming a protective film on the support sheet.

In the present invention, even after the film for forming a protective film is cured, as long as the laminated structure of the cured product of the support sheet and the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, this laminated structure is referred to as "for forming a protective film. Composite sheet”.

The thickness of the semiconductor wafer to be used for the composite sheet for forming a protective film of the present invention is not particularly limited, but is preferably 30 to 1000 µm, and 100 to 400 µm, in terms of easier division into semiconductor chips described later. It is more preferable.

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

◎ Support sheet

The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When a support sheet consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited, unless the effect of this invention is impaired.

Preferred support sheets include, for example, provided with a substrate, and the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate (the base material and the pressure-sensitive adhesive layer are directly contacted and laminated in this order); A base material, an intermediate layer and a pressure-sensitive adhesive layer are laminated in this order in direct contact in their thickness direction; And things consisting of only a substrate.

An example of the composite sheet for forming a protective film of the present invention will be described below with reference to the drawings for each type of the support sheet.

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

In the drawings subsequent to Fig. 2, the same components as those shown in the already described drawings are given the same reference numerals as those in the illustrated drawings, and detailed descriptions thereof are omitted.

The composite sheet 1A for forming a protective film shown here is provided with a substrate 11, is provided with an adhesive layer 12 on the substrate 11, and a film 13 for forming a protective film is formed on the adhesive layer 12. I have it. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for forming a protective film is, in other words, one surface of the support sheet 10 (in this specification, "the first It may be referred to as &quot;plane&quot;), and has a configuration in which the film 13 for forming a protective film is laminated on 10a. The composite sheet 1A for forming a protective film is further provided with a release film 15 on the film 13 for forming a protective film.

In the composite sheet 1A for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on one surface of the substrate 11 (sometimes referred to as "first surface" in this specification) 11a, and the pressure-sensitive adhesive layer A film 13 for forming a protective film is laminated on the entire surface of one surface (12) (sometimes referred to as a "first surface" in this specification) 12a, and the first film of the film 13 for forming a protective film A part of the surface 13a, that is, the adhesive layer 16 for a jig is laminated on an area near the periphery, and the adhesive layer 16 for a jig is laminated on the first surface 13a of the film 13 for forming a protective film The release film 15 is laminated on the surface 16a (top and side surfaces) of the adhesive layer 16 for the jig and the surface which is not there.

In the composite sheet 1A for forming a protective film, the film 13 for forming a protective film contains the energy ray-curable component (a), and the (a) is preferably the adduct-type acrylic polymer (a1-1). .

The jig adhesive layer 16 may be, for example, of a single-layer structure containing an adhesive component, or of a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet serving as a core material.

In the composite sheet 1A for forming a protective film shown in FIG. 2, the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film while the release film 15 is removed. In addition, the top surface of the surface 16a of the adhesive layer for jig 16 is attached to a jig such as a ring frame and is used.

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

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. 2 except that the adhesive layer 16 for a jig is not provided. That is, in the composite sheet 1B for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film is formed on the front surface of the first surface 12a of the pressure-sensitive adhesive layer 12. The forming film 13 is laminated, and the release film 15 is laminated on the entire surface of the first surface 13a of the protective film forming film 13.

In the composite sheet 1B for forming a protective film, the film 13 for forming a protective film contains the energy ray-curable component (a), and it is preferable that the product (a) is the adduct-type acrylic polymer (a1-1). .

The composite sheet 1B for forming a protective film shown in FIG. 3 is a semiconductor wafer (not shown) in a part of the central side of the first surface 13a of the film 13 for forming a protective film, with the release film 15 removed The back surface of (not shown) is affixed, and an area near the periphery is further affixed to a jig such as a ring frame and used.

4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment 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. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed of only the base 11. Then, the film 13 for forming a protective film is laminated on the first surface 11a (the first surface 10a of the support sheet 10) of the substrate 11, and the first surface of the film 13 for forming a protective film A part of (13a), that is, the adhesive layer for jig 16 is laminated in a region near the periphery, and the adhesive layer for jig 16 is not laminated on the first surface 13a of the film 13 for forming a protective film The release film 15 is laminated on the surface 16a (top and side surfaces) of the unused area and the adhesive layer for jig 16.

In the composite sheet 1C for forming a protective film, the film 13 for forming a protective film contains an energy ray-curable component (a), and the (a) is preferably the adduct-type acrylic polymer (a1-1). .

The composite sheet 1C for forming a protective film shown in FIG. 4 is the same as the composite sheet 1A for forming a protective film shown in FIG. 2, in a state where the release film 15 is removed, the first of the films 13 for forming a protective film The back surface of the semiconductor wafer (not shown) is affixed to the surface 13a, and an upper surface of the surface 16a of the adhesive layer 16 for the jig is attached to a jig such as a ring frame.

5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment 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. 4 except that the adhesive layer 16 for a jig is not provided. That is, in the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is laminated on the first surface 11a of the substrate 11, and the first surface 13a of the film 13 for forming a protective film A release film 15 is laminated on the entire surface of the.

In the composite sheet 1D for forming a protective film, the film 13 for forming a protective film contains an energy ray-curable component (a), and the (a) is preferably the adduct-type acrylic polymer (a1-1). .

The protective film forming composite sheet 1D shown in FIG. 5 is the same as the protective film forming composite sheet 1B shown in FIG. 3, with the release film 15 removed, the first surface of the protective film forming film 13 In (13a), a back surface of a semiconductor wafer (not shown) is affixed to a region on a central portion, and a region near the periphery is affixed to a jig such as a ring frame.

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

The composite sheet for forming a protective film 1E shown here is the same as the composite sheet for forming a protective film 1B shown in FIG. 3 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 provided with a substrate 11, an adhesive layer 12 is provided on the substrate 11, and a protective film forming film 23 is provided on the adhesive layer 12. Is done by The support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1E for forming a protective film, in other words, forms a protective film on the first surface 10a of the support sheet 10 The dragon film 23 has a stacked configuration. The composite sheet 1E for forming a protective film further includes a release film 15 on the film 23 for forming a protective film.

In the composite sheet 1E for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the center A film 23 for forming a protective film is laminated on the side region. Then, on the first surface 12a of the pressure-sensitive adhesive layer 12, the area where the film 23 for forming a protective film is not laminated and peeling on the surface 23a (top and side surfaces) of the film 23 for forming a protective film The film 15 is laminated.

When the composite sheet 1E for forming a protective film is viewed in a plan view from above, the film 23 for forming a protective film has a smaller surface area than the pressure-sensitive adhesive layer 12, and has, for example, a circular shape.

In the composite sheet 1E for forming a protective film, the film 23 for forming a protective film contains the energy ray-curable component (a), and the (a) is preferably the adduct-type acrylic polymer (a1-1). .

In the composite sheet 1E for forming a protective film shown in FIG. 6, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the film 23 for forming a protective film while the release film 15 is removed. In the first surface 12a of the pressure-sensitive adhesive layer 12, a region in which the film 23 for forming a protective film is not laminated is attached to a jig such as a ring frame and used.

In the composite sheet 1E for forming a protective film shown in FIG. 6, in the region where the film 23 for forming a protective film is not laminated, on the first surface 12a of the pressure-sensitive adhesive layer 12, shown in FIGS. 2 and 4 The adhesive layer for jig may be laminated|stacked like the same (not shown). The composite sheet 1E for forming a protective film provided with the adhesive layer for jigs is used in the same manner as the composite sheet for forming a protective film shown in FIGS. 2 and 4 with the surface of the adhesive layer for jigs attached to a jig such as a ring frame.

In this way, the composite sheet for forming a protective film may be provided with an adhesive layer for a jig even if the support sheet and the film for forming a protective film are in any form. However, as shown in Figs. 2 and 4, as a composite sheet for forming a protective film provided with an adhesive layer for jigs, it is preferable to provide an adhesive layer for jigs on a film for forming a protective film.

The composite sheet for forming a protective film according to one embodiment of the present invention is not limited to those shown in FIGS. 2 to 6, and within a range not impairing the effects of the present invention, some configurations of those shown in FIGS. 2 to 6 are It may be changed or deleted, or another configuration added to what has been described so far.

For example, in the composite sheet for forming a protective film shown in FIGS. 4 and 5, an intermediate layer may be formed between the substrate 11 and the film 13 for forming a protective film. Any intermediate layer can be selected according to the purpose.

In the composite sheet for forming a protective film shown in Figs. 2, 3, and 6, an intermediate layer may be formed between the base material 11 and the pressure-sensitive 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 laminating a substrate, an intermediate layer, and an adhesive layer in these thickness directions in this order. Here, the intermediate layer is the same as the intermediate layer which may be formed in the composite sheet for forming a protective film shown in FIGS. 4 and 5.

In the composite sheet for forming a protective film shown in Figs. 2 to 6, layers other than the intermediate layer may be formed at any point.

In the composite sheet for forming a protective film, some gaps may be formed between the release film and the layer in direct contact with the release film.

In the composite sheet for forming a protective film, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as described later, it is preferable that a layer in direct contact with the film for forming a protective film of a support sheet such as an adhesive layer is non-energy ray curable. Such a composite sheet for forming a protective film enables easier pickup of a semiconductor chip on which the protective film is formed.

The support sheet may be transparent, opaque or colored depending on the purpose.

Especially, in this invention in which the film for protective film formation has energy ray curability, it is preferable that a support sheet transmits an energy ray.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in this range, when the film for forming a protective film is irradiated with energy rays (ultraviolet rays) through a support sheet, the degree of curing of the film for forming a protective film is further improved.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.

When the transmittance of the light is in this range, it is possible to print more clearly when laser light is applied to the film or protective film for forming a protective film through a support sheet and printed thereon.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in this range, it is possible to print more clearly when laser light is applied to the film or protective film for forming a protective film through a support sheet and printed thereon.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within this range, the modified layer can be more easily formed on the semiconductor wafer by irradiating laser light to the semiconductor wafer through the support sheet and the film or protective film for forming the protective film.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1342 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

Next, each layer constituting the support sheet will be described in more detail.

○ List

The base material is in the form of a sheet or a film, and various resins are exemplified as its constituent materials.

Examples of the resin include polyethylene such as low density polyethylene (LDPE), straight chain low density polyethylene (LLDPE), and high density polyethylene (HDPE); Polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymer obtained by using ethylene as a monomer) ; Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resin obtained using vinyl chloride as a monomer); polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and all aromatic polyesters in which all constituent units have aromatic ring groups; Copolymers of two or more of the above polyesters; Poly(meth)acrylic acid esters; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; And polyether ketones.

As said resin, polymer alloys, such as a mixture of the said polyester and other resins, are also mentioned. It is preferable that the polymer alloy of the above-mentioned polyester and other resins has a relatively small amount of resin other than polyester.

As the resin, for example, one or two or more crosslinked resins of the above-mentioned resins have been crosslinked; And modified resins such as ionomers using one or two or more of the resins exemplified so far.

The resin constituting the base material may be one kind, or two or more kinds, and in the case of two or more kinds, combinations and ratios thereof may be arbitrarily selected.

The base material may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited. Does not.

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 100 μm. When the thickness of the substrate is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or semiconductor chip are further improved.

Here, "the thickness of the base material" means the thickness of the entire base material, and, for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

In the present specification, "thickness" is a value that is measured by measuring any five places of the object with a contact-type thickness gauge and showing the average.

It is preferable that the substrate has high precision in thickness, that is, variation in thickness is suppressed regardless of the portion. Among the above-mentioned constituent materials, materials that can be used for constructing a substrate having a high precision of such thickness include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers.

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

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. For example, the substrate may be transparent, opaque, colored depending on the purpose, or another layer may be deposited.

In addition, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the substrate transmits energy rays.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer formed thereon, the substrate is subjected to uneven treatment by sand blasting, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, Oxidation treatments, such as flame treatment, chromic acid treatment, and hot air treatment, may be applied to the surface.

The base material may have a surface treated with a primer.

The base material includes an antistatic coat layer; When the composite sheet for forming a protective film is overlapped and stored, it may have a layer that prevents the substrate from adhering to another sheet or a layer that prevents the substrate from adhering to the adsorption table.

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

○Adhesive layer

The pressure-sensitive adhesive layer is in the form of a sheet or a film, and contains an adhesive.

Examples of the pressure-sensitive adhesive include acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, adhesive resins such as polyvinyl ether, polycarbonate, and ester-based resins, and acrylic resins are preferred.

In the present invention, "adhesive resin" is a concept that includes both an adhesive resin and an adhesive resin, and, for example, the resin itself is not only adhesive but also used in combination with other components such as additives. Also includes resins exhibiting tackiness, resins exhibiting tackiness due to the presence of triggers such as heat or water.

The pressure-sensitive adhesive layer may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is particularly limited. Does not work.

The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

Here, the "thickness of the adhesive layer" means the entire thickness of the pressure-sensitive adhesive layer, and, for example, the thickness of the pressure-sensitive adhesive layer composed of multiple layers means the total thickness of all layers constituting the pressure-sensitive adhesive layer.

It is preferable that the optical properties of the pressure-sensitive adhesive layer satisfy the optical properties of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent, opaque, or colored according to the purpose.

Further, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the pressure-sensitive adhesive layer transmits energy rays.

The pressure-sensitive adhesive layer may be formed using an energy ray curable pressure sensitive adhesive, or may be formed using a non-energy ray curable pressure sensitive adhesive. The pressure-sensitive adhesive layer formed by using an energy ray-curable pressure-sensitive adhesive can easily control physical properties before and after curing.

<<adhesive composition>>

The pressure-sensitive adhesive layer can be formed using an pressure-sensitive adhesive composition containing an pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying it as necessary. A more specific method for forming the pressure-sensitive adhesive layer will be described in detail below, along with another method for forming the layer. In the pressure-sensitive adhesive composition, the content ratio of components that are not vaporized at normal temperature is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer.

Coating of the pressure-sensitive adhesive composition may be carried out by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, myer bar And a method of using various coaters such as a coater and a kiss coater.

The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferable to heat-dry. It is preferable to dry the pressure-sensitive adhesive composition containing a solvent, for example, at 70 to 130° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is an energy ray-curable pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive, that is, as the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray curable pressure-sensitive adhesive resin (I-1a) (hereinafter, ``adhesive resin ( I-1a)” and the pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-2a)"). Pressure-sensitive adhesive composition (I-2); And an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.

<Adhesive composition (I-1)>

As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a) and an energy ray-curable compound.

[Adhesive resin (I-1a)]

It is preferable that the said adhesive resin (I-1a) is an acrylic resin.

As said acryl-type resin, the acryl-type polymer which has a structural unit derived from (meth)acrylic-acid alkylester at least is mentioned, for example.

As for the structural unit which the said acrylic resin has, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the (meth)acrylic acid alkyl ester include those having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group is preferably linear or branched.

More specifically as the (meth)acrylic acid alkyl ester, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth)acrylic acid tert-butyl, (meth)pentyl acrylate, (meth)acrylic acid hexyl, (meth)acrylic acid heptyl, (meth)acrylic acid 2-ethylhexyl, (meth) Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate ((meth) (Also called lauryl acrylate), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl (also called (meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)acrylic acid) And palmityl), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl (also called (meth)acrylic acid stearyl), (meth)acrylic acid nonadecyl, (meth)acrylic acid icosyl, and the like.

From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, it is preferable that the acrylic polymer has a structural unit derived from (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group. From the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer, the number of carbon atoms in the alkyl group is preferably 4 to 12, and more preferably 4 to 8. The (meth)acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an alkyl methacrylate ester.

It is preferable that the said acrylic polymer has a structural unit derived from a functional group containing monomer in addition to the structural unit derived from (meth)acrylic acid alkylester.

As the functional group-containing monomer, for example, the functional group reacts with a crosslinking agent described later, or the starting point of crosslinking, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described below to introduce an unsaturated group into the side chain of the acrylic polymer. And what makes it possible.

Among the functional group-containing monomers, examples of the functional group include hydroxyl groups, carboxyl groups, amino groups, and epoxy groups.

That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, and (meth) (Meth)acrylic acid hydroxyalkyl, such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; And non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton).

Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid (monocarboxylic acids having ethylenically unsaturated bonds); Ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); Anhydride of the ethylenically unsaturated dicarboxylic acid; And (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

As for the functional group containing monomer which comprises the said acrylic polymer, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, and more preferably 3 to 30% by mass relative to the total mass of the structural unit. It is particularly preferred to be.

The said acrylic polymer may have a structural unit derived from another monomer other than the structural unit derived from the (meth)acrylic-acid alkylester and the functional group-containing monomer.

The other monomer is not particularly limited as long as it is copolymerizable with (meth)acrylic acid alkyl ester and the like.

Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

As for the said other monomer which comprises the said acrylic polymer, only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these may be arbitrarily selected.

The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1a).

On the other hand, among the acrylic polymers, a functional group having a functional group having an energy ray polymerizable unsaturated group (energy ray polymerizable group) reacted may be used as the energy ray curable adhesive resin (I-2a).

As for the adhesive resin (I-1a) contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive resin (I-1a) is preferably 5 to 99 mass%, and 10 to 95 mass%, based on the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferable, and it is particularly preferable that it is 15 to 90 mass%.

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include a monomer or oligomer that has an energy ray-polymerizable unsaturated group and is curable by irradiation with energy rays.

Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritolhexa(meth)acrylate, Polyvalent (meth)acrylates such as 1,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; Polyester (meth)acrylate; Polyether (meth)acrylate; And epoxy (meth)acrylates.

Among the energy ray-curable compounds, examples of the oligomer include oligomers formed by polymerizing the monomers exemplified above.

The energy ray-curable compound has a relatively high molecular weight, and urethane (meth)acrylate and urethane (meth)acrylate oligomers are preferable in that it is difficult to lower the storage elastic modulus of the pressure-sensitive adhesive layer.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, and 5 to 90% by mass relative to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferable, and it is particularly preferably 10 to 85% by mass.

[Crosslinking system]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkyl ester as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I-1) further comprises a crosslinking agent. It is preferable to contain.

The crosslinking agent is, for example, to react with the functional group to crosslink the adhesive resin (I-1a).

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents having glycidyl groups); Aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatrizine; Metal chelate-based crosslinking agents such as aluminum chelate (crosslinking agents having a metal chelate structure); And isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton).

It is preferable that the crosslinking agent is an isocyanate-based crosslinking agent from the viewpoint of improving the cohesive force of the pressure-sensitive adhesive, improving the adhesion of the pressure-sensitive adhesive layer, and ease of availability.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -15 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoate, methyl benzoin dimethyl ketal, and the like. Phosphorus compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenylketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; Benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone, etc. are mentioned.

Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; It is also possible to use photosensitizers such as amines.

As for the photoinitiator contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound. It is particularly preferable that it is a mass part.

[Other additives]

The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators ( Known additives such as catalysts).

The reaction delaying agent suppresses, for example, the undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) from being stored by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). As a reaction retarder, what forms a chelate complex by chelate with respect to a catalyst is mentioned, More specifically, what has 2 or more carbonyl groups (-C(=O)-) in 1 molecule is mentioned. .

As for the other additives contained in the pressure-sensitive adhesive composition (I-1), only one type may be used, or two or more types thereof may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of other additives is not particularly limited and may be appropriately selected depending on the type.

[menstruum]

The pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, coating suitability to a coating target surface is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Esters such as ethyl acetate (carboxylic acid ester); Ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; And alcohols such as 1-propanol and 2-propanol.

As said solvent, what was used at the time of manufacture of adhesive resin (I-1a), for example, may be used in adhesive composition (I-1) without removing from adhesive resin (I-1a), and adhesive resin ( A solvent of the same or different kind as that used in the preparation of I-1a) may be added separately in the preparation of the pressure-sensitive adhesive composition (I-1).

As for the solvent contained in the adhesive composition (I-1), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive composition (I-2)>

As described above, the pressure-sensitive adhesive composition (I-2) contains an energy ray-curable pressure-sensitive adhesive resin (I-2a) in which an unsaturated group is introduced into a side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a).

[Adhesive resin (I-2a)]

The said adhesive resin (I-2a) is obtained by making the functional group in the adhesive resin (I-1a) react with the unsaturated group containing compound which has an energy ray polymerizable unsaturated group, for example.

The unsaturated group-containing compound is a compound having a group capable of bonding with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.

Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), and (meth)acryloyl group. Is preferred.

Among the adhesive resins (I-1a), examples of a group capable of bonding with a functional group include, for example, an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group.

As said unsaturated group containing compound, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, etc. are mentioned, for example.

As for the adhesive resin (I-2a) contained in the adhesive composition (I-2), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive resin (I-2a) is preferably 5 to 99 mass%, and 10 to 95 mass%, based on the total mass of the pressure-sensitive adhesive composition (I-2). It is more preferable, and it is particularly preferably 10 to 90% by mass.

[Crosslinking system]

When using the said acrylic polymer which has the structural unit derived from the functional group containing monomer same as what is in an adhesive resin (I-1a), for example as an adhesive resin (I-2a), an adhesive composition (I-2) is You may contain a crosslinking agent further.

The thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned as said crosslinking agent in an adhesive composition (I-2).

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, combinations and ratios of these may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 100 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). It is especially preferable that it is -15 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).

As for the photoinitiator contained in the adhesive composition (I-2), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). It is especially preferable that it is 5 mass parts.

[Other additives]

The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention.

As the other additives in the pressure-sensitive adhesive composition (I-2), the same ones as the other additives in the pressure-sensitive adhesive composition (I-1) can be mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-2), only one type may be used, or two or more types thereof may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of other additives is not particularly limited and may be appropriately selected depending on the type.

[menstruum]

The adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

As the said solvent in an adhesive composition (I-2), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

As for the solvent contained in the adhesive composition (I-2), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive composition (I-3)>

The pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive (I-2a) and an energy ray-curable compound, as described above.

In the pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive adhesive (I-2a) is preferably 5 to 99 mass%, and 10 to 95 mass%, based on the total mass of the pressure-sensitive adhesive composition (I-3). It is more preferable, and it is particularly preferable that it is 15 to 90 mass%.

[Energy ray curable compound]

Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition (I-1) contains The same thing as the energy ray curable compound can be mentioned.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferable, and it is particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

The same photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).

As for the photoinitiator contained in the adhesive composition (I-3), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. The denier is more preferable, and it is particularly preferably 0.05 to 5 parts by mass.

[Other additives]

The pressure-sensitive adhesive composition (I-3) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention.

As said other additive, the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-3), only one kind may be used, or two or more kinds thereof may be used, and in the case of two or more kinds, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of other additives is not particularly limited and may be appropriately selected depending on the type.

[menstruum]

The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in an adhesive composition (I-3), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

As for the solvent contained in the adhesive composition (I-3), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive compositions other than adhesive composition (I-1) to (I-3)>

So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but what is described as the content of these components is the overall pressure-sensitive adhesive composition other than these three pressure-sensitive adhesive compositions ( In this specification, it can also be used similarly to "it is called an adhesive composition other than an adhesive composition (I-1)-(I-3)".

As the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive composition (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, a non-energy ray curable pressure-sensitive adhesive composition is also exemplified.

Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable pressure-sensitive adhesive resins (I-1a) such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. ) And the pressure-sensitive adhesive composition (I-4), and preferably contains an acrylic resin.

It is preferable that the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive composition (I-1) to (I-3) contains one or more crosslinking agents, and the content thereof is the same as in the case of the pressure-sensitive adhesive composition (I-1) or the like. can do.

<Adhesive composition (I-4)>

As a preferable thing for an adhesive composition (I-4), what contains the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)]

The thing similar to the adhesive resin (I-1a) in an adhesive composition (I-1) is mentioned as an adhesive resin (I-1a) in an adhesive composition (I-4).

As for the adhesive resin (I-1a) contained in the adhesive composition (I-4), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive resin (I-1a) is preferably 5 to 99 mass%, and 10 to 95 mass%, based on the total mass of the pressure-sensitive adhesive composition (I-4). It is more preferable, and it is particularly preferable that it is 15 to 90 mass%.

[Crosslinking system]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from (meth)acrylic acid alkyl ester as the adhesive resin (I-1a), the adhesive composition (I-4) is additionally It is preferable to contain a crosslinking agent.

As a crosslinking agent in an adhesive composition (I-4), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and preferably 0.3 to 20 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -15 parts by mass.

[Other additives]

The pressure-sensitive adhesive composition (I-4) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

As said other additive, the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

As for the other additives contained in the pressure-sensitive adhesive composition (I-4), only one type may be used, or two or more types thereof may be used, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of other additives is not particularly limited and may be appropriately selected depending on the type.

[menstruum]

The adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

As the said solvent in an adhesive composition (I-4), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

As for the solvent contained in the adhesive composition (I-4), only 1 type may be sufficient, 2 or more types may be sufficient, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.

In the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because, when the pressure-sensitive adhesive layer is energy ray-curable, it may not be possible to suppress curing of the pressure-sensitive adhesive layer at the same time when curing the film for forming a protective film by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, after curing, the protective film-forming film and the pressure-sensitive adhesive layer may be affixed to the extent that they cannot be peeled off at their interfaces. In that case, it is difficult to peel the film for forming a protective film after curing, that is, a semiconductor chip (a semiconductor chip with a protective film) provided on the back surface from the support sheet with the adhesive layer after curing, and the semiconductor chip with a protective film normally You will not be able to pick up. In the support sheet, by making the pressure-sensitive adhesive layer non-energy ray curable, such a problem can be reliably avoided, and a semiconductor chip with a protective film can be more easily picked up.

Although the effect in the case where the pressure-sensitive adhesive layer is non-energy ray-curable has been described here, the same effect is provided if the layer in direct contact with the film for forming a protective film of the support sheet is a layer other than the pressure-sensitive adhesive layer, but this layer is non-energy ray curable. Indicates.

<<The manufacturing method of an adhesive composition>>

Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3) such as pressure-sensitive adhesive compositions (I-1) to (I-3), pressure-sensitive adhesive compositions (I-4), the pressure-sensitive adhesive and, if necessary It is obtained by compounding each component for constituting an adhesive composition, such as a component other than the said adhesive.

The order of addition when mixing each component is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be mixed with any other blending component other than the solvent to dilute the blending component in advance, or may be used without diluting any blending component other than the solvent in advance, and the solvent mixed with these blending components. You may use it by doing.

The method of mixing each component when compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; A method of mixing using a mixer; You may select suitably from well-known methods, such as the method of adding and mixing ultrasonic waves.

The temperature and time during addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Method of manufacturing a composite sheet for forming a protective film

The composite sheet for forming a protective film can be produced by laminating each of the layers described above in a corresponding positional relationship. Each layer is formed as described above.

For example, when manufacturing a support sheet, when laminating an adhesive layer on a base material, you may apply the above-mentioned adhesive composition on a base material, and dry as needed.

On the other hand, for example, in the case of additionally laminating a film for forming a protective film on the pressure-sensitive adhesive layer laminated on a substrate, it is possible to directly form a protective film-forming film by coating a composition for forming a protective film on the pressure-sensitive adhesive layer. Do. Layers other than the film for forming a protective film can also be laminated on the pressure-sensitive adhesive layer by the same method using a composition for forming this layer. In this way, when using one of the compositions to form a continuous two-layer laminate structure, it is possible to form a new layer by further coating the composition on the layer formed from the composition.

However, the layer to be laminated later among these two layers is previously formed using the composition on another release film, and the side of the formed layer in contact with the release film exposes the exposed side of the other side of the remaining layer already formed. It is preferable to form a laminated structure of two consecutive layers by bonding with the surface. At this time, it is preferable that the composition is coated on the release treatment surface of the release film. The release film may be removed as necessary after formation of the laminated structure.

For example, a composite sheet for forming a protective film (a composite sheet for forming a protective film in which a support sheet is a laminate of a substrate and an adhesive layer) is prepared by laminating an adhesive layer on a substrate and a film for forming a protective film laminated on the adhesive layer. In the case of peeling by coating the pressure-sensitive adhesive composition on the substrate and drying it as necessary, the pressure-sensitive adhesive layer is laminated on the substrate, and separately coated with a composition for forming a protective film on the release film and dried as necessary. A film for forming a protective film is formed on the film. Then, the composite sheet for forming a protective film is obtained by bonding the exposed surface of the film for forming a protective film with the exposed surface of the pressure-sensitive adhesive layer laminated on a substrate, and laminating the film for forming a protective film on the pressure-sensitive adhesive layer.

In the case of laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, by coating the pressure-sensitive adhesive composition on a release film and drying as necessary, the pressure-sensitive adhesive layer on the release film By forming and bonding the exposed surface of this layer with one surface of the substrate, the pressure-sensitive adhesive layer may be laminated on the substrate.

In either method, the release film may be removed at an arbitrary timing after forming the target laminate structure.

In this way, all of the layers other than the base material constituting the composite sheet for forming a protective film are previously formed on the release film and can be laminated by a method of bonding to the surface of the target layer. It is sufficient to select a layer to be appropriately prepared to produce a composite sheet for forming a protective film.

The composite sheet for forming a protective film is usually stored in a state where a release film is pasted on the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side to the support sheet. Therefore, by coating a composition for forming a layer constituting the outermost layer such as a composition for forming a protective film on this release film (preferably, the release treatment surface), and drying as necessary, the outermost layer on the release film A layer constituting is formed, and each remaining layer is laminated on any exposed surface on the opposite side to the side in contact with the release film of this layer by any of the methods described above, in a state of bonding without removing the release film. By doing so, a composite sheet for forming a protective film is obtained.

◇Semiconductor chip manufacturing method

The film for forming a protective film and the composite sheet for forming a protective film can be used for the production of semiconductor chips.

As a method for manufacturing a semiconductor chip at this time, for example, a step of attaching a film for forming a protective film which does not constitute the composite sheet for forming a protective film or a film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer ( Hereinafter, there may be abbreviated as "attachment process"), and after attaching to the semiconductor wafer, the process for forming a protective film by irradiating ultraviolet rays to the film for forming a protective film (hereinafter, abbreviated as "protective film formation process") And), by cutting the semiconductor wafer together with the protective film or the film for forming a protective film to divide and obtain a plurality of semiconductor chips (hereinafter sometimes referred to as a "splitting process").

Hereinafter, the manufacturing method described above will be described with reference to the drawings. 7 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip in the case of using a film for forming a protective film that does not form a composite sheet for forming a protective film. 8 is a cross-sectional view for schematically explaining one embodiment of a method for manufacturing a semiconductor chip in the case of using a composite sheet for forming a protective film in which the film for forming a protective film is previously integrated with a support sheet.

<<The manufacturing method of a semiconductor chip in the case of using the film for protective film formation which does not comprise the composite sheet for protective film formation>>

First, an embodiment of a manufacturing method in the case of using a film for forming a protective film that does not constitute a composite sheet for forming a protective film will be described taking an example where the film for forming a protective film is shown in FIG. 1 (this embodiment) The form may be referred to as "manufacturing method (1)").

In the above-mentioned attaching process of the manufacturing method (1), as shown in Fig. 7(a), the film 13 for forming a protective film on the back surface (opposite to the electrode formation surface) 9b of the semiconductor wafer 9 Affixed. Here, when the first peeling film 151 is removed from the film 13 for forming a protective film, and the first surface 13a of the film 13 for forming a protective film is pasted to the back surface 9b of the semiconductor wafer 9 Is shown. Here, in the semiconductor wafer 9, illustration of bumps or the like on the circuit surface is omitted.

After the affixing step of the manufacturing method (1), in the protective film forming step, the film 13 for forming a protective film after being affixed to the semiconductor wafer 9 is irradiated with ultraviolet light, as shown in Fig. 7(b), A protective film 13' is formed on the semiconductor wafer 9. The irradiation of ultraviolet rays may be performed after removing the second release film 152 from the film 13 for forming a protective film.

After the protective film forming step of the manufacturing method (1), as shown in Fig. 7(c), before the dividing step, the surface on the side where the semiconductor wafer 9 of the protective film 13' is affixed (this specification) In the case, the support sheet 10 is attached to the surface (may be referred to as the "second surface" in this specification) 13b' on the side opposite to the "first surface" (13a'). Affixed. The support sheet 10 is shown in Fig. 2 and the like, and is attached to the protective film 13' by the pressure-sensitive adhesive layer 12.

Subsequently, in the above-described dividing step of the manufacturing method (1), the semiconductor wafer 9 is divided by dicing or the like to cut the semiconductor wafer 9 together with the protective film 13', and shown in Fig. 7(d). As described above, a plurality of semiconductor chips 9'are obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9'. The protective film 13' after cutting is denoted by reference numeral 130'.

Fig. 7 shows a case where the support sheet 10 is attached to the protective film 13' after the protective film forming step is performed. However, in the manufacturing method (1), after attaching the support sheet 10 to the film 13 for protective film formation, you may perform a protective film formation process.

In the manufacturing method (1), a division step is performed after the protective film forming step, but in the method for manufacturing a semiconductor chip according to the present embodiment, the protective film forming step is not performed, and the division step is performed to perform the protective film forming step after the division step. May be

<<The manufacturing method of a semiconductor chip when using the composite sheet for protective film formation in which the film for protective film formation was previously integrated with the support sheet>

Next, an embodiment of a manufacturing method in the case of using a composite sheet for forming a protective film in which a film for forming a protective film is integrated with a support sheet in advance is described as an example when the composite sheet for forming a protective film is shown in FIG. 2 as an example. (This embodiment may be referred to as "manufacturing method (2)").

In the pasting step of the manufacturing method (2), as shown in Fig. 8(a), the film 13 for forming a protective film in the composite sheet 1A for forming a protective film on the back surface 9b of the semiconductor wafer 9 Affixed.

The composite sheet 1A for forming a protective film is used by removing the release film 15.

After the affixing step of the manufacturing method (2), in the protective film forming step, the film 13 for forming a protective film after being affixed to the semiconductor wafer 9 is irradiated with ultraviolet light, as shown in Fig. 8(b), A protective film 13' is formed on the semiconductor wafer 9. At this time, ultraviolet rays are irradiated to the film 13 for forming a protective film via the support sheet 10.

Here, the composite sheet for forming a protective film after the film 13 for forming a protective film becomes the protective film 13' is denoted by reference numeral 1A'. This is the same also in subsequent drawings.

After the affixing step of the manufacturing method 2, in the dividing step of the manufacturing method 2, the semiconductor wafer 9 is divided by cutting the semiconductor wafer 9 together with the protective film 13' by dicing or the like, As shown in Fig. 8C, a plurality of semiconductor chips 9'is obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9'to become the protective film 130'.

By the above, the target semiconductor chip 9'is obtained as a semiconductor chip on which a protective film is formed.

In the manufacturing method (2), the division step is performed after the protective film forming step, but in the method for manufacturing a semiconductor chip according to the present embodiment, the protective film forming step is not performed, but the division step is performed to perform the protective film forming step after the division step. May be

Up to this point, the method of manufacturing the semiconductor chip in the case of using the film 13 for forming a protective film shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for forming a protective film shown in FIG. 2 has been described. , The method for manufacturing a semiconductor chip of the present invention is not limited thereto.

For example, when a composite sheet for forming a protective film is used, the composite sheet for forming a protective film (1B) to (1E) shown in FIGS. 3 to 6, a composite sheet for forming a protective film further provided with the intermediate layer, and the like, Even if other than the composite sheet 1A for forming a protective film shown in FIG. 2 is used, a semiconductor chip can be similarly produced.

As described above, a semiconductor chip can be similarly produced even if a substrate other than the supporting sheet 10 shown in FIG. 2 is used, such as a substrate or an intermediate layer laminated.

As described above, in the case of using the composite sheet for forming a protective film or the support sheet of another embodiment, based on the difference in the structure of these sheets, in the above-described manufacturing method, the process is added, changed, deleted, or the like as appropriate. A semiconductor chip can be manufactured.

◇Semiconductor device manufacturing method

After the semiconductor chip is obtained by the above-described manufacturing method, the semiconductor chip is separated from the support sheet and picked up (not shown) in a state where the protective film after division is attached (that is, as the semiconductor chip on which the protective film is formed).

The semiconductor chip of the obtained semiconductor chip with a protective film is arrange|positioned on the circuit surface of a board|substrate by a face down method, and it flip-chip-connects by heating the surface with the protective film of a semiconductor chip at 100-280 degreeC, and it is set as a semiconductor package. Then, a target semiconductor device may be manufactured using this semiconductor package (not shown).

Example

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

<Manufacturing raw material for composition for forming a protective film>

The raw materials used for the preparation of the composition for forming a protective film are shown below.

[Energy ray-curable component (a1-1)]

(a1-1)-1: 2-hydroxyethylacrylic of an acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) UV-curable groups are added to the side chain obtained by reacting 2-methacryloyloxyethyl isocyanate ("Karenzu MOI (registered trademark)" manufactured by Showa Electric Works) in an amount equivalent to 10 mol with respect to 100 mol of hydroxyl groups derived from the rate. Adduct type acrylic polymer introduced (weight average molecular weight 350000, glass transition temperature 6°C).

(a1-1)-2: The amount equivalent to 30 mol with respect to 100 mol of hydroxyl groups derived from 2-hydroxyethyl acrylate of the acrylic polymer formed by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) Adduct type acrylic polymer (weight average molecular weight 350000, glass transition temperature 6°C) in which an ultraviolet curable group is introduced into a side chain obtained by reacting 2-methacryloyloxyethyl isocyanate (manufactured by Showa Electric Co., Ltd.).

[Energy ray curable component (a2)]

(a2)-1: epsilon-caprolactone-modified tris(2-acryloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional ultraviolet curable compound).

[Polymer (b) having no energy ray-curable groups]

(b)-1: Acrylic polymer (weight average molecular weight 350000, glass transition temperature 6°C) obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass).

[Photopolymerization initiator (c)]

(c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF Corporation)).

[Filling material (d)]

(d)-1: Silica filler (melted quartz filler, average particle diameter 8 µm).

[Coupling agent]

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

[Colorant (g)]

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

The weight average molecular weight of the adduct-type acrylic polymer ((a1-1)-1, (a1-1)-2) and the polymer ((b)-1) having no energy ray-curable group is obtained by the following method. Using 1 mL of a sample sample containing 0.005 g of a polymer ((a1-1)-1, (a1-1)-2, or (b)-1) using tetrahydrofuran as a solvent, as a mobile phase at room temperature. From the data obtained by measuring by gel permeation chromatography using tetrahydrofuran, a weight average molecular weight was obtained as a polystyrene conversion value.

[Example 1]

<Production of a composite sheet for forming a protective film>

(Preparation of composition for forming a protective film (IV-1))

With respect to 100 parts by mass of solid content, 10 parts by mass of energy ray-curable component ((a2)-1), 28 parts by mass of adduct-type acrylic polymer ((a1-1)-1), photopolymerization initiator ((c)- 1) methyl ethyl ketone so that 0.6 parts by mass, 57 parts by mass of the filler ((d)-1), 0.4 parts by mass of the coupling agent ((e)-1) and 3 parts by mass of the colorant ((g)-1) The composition for forming a protective film (IV-1) having a solid content concentration of 50% by mass was prepared by dissolving or dispersing in the mixture and stirring at 23°C.

(Preparation of adhesive composition (I-4))

Contains an acrylic polymer (100 parts by mass, solids) and an isocyanate-based crosslinking agent ("Coronate L" manufactured by Nippon Polyurethane, a tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solids), and further A non-energy ray-curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30 mass% containing methyl ethyl ketone as a solvent was prepared. The acrylic polymer has a weight average molecular weight of 600000 by copolymerization of 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass).

(Production of support sheet)

The pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film ("SP-PET381031" manufactured by Lintec, thickness: 38 mu m) on which one side of the polyethylene terephthalate film was subjected to a release treatment by silicone treatment. After coating and heating and drying at 120°C for 2 minutes, a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 µm was formed.

Subsequently, by attaching a polypropylene-based film (80 µm thick) as a base material to the exposed surface of the pressure-sensitive adhesive layer, a support sheet comprising a base material, a pressure-sensitive adhesive layer, and a release film laminated in their thickness direction in this order was obtained. .

(Production of a composite sheet for forming a protective film)

For forming the protective film obtained on the above-mentioned peeling treatment surface of a release film (second release film, "SP-PET382150" manufactured by Lintec Co., Ltd., thickness 38 µm) on which one side of the polyethylene terephthalate film was peeled off by silicon treatment. By coating the composition (IV-1) and drying at 100° C. for 2 minutes, a film for forming an energy ray-curable protective film having a thickness of 25 μm was prepared.

By attaching the release treatment surface of the release film (first release film, "SP-PET381031" manufactured by Lintec, thickness 38 µm) to the exposed surface on the side not provided with the second release film of the film for forming a protective film further obtained, A laminated film having a first release film on one surface of the film for forming a protective film and a second release film on the other surface was obtained.

Next, the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. The 1st peeling film was removed from the laminated film obtained above. Then, by bonding the exposed surface of the pressure-sensitive adhesive layer formed by removing the release film and the exposed surface of the film for forming a protective film formed by removing the first release film, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the second release film In this order, a composite sheet for forming a protective film that was laminated in these thickness directions was produced.

<Evaluation of the protective film>

(Measurement of gloss value (glossiness) of the protective film)

The first release film was removed from the laminated film obtained above, and the exposed surface of the film for forming a protective film thus formed was adhered to a #2000 polished surface of an 8-inch silicon wafer (300 µm thick).

Next, the 2nd peeling film was removed from this film for protective film formation, and the film for protective film formation was exposed. The release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above to expose the pressure-sensitive adhesive layer. Then, by bonding the exposed surface of the pressure-sensitive adhesive layer to the exposed surface of the film for forming a protective film and attaching it to the ring frame, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film and the silicon wafer are in this order, in their thickness direction. The laminated body formed by lamination was fixed to the ring frame and left for 30 minutes.

Subsequently, by using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec) under conditions of an illuminance of 195 mW/cm 2 and a light amount of 170 mJ/cm 2, the protective film forming film was irradiated with ultraviolet light through the substrate and the adhesive layer. The film for forming a protective film was cured to obtain a protective film.

The gloss value (gloss value before heating) of the surface of the formed protective film was measured under the condition that the angle of incidence was 60° using a gloss meter ("VG7000" manufactured by Nippon Electric Industries, Ltd.). Table 1 shows the measured gloss values (gloss values before heating).

Subsequently, the silicon wafer on which the protective film was formed was heated at 260°C for 5 minutes using an oven. Thereafter, the gloss value (gloss value after heating) on the surface of the protective film was measured under the same conditions as the measurement of the gloss value before heating. It was judged that the case in which the rate of decrease in the gloss value after heating from the gloss value before heating was 30% or less was satisfactory. Table 1 shows the measured gloss values before heating, the gloss values after heating, and the gloss values after heating.

[Example 2]

Except that the adduct-type acrylic polymer ((a1-1)-1) was used as the adduct-type acrylic polymer ((a1-1)-2) at the time of production of the protective film-forming composition (IV-1), it was carried out. In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were produced to evaluate the protective film. Table 1 shows the results.

[Comparative Example 1]

Except that the adduct-type acrylic polymer ((a1-1)-1) at the time of production of the protective film-forming composition (IV-1) was used as a polymer having no energy ray-curable group ((b)-1). In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were produced to evaluate the protective film. Table 1 shows the results.

As apparent from the above results, in Example 1, the gloss value before heating and the gloss value after heating on the surface of the protective film were both high at 80 and 65, and the rate of decrease in the gloss value after heating was also low at 19%. In Example 2, both the gloss value before heating and the gloss value after heating of the protective film surface were high at 80 and 72, and the rate of decrease in the gloss value after heating was also low at 10%. It is considered that since the adduct type acrylic polymer was polymerized by ultraviolet irradiation, low-molecular-weight polymer was hardly contained in the protective film, and the low-molecular-weight polymer was not segregated on the surface of the protective film even when the protective film was heated.

In contrast, in Comparative Example 1, the gloss value before heating of the protective film surface was high at 80, whereas the gloss value after heating was decreased to 9. This is compared with the case of Examples 1 and 2, in Comparative Example 1, the polymer (b) having a low molecular weight energy ray-curable group is contained in the protective film and the protective film is segregated on the surface of the protective film by heating the protective film. Since it is, it is thought that the gloss value has decreased.

From the results of these Examples and Comparative Examples, it was clearly confirmed that the reduction of the gloss value due to heating of the protective film surface was suppressed by making the polymer (b) having no energy ray-curable group in the protective film into the adduct-type acrylic polymer (a1-1). Was confirmed.

The present invention can be used in the manufacture of semiconductor devices.

1A, 1A', 1B, 1C, 1D, 1E... Composite sheet for forming a protective film, 10… Support sheet, 10a... The surface of the support sheet (first side), 11... List, 11a... The surface of the substrate (first side), 12... Adhesive layer, 12a... The surface of the pressure-sensitive adhesive layer (first side), 13, 23... Protective film forming film, 13a, 23a... The surface of the film for forming a protective film (first side), 13b… The surface of the film for forming a protective film (second side), 13'… Shield, 130'… Protective film after cutting, 15... Release film, 151... First release film, 152... 2nd release film, 16... Jig adhesive layer, 16a… The surface of the adhesive layer for jigs, 9... Semiconductor wafer, 9b... The back side of the semiconductor wafer, 9'… Semiconductor chip

Claims (3)

As a film for forming an energy ray curable protective film,
The film for forming a protective film is adhered to a semiconductor wafer, and the film for forming a protective film is adhered to a semiconductor wafer for the gloss value measured after irradiating energy rays, irradiated with energy rays, and further heated at 260° C. for 5 minutes. A film for forming a protective film having a decrease rate of the gloss value measured after 30% or less. A composite sheet for forming a protective film comprising a support sheet and comprising the film for forming a protective film of claim 1 on the support sheet. A step of attaching the film for forming a protective film in the protective film forming film of claim 1 or the composite sheet for forming a protective film of claim 2 to a semiconductor wafer;
Forming a protective film by irradiating ultraviolet rays on the film for forming a protective film after being attached to the semiconductor wafer; and cutting the semiconductor wafer together with the protective film or a film for forming a protective film to divide the semiconductor wafer to form a plurality of semiconductor chips The manufacturing method of a semiconductor chip which has a process of obtaining.

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