JPWO2019082966A1 - Method for manufacturing protective film forming film, protective film forming composite sheet, and semiconductor chip - Google Patents

Abstract

The present invention relates to an energy ray-curable protective film forming film 13, and the protective film forming is formed with respect to a gloss value (G1) measured after the protective film forming film 13 is attached to a semiconductor wafer and irradiated with energy rays. The reduction rate (G1-G2) / G1 × 100 of the gloss value (G2) measured after the film 13 for use is attached to the semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes is 30% or less. ..

Description

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.
The present application claims priority based on Japanese Patent Application No. 2017-208437 filed in Japan on October 27, 2017, the contents of which are incorporated herein by reference.

In recent years, semiconductor devices to which a mounting method called a so-called face down method has been applied have been manufactured. In the face-down method, a semiconductor chip having an electrode such as a bump on the circuit surface is used, and the electrode is bonded to the substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may 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 may be incorporated into a semiconductor device as a semiconductor chip with a protective film.
The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.

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

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

Patent Document 1 discloses an energy ray-curable chip protective film attached to the back surface of a circuit forming surface of a wafer. 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 cambium contains a non-energy ray-curable component as a binder polymer component in addition to the energy ray-curable component.

Japanese Unexamined Patent Publication No. 2010-056328

A semiconductor chip on which a 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-curable components contained in the protective film, components having a relatively low molecular weight (so-called bleed-out components) may segregate on the surface of the protective film, and the surface gloss of the protective film may be significantly reduced. As a result, the design of the protective film is deteriorated, and the visibility when printed on the surface of the protective film is deteriorated.

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

In order to solve the above problems, the present invention is an energy ray-curable protective film forming film, wherein the protective film forming film is attached to a semiconductor wafer and irradiated with energy rays, and then measured with respect to a gloss value. Provided is a protective film forming film in which the reduction rate of the gloss value measured after attaching the protective film forming film to a semiconductor wafer, irradiating it with energy rays, and further heating it at 260 ° C. for 5 minutes is 30% or less.

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

The present invention relates to a step of attaching the protective film forming film or the protective film forming film in the protective film forming composite sheet to a semiconductor wafer, and the protective film forming film after being attached to the semiconductor wafer. A step of irradiating the semiconductor wafer with ultraviolet rays to form a protective film, 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. To provide a method for manufacturing a semiconductor chip having.

The protective film-forming film of the present invention reduces the surface gloss of the protective film even when a semiconductor chip having a protective film, which is a cured product of the protective film-forming film, is heated on the back surface for the purpose of bonding or the like. Can be suppressed. Further, according to the present invention, there is provided a protective film forming composite sheet provided with the protective film forming film, and a method for manufacturing a semiconductor chip using the protective film forming film or the protective film forming composite sheet. ..

It is sectional drawing which shows typically the film for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining one Embodiment of the manufacturing method of the semiconductor chip when the film for forming a protective film is used. It is sectional drawing for schematically explaining one Embodiment of the manufacturing method of the semiconductor chip when the composite sheet for forming a protective film is used.

Protective film forming film The protective film forming film according to an embodiment of the present invention is an energy ray-curable protective film forming film, and the protective film forming film is attached to a semiconductor wafer to generate energy rays. The reduction rate of the gloss value measured after the protective film forming film was attached to the semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes with respect to the gloss value measured after the irradiation was 30% or less. Yes, it is preferably 25% or less, and more preferably 20% or less.
When the reduction rate of the gloss value is not more than the upper limit value, even when a semiconductor chip having a protective film which is a cured product of a protective film forming film on the back surface is heated for the purpose of bonding or the like, the protective film It is possible to suppress a decrease in surface gloss.
The reduction rate of the gloss value is most preferably 0%, but even when a semiconductor chip having a protective film which is a cured product of a protective film forming film on the back surface is heated for the purpose of bonding or the like. The reduction rate may be low enough to sufficiently suppress the deterioration of the surface gloss of the protective film. From this point of view, the rate of decrease in the gloss value may be 1% or more, or 2% or more.
Examples of the combination of the upper limit value and the lower limit value include 0% or more and 30% or less, 1% or more and 25% or less, and 2% or more and 20% or less.
The gloss value can be measured with a gloss meter (for example, "VG7000" manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the condition that the incident angle is 60 °.
In the present specification, the "decrease rate of 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, the protective film forming composite sheet can be formed by providing the protective film forming film on the support sheet.

The protective film-forming film is cured by irradiation with energy rays to become a protective film. This protective film protects the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the electrode forming surface). The protective film forming film is soft and can be easily attached to the object to be attached.
Since the protective film-forming film is energy ray-curable, the protective film can be formed by curing in a shorter time than the thermosetting protective film-forming film.

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

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

The energy ray-curable component is preferably uncured, preferably sticky, and more preferably uncured and sticky.

In the present invention, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. ..

The protective film forming film may be only one layer (single layer), may be two or more layers, and when there are a plurality of layers, the plurality of layers may be the same or different from each other, and the plurality of layers may be used. The combination is not particularly limited.
In the present specification, not only in the case of a film for forming a protective film, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers may be the same". It may be different, and only a part of the layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means“ at least one of the constituent materials and the thickness of each layer is different from each other ”. Means that.

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. When the thickness of the protective film forming film is at least the above lower limit value, a protective film having a higher protective ability can be formed. When the thickness of the protective film forming film is not more than the upper limit value, it is possible to prevent the protective film from becoming excessively thick.
Here, the "thickness of the protective film forming film" means the thickness of the entire protective film forming film, and for example, the thickness of the protective film forming film composed of a plurality of layers means the protective film forming film. It means the total thickness of all the layers that make up.

The curing conditions when the protective film for forming the protective film is cured to form the protective film are not particularly limited as long as the degree of curing is such that the protective film sufficiently exerts its function, and the type of the protective film forming film can be used. Depending on the situation, it may be appropriately selected.
For example, the illuminance of the energy rays at the time of curing the protective film forming film is preferably ⁴ to 280 mW / cm ² . The amount of light of the energy rays at the time of curing is preferably ³ to 1000 mJ / cm ² .

FIG. 1 is a cross-sectional view schematically showing a protective film forming film according to an embodiment of the present invention. In the drawings used in the following description, in order to make the features of the present invention easy to understand, the main parts may be enlarged for convenience, and the dimensional ratios and the like of each component are the same as the actual ones. Not necessarily.

The protective film forming film 13 shown here includes a first release film 151 on one surface (sometimes referred to as a "first surface" in the present specification) 13a, and the first surface 13a Provided a second release film 152 on the other surface (sometimes referred to herein as the "second surface") 13b on the opposite side.
Such a protective film forming film 13 is suitable for storage, for example, in the form of a roll.

The protective film forming film 13 can be formed by using the protective film forming composition described later.
The protective film forming film 13 is energy ray curable.

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

In the protective film forming film 13 shown in FIG. 1, either one of the first release film 151 and the second release film 152 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the generated exposed surface. Then, the other remaining of the first release film 151 and the second release film 152 is removed, and the generated exposed surface becomes the attachment surface of the support sheet.

<< Composition for forming a protective film >>
The protective film forming film can be formed by using a protective film forming composition containing the constituent material. For example, a protective film-forming film can be formed at a target site by applying the protective film-forming composition to the surface to be formed of the protective film-forming film and drying it if necessary.
The ratio of the contents of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the ratio of the contents of the components in the protective film-forming film. In the present specification, the "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The composition for forming a protective film may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like. A method using various coaters such as a screen coater, a Meyer bar coater, and a knife coater can be mentioned.

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

<Composition for forming a protective film (IV-1)>
Examples of the protective film-forming composition include a protective film-forming composition (IV-1) containing at least an energy ray-curable component (a).

[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 property, flexibility, and the like to the protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000, and an energy ray-curable group having a molecular weight of 100 or more and less than 80,000. Compound (a2) can be mentioned. At least a part of the polymer (a1) may be crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
In the present specification, the weight average molecular weight means a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000)
As an example of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000, the above-mentioned adduct-type acrylic polymer (a1-1) can be mentioned as an example. The adduct-type acrylic polymer (a1-1) is an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, a group reacting with the functional group, and an energy ray-curable double. It can be obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as a bond.

Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (hereinafter, “substituted amino group” means one or two hydrogens of the amino group. A group in which an atom is substituted with a group other than a hydrogen atom), an epoxy group and the like can be mentioned. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably 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 the acrylic monomer having the functional group and the acrylic monomer having no functional group. In addition to the monomer, a monomer other than the acrylic monomer (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 carboxy 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 hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). (Meta) hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.

In the present specification, "(meth) acrylic acid" is a concept that includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary. You can choose.

Examples of the acrylic monomer having no functional group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, n-octyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Undecyl acrylate, dodecyl (meth) acrylate (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also called myristyl acrylate), (meth) acrylate Consists of alkyl esters such as pentadecyl, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate). Examples thereof include (meth) acrylic acid alkyl esters in which the alkyl group has a chain structure having 1 to 18 carbon atoms.

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

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

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

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

The acrylic polymer (a11) constituting the adduct-type acrylic polymer (a1-1) may be of only one type, may be of two or more types, and when there are two or more types, a combination and ratio thereof. Can be selected arbitrarily.

In the protective film-forming composition (IV-1), the content of the adduct-type acrylic polymer (a1-1) is 1 to 1 with respect to the total mass of the protective film-forming composition (IV-1). It is preferably 50% by mass, 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 one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferable, and those having an isocyanate group as the group are more preferable. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl). Ethyl isocyanate;
Acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and a 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 only one kind, two or more kinds, and when two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

In the adduct-type acrylic polymer (a1-1), the energy ray-curable group derived from the energy ray-curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). The ratio of the content of is preferably 1 to 90 mol%, more preferably 5 to 80 mol%, further preferably 10 to 70 mol%, and 20 to 40 mol%. Is particularly preferable. When the ratio of the content is in such a range, the adhesive force of the protective film formed by curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%, but the energy ray. When the curable compound (a12) is a polyfunctional compound (having two or more of the 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 100,000 to 20,000, more preferably 300,000 to 1,500,000.

When the polymer (a1) is at least partially crosslinked with a cross-linking agent (f), the polymer (a1) has been described as constituting the acrylic polymer (a11). , A monomer that does not correspond to any of the above-mentioned monomers and has a group that reacts with the cross-linking agent (f) may be polymerized and cross-linked at the group that reacts with the cross-linking agent (f). , The group that reacts with the functional group derived from the energy ray-curable compound (a12) may be crosslinked.

The protective film-forming composition (IV-1) and the polymer (a1) contained in the protective film-forming film may be of only one type, may be two or more types, and when two or more types are used. The combination and ratio can be selected arbitrarily.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 or more and less than 80,000)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 or more and less than 80,000 include a group containing an energy ray-curable double bond, and preferred ones are ( Meta) Acryloyl group, vinyl group and the like can be mentioned.

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

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4. -((Meta) acryloxipolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxidiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate (tri) Cyclodecanedimethylol di (meth) acrylate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycoldi (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy- Bifunctional (meth) acrylates such as 1,3-di (meth) acryloxypropane;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as meta) acrylates;
Examples thereof include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group are described in, for example, paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102". Can be used. Such a resin also corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.

The molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.
When the compound (a2) is a monomer, the molecular weight can be calculated from the formula. When the compound (a2) is an oligomer, its molecular weight means a weight average molecular weight.

The protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two or more kinds, or a combination thereof when there are two or more kinds. And the ratio can be selected arbitrarily.

Since the protective film-forming film (protective film-forming composition) contains the energy ray-curable component (a), energy is generated by the energy ray-curable group by irradiation with ultraviolet rays to make the protective film-forming film a protective film. As a result of the linear curable component (a) being polymerized and the protective film containing almost no low molecular weight polymer, it becomes difficult for the low molecular weight polymer to segregate on the surface of the protective film even when the protective film is heated.

Since the protective film-forming film (protective film-forming composition) contains the energy ray-curable component (a), the protective film-forming film is attached to a semiconductor wafer and the gloss measured after irradiation with energy rays. With respect to the value, the reduction rate of the gloss value measured after the protective film forming film is attached to the semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes is as low as 30% or less.

[Polymer without energy ray-curable group (b)]
The protective film-forming composition (IV-1) and the protective film-forming film may contain a polymer (b) having no energy ray-curable group.
The polymer (b) may be at least partially crosslinked by a cross-linking agent (f) described later, or may not be cross-linked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethanes. Examples include resin.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").

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

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, and (meth) acrylic acid ester containing a glycidyl group. Examples thereof include a hydroxyl group-containing (meth) acrylic acid ester and a substituted amino group-containing (meth) acrylic acid ester. Here, the "substituted amino group" is as described above.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) ) 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) n-octyl acrylate, (meth) n-nonyl acrylate, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (also called lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also called myristyl (meth) acrylate), pentadecyl (meth) acrylate , Hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate), etc. Examples thereof include (meth) acrylic acid alkyl esters having a chain structure having 1 to 18 carbon atoms as a group.

Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
Examples thereof include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

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

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 no energy ray-curable group, which is at least partially crosslinked by the cross-linking agent (f), for example, the reactive functional group in the polymer (b) is the cross-linking agent (f). ) And those that reacted.
The reactive functional group may be appropriately selected depending on the type of the cross-linking agent (f) and the like, and is not particularly limited. For example, when the cross-linking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having a high reactivity with an isocyanate group. Is preferable. When the cross-linking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group and the like, and among these, a carboxy group having a high reactivity with an epoxy group is used. preferable. However, in terms of preventing corrosion of circuits of semiconductor wafers and semiconductor chips, the reactive functional group is preferably a group other than a carboxy group.

Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer listed as the monomers constituting the acrylic polymer (b-1) having the reactive functional group. It may be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester, and in addition to the above-mentioned acrylic. Examples of the based monomer and the non-acrylic monomer obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional group can be 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 the reactive functional group to the total amount of the structural units constituting the polymer (b) is 1 to 25. It is preferably by mass, more preferably 2 to 20% by mass. When the ratio is in such a range, the degree of cross-linking in the polymer (b) becomes a more preferable range.

When the content of the polymer (b) having no low molecular weight energy ray-curable group is large in the protective film forming film, the semiconductor chip provided with the protective film which is a cured product of the protective film forming film is bonded or the like. When heated for the purpose of, the surface gloss of the protective film is reduced.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 200,000 or more, more preferably 250,000 or more, and further preferably 300,000 or more. When the weight average molecular weight of the polymer (b) having no energy ray-curable group is equal to or higher than the lower limit, a semiconductor chip having a protective film which is a cured product of a protective film forming film on the back surface is heated by bonding or the like. Even in such a case, the gloss of the protective film surface is unlikely to decrease. The upper limit of the weight average molecular weight of the polymer (b) having no energy ray-curable group is not particularly limited, but the weight having no energy ray-curable group is easy in that the composite sheet for forming a protective film can be easily produced. The weight average molecular weight of the coalescence (b) 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, the dispersibility in the protective film-forming composition (IV-1) becomes good.
Examples of the combination of the upper limit value and the lower limit value include 200,000 or more and 20000 or less, 250,000 or more and 20000 or less, and 300,000 or more and 20000 or less.

When the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is less than the above lower limit value, the polymer (b) having no energy ray-curable group is used as an adduct and an energy ray. It is preferable to introduce an energy ray-curable group such as a curable double bond.
Specifically, the adduct of the polymer (b) having no energy ray-curable group is a polymer (b) having no energy ray-curable group having a functional group capable of reacting with a group possessed by another compound. It can be obtained by reacting a group that reacts with the functional group with an energy ray-curable compound having an energy ray-curable group such as an energy ray-curable double bond.

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

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, ultraviolet irradiation is performed to make the protective film-forming film a protective film. The polymer is polymerized by the energy ray-curable group, and the protective film contains almost no low molecular weight polymer, and even if the protective film is heated, the low molecular weight polymer is less likely to segregate on the surface of the protective film.

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, the protective film-forming film is attached to the semiconductor wafer to generate energy. The rate of decrease in the gloss value measured after the protective film forming film was attached to the semiconductor wafer, irradiated with energy rays, and further heated at 260 ° C. for 5 minutes with respect to the gloss value measured after irradiation with the rays was 30% or less. It becomes a low value.

The polymer (b) having no energy ray-curable group contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind or two or more kinds. In the case of species or more, their combinations and ratios can be arbitrarily selected.

The protective film-forming composition (IV-1) preferably contains the compound (a2) and the polymer (a1). The protective film-forming composition (IV-1) does not contain the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group. Is also preferable. The protective film-forming composition (IV-1) may not contain the compound (a2) but may contain the polymer (a1).
As the polymer (a1), an adduct-type acrylic polymer (a1-1) is preferable.

When the protective film-forming composition (IV-1) contains the polymer (a1) and the compound (a2), the protective film-forming composition (IV-1) contains the compound (a2). The amount is preferably 10 to 400 parts by mass and more preferably 30 to 350 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1).

In the protective film forming composition (IV-1), the content of the energy ray-curable component (a) is preferably 12 to 90% by mass, preferably 15 to 50% by mass, based on the total content of the components other than the solvent. It is more preferably 80% by mass, particularly preferably 20 to 70% by mass, and may be, for example, 25 to 60% by mass, or 30 to 50% by mass. When the content is in such a range, the energy ray curability of the protective film forming film becomes better.

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

The protective film-forming composition (IV-1) is a photopolymerization initiator (c) other than the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, depending on the purpose. , Filler (d), coupling agent (e), cross-linking agent (f), colorant (g), thermosetting component (h), curing accelerator (i), and general-purpose additive (z). It may contain one or more selected from the group.
For example, the protective film-forming film formed by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h) is heated. The adhesive force to the adherend is improved, and the strength of the protective film formed from the protective film forming film is also improved.

[Photopolymerization Initiator (c)]
Examples of the photopolymerization initiator (c) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate and benzoin dimethyl ketal; acetophenone, 2 Acetphenone compounds such as −hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, Benzophenone compounds such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl Benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can also be used.

The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

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

[Filler (d)]
Since the protective film-forming film contains the filler (d), the thermal expansion coefficient of the protective film obtained by curing the protective film-forming film can be easily adjusted. Then, by optimizing this coefficient of thermal expansion for the object to be formed of the protective film, the reliability of the package obtained by using the composite sheet for forming the protective film is further improved. When the protective film-forming film contains the filler (d), the hygroscopicity of the protective film can be reduced and the heat dissipation can be improved.
Examples of the filler (d) include those made of a heat conductive material.

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 of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The average particle size 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 size of the filler (d) is in such a range, it is possible to suppress a decrease in the light transmittance of the protective film while maintaining the adhesiveness of the protective film to the object to be formed.
In the present specification, the "average particle size" means the value of the particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction / scattering method unless otherwise specified.

The protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all the components other than the solvent in the protective film forming composition (IV-1) (that is, for forming the protective film). The content of the filler (d) in the film) is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, particularly preferably 30 to 75% by mass, for example. It may be any of 40 to 70% by mass and 45 to 65% by mass. When the content of the filler (d) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.

[Coupling agent (e)]
By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesion of the protective film forming film to the adherend can be improved. By using the coupling agent (e), the protective film obtained by curing the protective film-forming film has improved water resistance without impairing heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group of an energy ray-curable component (a), a polymer (b) having no energy ray-curable group, or the like. More preferably, it is a silane coupling agent.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

The protective film forming composition (IV-1) and the coupling agent (e) contained in the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

When the coupling agent (e) is used, the content of the coupling agent (e) in the protective film forming composition (IV-1) and the protective film forming film is the content of the energy ray-curable component (a). The amount is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved and the adhesiveness of the protective film forming film to the adherend is improved. The effect of using the coupling agent (e) is more remarkable. Further, when the content of the coupling agent (e) is equal to or less than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (f)]
By cross-linking the above-mentioned energy ray-curable component (a) or polymer (b) having no energy ray-curable group using a cross-linking agent (f), the initial adhesive strength and aggregation of the protective film forming film You can adjust the force.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”. (May be abbreviated); trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the like with a polyol compound. And so on. The "adduct" includes the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound, or the alicyclic polyvalent isocyanate compound, and low ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like. It means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct body include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. The "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4. , 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of the hydroxyl groups of a polyol such as propane; lysine diisocyanate and the like can be mentioned.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylpropan-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking 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 cross-linking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the cross-linking agent (f) and the energy ray-curable The crosslinked structure can be easily introduced into the protective film-forming film by the reaction with the component (a) or the polymer (b) having no energy ray-curable group.

The cross-linking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two or more kinds, or a combination thereof when two or more kinds are used. And the ratio can be selected arbitrarily.

When the cross-linking agent (f) is used, in the protective film forming composition (IV-1), the content of the cross-linking agent (f) is a weight having no energy ray-curable component (a) and an energy ray-curable group. The total content of the coalescence (b) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass. It is particularly preferable to have. When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) is more remarkable. When the content of the cross-linking agent (f) is not more than the upper limit value, the excessive use of the cross-linking agent (f) is suppressed.

[Colorant (g)]
Examples of the colorant (g) include known ones such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, and phthalocyanines. Colors, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments , Pyrol pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indolphenol pigments, triallylmethane pigments, anthraquinone pigments, naphthol pigments, azomethine pigments, benzimidezo Examples thereof include Ron dyes, Pyranthron dyes and Slen 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 ( Examples thereof include indium tin oxide) dyes and ATO (antimons tin oxide) dyes.

The colorant (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, or a combination thereof when there are two or more kinds. And the ratio can be selected arbitrarily.

When the colorant (g) is used, the contents of the protective film-forming composition (IV-1) and the colorant (g) of the protective film-forming film may be appropriately adjusted according to the intended purpose. For example, when the print visibility is adjusted by adjusting the content of the colorant (g) and the light transmittance of the protective film, in the protective film forming composition (IV-1), other than the solvent. The ratio of the content of the colorant (g) to the total content of all the components (that is, the content of the colorant (g) of the protective film forming film) is preferably 0.1 to 10% by mass. , 0.4 to 7.5% by mass is more preferable, and 0.8 to 5% by mass is particularly preferable. When the content of the colorant (g) is at least the lower limit value, the effect of using the colorant (g) is more remarkable. When the content of the colorant (g) is not more than the upper limit, the excessive use of the colorant (g) is suppressed.

[Thermosetting component (h)]
The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, they are used. The combination and ratio of are arbitrarily selectable.

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

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).
The epoxy-based thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

-Epoxy resin (h1)
Examples of the epoxy resin (h1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene type epoxy resin. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds can be mentioned.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meta) acrylamide group and the like, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, preferably 400 to 10000, from the viewpoint of curability of the protective film forming film and the strength and heat resistance of the protective film. It is more preferable that there is, and it is particularly preferable that it is 500 to 3000.
As used herein, "number average molecular weight" means a number average molecular weight represented by a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified. The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.
In the present specification, "epoxy equivalent" means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

As the epoxy resin (h1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

・ Thermosetting agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with epoxy groups 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 anhydrous, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrous. It is preferably a group, more preferably a phenolic 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, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins.
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.
The thermosetting agent (h2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, which is not suitable for the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

When a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) preferably has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. ..
In the present specification, the "glass transition temperature" is represented by the temperature of the inflection point of the obtained DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.

Among the thermosetting agents (h2), the number average molecular weight of the resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene phenol resin, and aralkylphenol resin is preferably 300 to 30,000. It is more preferably 400 to 10000, and particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (h2) is not particularly limited, but is preferably 60 to 500, for example.

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

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

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, epoxy resin (h1) and heat) in the protective film forming composition (IV-1) and the protective film forming film. The total content of the curing agent (h2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the content of the polymer (b) having no energy ray-curable group.

[Curing accelerator (i)]
The curing accelerator (i) is a component for adjusting the curing rate of the protective film forming film.
Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles; tributylphosphine, diphenylphosphine, triphenylphosphine and the like. Organic phosphins; tetraphenylphosphonium tetraphenylborate, tetraphenylborone salts such as triphenylphosphine tetraphenylborate and the like can be mentioned.

As the curing accelerator (i), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.
When the curing accelerator (i) is used, the content of the protective film forming composition (IV-1) and the curing accelerator (i) of the protective film forming film is not particularly limited, and depends on the components to be used in combination. It may be selected as appropriate.

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, plasticizers, antistatic agents, antioxidants, gettering agents and the like. Can be mentioned.

The general-purpose additive (z) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.
When the general-purpose additive (z) is used, the content of the protective film-forming composition (IV-1) and the general-purpose additive (z) of the protective film-forming film is not particularly limited and may be appropriately selected depending on the intended purpose. do it.

[solvent]
The protective film forming composition (IV-1) preferably further contains a solvent. The composition for forming a protective film (IV-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred ones include, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol and the like. Alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond) and the like.
The solvent contained in the protective film forming composition (IV-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

One aspect of the present invention is that the protective film-forming film has an adduct-type acrylic polymer (a1-1) as the polymer (a1) having an energy ray-curable group, and the total mass of the protective film-forming film. On the other hand, as the compound (a2) having 25 to 35% by mass and an energy ray-curable group, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate was added as 5 to 5 to the total mass of the protective film-forming film. 15% by mass of 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone as the photopolymerization initiator (c) was added to the total mass of the protective film forming film. 3 to 0.9% by mass, silica filler as filler (d), 52 to 62% by mass based on the total mass of the protective film forming film, and 3-methacryloxypropyltrimethoxy as coupling agent (e). It is a protective film forming film containing silane in an amount of 0.1 to 0.7% by mass based on the total mass of the protective film forming film.
The adduct-type acrylic polymer (a1-1) is 2 as an energy-curable compound (a12) with an acrylic polymer (a11) obtained by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate. -Preferably, it is obtained by reacting with methacryloyloxyethyl isocyanate.
Further, the ratio of the content 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 5 to 50 mol%. It is preferably present, and more preferably 20 to 40 mol%. Further, the above ratio may be 2 to 15 mol%.
Further, it is preferable that the protective film forming film does not contain the polymer (b) having no energy ray-curable group.
Another aspect of the present invention further comprises 25 to 40 parts by mass of a phthalocyanine blue dye, 10 to 25 parts by mass of an isoindolinone yellow dye, and 40 to 60 parts by mass of an anthraquinone red dye as a colorant (g). And pigmented so that the total of the above three dyes / the amount of styrene acrylic resin = 1/3 (mass ratio), the pigment obtained is 1 to 1 with respect to the total mass of the protective film forming film. A protective film-forming film containing 5% by mass is preferable.

<< Manufacturing method of protective film forming composition >>
A protective film-forming composition such as the protective film-forming composition (IV-1) can be obtained by blending each component for constituting the protective film-forming composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◇ Method for producing a protective film-forming film The protective film-forming film can be produced by applying a protective film-forming composition on a release film (preferably the release-treated surface thereof) and drying it if necessary. .. The manufacturing method at this time is as described above.
As shown in FIG. 1, for example, the protective film-forming film is usually stored with release films bonded to both sides thereof. For that purpose, the exposed surface of the protective film forming film formed on the release film as described above (the surface opposite to the side on which the release film is provided) is further covered with the release film (preferably the release-treated surface thereof). Should be pasted together.

◇ How to use the protective film forming film By providing the protective film forming film on the support sheet as described above, the protective film forming composite sheet can be formed. The protective film-forming composite sheet is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode-forming surface) by the protective film-forming film. Hereinafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

On the other hand, the protective film forming film may be provided first on the back surface of the semiconductor wafer instead of the support sheet. For example, first, the protective film forming film is attached to the back surface of the semiconductor wafer, and then the support sheet is attached to the exposed surface (the surface opposite to the side attached to the semiconductor wafer) of the protective film forming film. Or, the protective film forming film in the attached state is irradiated with energy rays and cured to form a protective film, and then the exposed surface of this protective film (the surface opposite to the side attached to the semiconductor wafer). A support sheet is attached to the composite sheet to form a protective film. Hereinafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

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

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

The thickness of the semiconductor wafer to which the composite sheet for forming the protective film of the present invention is used is not particularly limited, but is preferably 30 to 1000 μm in that it can be more easily divided into semiconductor chips, which will be described later. More preferably, it is 100 to 400 μm.
Hereinafter, the configuration of the composite sheet for forming the 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 the support sheet is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

As a preferable support sheet, for example, a base material is provided, and a pressure-sensitive adhesive layer is directly contacted and laminated on the base material (a base material and a pressure-sensitive adhesive layer are directly contacted and laminated in this order). ); The base material, the intermediate layer and the pressure-sensitive adhesive layer are laminated in this order in direct contact with each other in the thickness direction thereof; those made of only the base material and the like can be mentioned.
An example of the composite sheet for forming a protective film of the present invention will be described below for each type of such support sheet with reference to the drawings.

FIG. 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 after FIG. 2, the same components as those shown in the already described figures are designated by the same reference numerals as in the case of the already described figures, and detailed description thereof will be omitted.

The protective film forming composite sheet 1A shown here includes a base material 11, a pressure-sensitive adhesive layer 12 on the base material 11, and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the protective film-forming composite sheet 1A is, in other words, one surface of the support sheet 10 (in this specification, the "first surface"). It has a structure in which a protective film forming film 13 is laminated on 10a (which may be referred to as). The protective film forming composite sheet 1A further includes a release film 15 on the protective film forming film 13.

In the protective film forming composite sheet 1A, the pressure-sensitive adhesive layer 12 is laminated on one surface of the base material 11 (sometimes referred to as the "first surface" in the present specification) 11a, and the pressure-sensitive adhesive layer 12 is formed. A protective film-forming film 13 is laminated on the entire surface of one surface (sometimes referred to as a "first surface" in the present specification) 12a, and a part of the first surface 13a of the protective film-forming film 13. That is, the adhesive layer 16 for jigs is laminated in the region near the peripheral edge portion, and the surface of the first surface 13a of the protective film forming film 13 on which the adhesive layer 16 for jigs is not laminated and the jig. The release film 15 is laminated on the surface 16a (upper surface and side surface) of the adhesive layer 16 for use.

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

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may be of a structure.

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

FIG. 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 protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2, except that it does not include the jig adhesive layer 16. That is, in the protective film forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming film 13 is laminated on the entire surface of the first surface 12a of the pressure-sensitive adhesive layer 12. The release film 15 is laminated on the entire surface of the first surface 13a of the protective film forming film 13.

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

In the protective film forming composite sheet 1B shown in FIG. 3, a semiconductor wafer (not shown) is formed in a part of the first surface 13a of the protective film forming film 13 on the central side in a state where the release film 15 is removed. ) Is affixed, and the area near the peripheral edge is affixed to a jig such as a ring frame for use.

FIG. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2, except that the pressure-sensitive adhesive layer 12 is not provided. That is, in the protective film forming composite sheet 1C, the support sheet 10 is composed of only the base material 11. Then, the protective film forming film 13 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10), and a part of the first surface 13a of the protective film forming film 13, that is, the peripheral edge portion. The adhesive layer 16 for jigs is laminated in the vicinity, and the area 13a of the first surface 13a of the protective film forming film 13 where the adhesive layer 16 for jigs is not laminated and the adhesive layer for jigs. The release film 15 is laminated on the surface 16a (upper surface and side surface) of the 16.

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

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

FIG. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
The protective film-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 4, except that it does not include the jig adhesive layer 16. That is, in the protective film forming composite sheet 1D, the protective film forming film 13 is laminated on the first surface 11a of the base material 11, and the release film 15 is laminated on the entire surface of the first surface 13a of the protective film forming film 13. Has been done.

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

Similar to the protective film-forming composite sheet 1B shown in FIG. 3, the protective film-forming composite sheet 1D shown in FIG. 5 has the first surface 13a of the protective film-forming film 13 with the release film 15 removed. Of these, the back surface of the semiconductor wafer (not shown) is attached to a part of the central side, and the area near the peripheral edge is attached to a jig such as a ring frame for use.

FIG. 6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.
The protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 3, except that the shape of the protective film-forming film is different. That is, the protective film forming composite sheet 1E includes a base material 11, a pressure-sensitive adhesive layer 12 on the base material 11, and a protective film forming film 23 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1E has the protective film-forming film 23 laminated on the first surface 10a of the support sheet 10. Has a structure. The protective film forming composite sheet 1E further includes a release film 15 on the protective film forming film 23.

In the protective film forming composite sheet 1E, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, on the central region. The film 23 for use is laminated. Then, on the first surface 12a of the pressure-sensitive adhesive layer 12, the region where the protective film forming film 23 is not laminated and the surface 23a (upper surface and side surface) of the protective film forming film 23, the release film 15 is formed. It is laminated.

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

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

In the protective film forming composite sheet 1E shown in FIG. 6, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film forming film 23 in a state where the release film 15 is removed, and further, an adhesive layer is formed. Of the first surface 12a of 12, the region where the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.

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

As described above, the protective film-forming composite sheet may be provided with an adhesive layer for jigs regardless of the form of the support sheet and the protective film-forming film. However, as shown in FIGS. 2 and 4, usually, as a composite sheet for forming a protective film provided with an adhesive layer for a jig, a composite sheet for forming a protective film provided with an adhesive layer for a jig on the protective film forming film. Is preferable.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to those shown in FIGS. 2 to 6, and is a part of those shown in FIGS. 2 to 6 within a range that does not impair the effects of the present invention. The configuration of the above may be changed or deleted, or other configurations may be added to those described above.

For example, in the protective film forming composite sheet shown in FIGS. 4 and 5, an intermediate layer may be provided between the base material 11 and the protective film forming film 13. As the intermediate layer, any one can be selected according to the purpose.
In the protective film forming composite sheet shown in FIGS. 2, 3 and 6, an intermediate layer may be provided 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 base material, an intermediate layer, and an adhesive layer in this order in the thickness direction thereof. Here, the intermediate layer is the same as the intermediate layer that may be provided in the protective film forming composite sheet shown in FIGS. 4 and 5.
In the composite sheet for forming a protective film shown in FIGS. 2 to 6, a layer other than the intermediate layer may be provided at an arbitrary position.
In the composite sheet for forming a protective film, a partial gap 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 protective film-forming composite sheet of the present invention, as will be described later, it is preferable that the layer in direct contact with the protective film-forming film of the support sheet, such as the adhesive layer, is non-energy ray-curable. .. Such a composite sheet for forming a protective film enables easier pick-up of a semiconductor chip with a protective film.

The support sheet may be transparent, opaque, or colored depending on the purpose.
Among them, in the present invention in which the protective film forming film has energy ray curability, the support sheet preferably allows energy rays to pass through.

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 light transmittance is in such a range, the degree of curing of the protective film-forming film is further improved when the protective film-forming film is irradiated with energy rays (ultraviolet rays) via the support sheet.
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 light transmittance 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 light transmittance is in such a range, the protective film forming film or the protective film is irradiated with laser light via the support sheet, and when printed on these, printing can be performed more clearly.
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 light transmittance 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 light transmittance is in such a range, the protective film forming film or the protective film is irradiated with laser light via the support sheet, and when printed on these, printing can be performed more clearly.
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 light transmittance 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 light transmittance is in such a range, the semiconductor wafer is irradiated with laser light via the support sheet and the protective film forming film or protective film, and the modified layer is further formed on the semiconductor wafer. It can be easily formed.
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 light transmittance may be 95% or less.
Next, each layer constituting the support sheet will be described in more detail.

○ Base material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; polyethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and ethylene-norbornene copolymer (ethylene as monomer) (Copolymer obtained using); Vinyl chloride resin such as polyvinyl chloride, vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyethylene terephthalate, polyethylene Polyethylenes such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all aromatic polyesters in which all constituent units have an aromatic cyclic group; co-operation of two or more of the above polyesters. Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
Examples of the resin include crosslinked resins obtained by cross-linking one or more of the resins exemplified above; and modified resins such as ionomers using one or more of the resins exemplified so far. Can be mentioned.

The resin constituting the base material may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming the protective film and the stickability to the semiconductor wafer or the semiconductor chip are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material, for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.
In the present specification, the "thickness" is a value expressed by measuring arbitrary five points of an object with a contact-type thickness gauge and averaging them.

It is preferable that the base material has a high accuracy of thickness, that is, a base material in which variation in thickness is suppressed regardless of the site. Among the above-mentioned constituent materials, as a material that can be used to construct a base material having such a high accuracy of thickness, for example, polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer and the like are used. Can be mentioned.

In addition to the main constituent materials such as the resin, the base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). May be.

It is preferable that the optical characteristics of the base material satisfy the optical characteristics of the support sheet described above. For example, the base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
In the present invention in which the protective film forming film has energy ray curability, the base material preferably transmits energy rays.

In order to improve the adhesion of the base material to other layers such as the adhesive layer provided on the base material, the base material is subjected to sandblasting treatment, solvent treatment or other unevenness treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment. , Ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments may be applied to the surface.
The surface of the base material may be primer-treated.
The base material is an antistatic coat layer; a layer that prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the composite sheets for forming a protective film are stacked and stored. It may have.

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

In the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness. For example, not only the resin itself having adhesiveness but also an additive. It also includes a resin that exhibits adhesiveness when used in combination with other components such as, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.

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

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 pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

It is preferable that the optical characteristics of the pressure-sensitive adhesive layer satisfy the optical characteristics of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose.
In the present invention in which the protective film forming film has energy ray curability, the pressure-sensitive adhesive layer preferably allows energy rays to pass through.

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

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and a screen coater. , A method using various coaters such as a Meyer bar 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 the pressure-sensitive adhesive composition. The solvent-containing pressure-sensitive adhesive composition is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, is a non-energy ray-curable pressure-sensitive adhesive. Adhesive composition (I-1) containing a resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound; non-energy An energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear curable adhesive resin (I-1a) (hereinafter referred to as "adhesive resin (I-2a)"). A pressure-sensitive adhesive composition (I-2) containing (may be abbreviated); a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive resin (I-2a) and an energy ray-curable compound, etc. Can be mentioned.

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from (meth) acrylic acid alkyl ester.
The structural unit of the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferable.
More specifically, as the (meth) acrylic acid alkyl ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (also called (meth) lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also called myristyl (meth) acrylate), (meth) acrylic Pentadecyl acrylate, hexadecyl (meth) acrylate (also called palmityl acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also called stearyl acrylate), nonadecil (meth) acrylate , (Meta) icosyl acrylate and the like.

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

The acrylic polymer preferably has 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 functional group-containing monomer, for example, the functional group may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

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

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

As the functional group-containing monomer, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.

The functional group-containing monomer constituting the acrylic polymer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can 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, based on the total mass of the structural unit. It is preferably 3 to 30% by mass, and particularly preferably 3 to 30% by mass.

The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with a (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The other monomer constituting the acrylic polymer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can 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, a product obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group) has the above-mentioned energy ray-curable adhesiveness. It can be used as a resin (I-2a).

The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive adhesive resin (I-1a) may be 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Polyvalent (meth) acrylates such as −butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound has a relatively large molecular weight, and urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable in that the storage elastic modulus of the pressure-sensitive adhesive layer is unlikely to be lowered.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can 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 with respect to the total mass of the pressure-sensitive adhesive composition (I-1). , 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

[Crosslinking agent]
When 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 is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( I-1) preferably further contains a cross-linking agent.

The cross-linking agent, for example, reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.
Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; and epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (crosslinking agents). Crosslinking agent having a glycidyl group); Isocyanate-based crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (crosslinking agent having an aziridinyl group); Metal chelate-based crosslinking agent such as aluminum chelate (metal chelate) Crosslinking agent having a structure); Isocyanurate-based crosslinking agent (crosslinking agent having an isocyanurate skeleton) and the like can be mentioned.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive to improve the adhesive force of the pressure-sensitive adhesive layer and being easily available.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can 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 with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 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 compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone and 2-hydroxy. Acetphenone compounds such as -2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone; azo Azo compounds such as bisisobutyronitrile; titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane 2-Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can also be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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 with respect to 100 parts by mass of the content of the energy ray-curable compound, and is 0. It is more preferably .03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antioxidants, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction retarder means that, for example, an unintended cross-linking reaction proceeds in the pressure-sensitive adhesive composition (I-1) being stored by the action of a catalyst mixed in the pressure-sensitive adhesive composition (I-1). Suppress. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated 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 esters); ethers such as tetrahydrofuran and dioxane; cyclohexane, n-hexane and the like. Hydrophilic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the solvent, for example, the solvent used in the production of the pressure-sensitive adhesive resin (I-1a) may be used as it is in the pressure-sensitive adhesive composition (I-1) without being removed from the pressure-sensitive adhesive resin (I-1a). However, the same or different type of solvent as that used in the production of the pressure-sensitive adhesive resin (I-1a) may be added separately during the production of the pressure-sensitive adhesive composition (I-1).

The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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) is an energy ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.

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

In addition to the energy ray-polymerizable unsaturated group, the unsaturated group-containing compound can further bind to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (also referred to as an ethenyl group), an allyl group (also referred to as a 2-propenyl group), and the like, and a (meth) acryloyl group is preferable. ..
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

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

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive adhesive resin (I-2a) may be 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-2). It is preferably 10 to 95% by mass, more preferably 10 to 90% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the pressure-sensitive adhesive composition ( I-2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can 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 with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 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 initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a). , 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive resin (I-2a) and an energy ray-curable compound.

In the pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive adhesive resin (I-2a) may be 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-3). It is preferably 10 to 95% by mass, more preferably 15 to 90% by 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. Examples thereof include the same energy ray-curable compounds contained in the substance (I-1).
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

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

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound. The amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and 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 fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
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).
Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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 compositions (I-1) to (I-3)>
Up to this point, 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 those described as the components contained therein have been described. General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to in this specification as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") However, it can be used in the same way.

Examples of the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions as well as energy-ray-curable pressure-sensitive adhesive compositions.
Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Examples thereof include a pressure-sensitive adhesive composition (I-4) containing a sex-sensitive pressure-sensitive resin (I-1a), and those containing an acrylic resin are preferable.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. The same can be applied to the case of (I-1) and the like.

<Adhesive composition (I-4)>
Preferred pressure-sensitive adhesive compositions (I-4) include, for example, those containing the pressure-sensitive adhesive resin (I-1a) and a cross-linking agent.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same adhesive resin (I-1a) as in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive adhesive resin (I-1a) may be 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-4). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.

[Crosslinking agent]
When 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 is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( I-4) preferably further contains a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-4) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof 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 if the pressure-sensitive adhesive layer is energy ray-curable, it may not be possible to suppress the curing of the pressure-sensitive adhesive layer at the same time when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to each other to the extent that they cannot be peeled off at these interfaces. In that case, it becomes difficult to peel off the cured protective film forming film, that is, the semiconductor chip having the protective film on the back surface (semiconductor chip with the protective film) from the support sheet having the cured adhesive layer. The semiconductor chip with a protective film cannot be picked up normally. By making the pressure-sensitive adhesive layer non-energy ray-curable in the support sheet, such a defect can be surely avoided, and the semiconductor chip with a protective film can be picked up more easily.

Here, the effect when the pressure-sensitive adhesive layer is non-energy ray-curable has been described, but even if the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer. If the layer is non-energy ray curable, the same effect can be achieved.

<< Manufacturing method of adhesive composition >>
Adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive composition (I-4) , The pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive, and the like, are obtained by blending each component for forming a pressure-sensitive adhesive composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◇ Method for manufacturing a composite sheet for forming a protective film The composite sheet for forming a protective film can be manufactured by laminating the above-mentioned layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, when the pressure-sensitive adhesive layer is laminated on the base material when the support sheet is manufactured, the above-mentioned pressure-sensitive adhesive composition may be applied on the base material and dried if necessary.

On the other hand, for example, when a protective film-forming film is further laminated on the pressure-sensitive adhesive layer already laminated on the base material, the protective film-forming composition is applied on the pressure-sensitive adhesive layer to form a protective film. It is possible to directly form a forming film. For layers other than the protective film-forming film, this layer can be laminated on the pressure-sensitive adhesive layer in the same manner by using the composition for forming this layer. As described above, when a continuous two-layer laminated structure is formed by using any of the compositions, the composition is further applied on the layer formed from the composition to form a new layer. It is possible to form.
However, of these two layers, the layer to be laminated afterwards is formed in advance on another release film using the composition, and the side of the formed layer in contact with the release film is It is preferable to form a laminated structure of two continuous layers by laminating the exposed surface on the opposite side with the exposed surface of the remaining layers that have already been formed. At this time, it is preferable that the composition is applied to the peeled surface of the release film. The release film may be removed if necessary after the laminated structure is formed.

For example, a protective film-forming composite sheet in which an adhesive layer is laminated on a base material and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of a base material and an adhesive layer). When producing a protective film-forming composite sheet), an adhesive composition is applied onto the base material and dried as necessary to laminate an adhesive layer on the base material, which is separately provided. , The protective film-forming composition is applied onto the release film and dried if necessary to form the protective film-forming film on the release film. Then, the exposed surface of the protective film forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer already laminated on the base material, and the protective film-forming film is laminated on the pressure-sensitive adhesive layer to form the protective film. Composite sheet for use is obtained.

When laminating the pressure-sensitive adhesive layer on the base material, it is necessary to coat the pressure-sensitive adhesive composition on the release film instead of the method of coating the pressure-sensitive adhesive composition on the base material as described above. A pressure-sensitive adhesive layer is formed on the release film by drying according to the above, and the exposed surface of this layer is bonded to one surface of the base material to laminate the pressure-sensitive adhesive layer on the base material. You may.
In either method, the release film may be removed at an arbitrary timing after the desired laminated structure is formed.

As described above, all the layers other than the base material constituting the protective film forming composite sheet can be laminated in advance by forming them on the release film and laminating them on the surface of the target layer. A layer for adopting such a process may be appropriately selected to produce a composite sheet for forming a protective film.

The protective film-forming composite sheet is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, the protective film-forming film) on the opposite side of the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied onto the release film (preferably the release-treated surface thereof), and the composition is dried if necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface on the side opposite to the side in contact with the release film of this layer by any of the above methods. However, a composite sheet for forming a protective film can also be obtained by leaving the release film in a bonded state without removing it.

◇ Method for manufacturing a semiconductor chip The protective film forming film and the protective film forming composite sheet can be used for manufacturing a semiconductor chip.
As a method for manufacturing the semiconductor chip at this time, for example, a protective film forming film that does not constitute the protective film forming composite sheet, or a protective film forming film in the protective film forming composite sheet is used as a semiconductor wafer. (Hereinafter, it may be abbreviated as "sticking step") and a step of irradiating the protective film forming film after sticking to the semiconductor wafer with ultraviolet rays to form a protective film (hereinafter, "pasting step"). A step of obtaining a plurality of semiconductor chips by cutting the semiconductor wafer together with the protective film or the protective film forming film (hereinafter, may be abbreviated as "protective film forming step"). It may be abbreviated as "process"), and those having.

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

<< Manufacturing method of semiconductor chip when a protective film forming film that does not form a protective film forming composite sheet is used >>
First, regarding one embodiment of the manufacturing method in the case of using the protective film forming film that does not constitute the protective film forming composite sheet, the case where the protective film forming film is shown in FIG. 1 is taken as an example. This embodiment will be described (the present embodiment may be referred to as "manufacturing method (1)").

In the sticking step of the manufacturing method (1), as shown in FIG. 7A, the protective film forming film 13 is stuck on the back surface (the surface opposite to the electrode forming surface) 9b of the semiconductor wafer 9. Here, the case where the first release film 151 is removed from the protective film forming film 13 and the first surface 13a of the protective film forming film 13 is attached to the back surface 9b of the semiconductor wafer 9 is shown. Here, in the semiconductor wafer 9, the illustration of bumps and the like on the circuit surface is omitted.

After the sticking step of the manufacturing method (1), in the protective film forming step, the protective film forming film 13 after sticking to the semiconductor wafer 9 is irradiated with ultraviolet rays, and as shown in FIG. 7B, the semiconductor A protective film 13'is formed on the wafer 9. The irradiation with ultraviolet rays may be performed after removing the second release film 152 from the protective film forming film 13.

After the protective film forming step of the manufacturing method (1), prior to the dividing step, as shown in FIG. 7 (c), the surface of the protective film 13'on the side to which the semiconductor wafer 9 is attached (the present specification). The support sheet 10 is attached to the surface (sometimes referred to as the "second surface" in the present specification) 13b'opposite to the 13a' (which may be referred to as the "first surface"). .. 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.

Next, in the division step of the manufacturing method (1), the semiconductor wafer 9 is divided by cutting the semiconductor wafer 9 together with the protective film 13'by dicing or the like, and as shown in FIG. 7D, a plurality of semiconductor wafers 9 are divided. Obtain a semiconductor chip 9'. At this time, the protective film 13'is cut (divided) at a position along the peripheral edge of the semiconductor chip 9'. The protective film 13'after this cutting is indicated 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), the protective film forming step may be performed after the support sheet 10 is attached to the protective film forming film 13.

In the manufacturing method (1), the dividing step is performed after the protective film forming step, but in the method for manufacturing the semiconductor chip according to the present embodiment, the dividing step is performed without performing the protective film forming step, and the protective film is performed after the dividing step. The forming step may be performed.

<< Manufacturing method of semiconductor chip when 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 used >>
Next, regarding one embodiment of the manufacturing method in the case of using the protective film forming composite sheet in which the protective film forming film is integrated with the support sheet in advance, the case where the protective film forming composite sheet is shown in FIG. Will be described by way of example (this embodiment may be referred to as "manufacturing method (2)").

In the pasting step of the manufacturing method (2), as shown in FIG. 8A, the protective film forming film 13 in the protective film forming composite sheet 1A is pasted on the back surface 9b of the semiconductor wafer 9.
The protective film forming composite sheet 1A is used after removing the release film 15.

After the sticking step of the manufacturing method (2), in the protective film forming step, the protective film forming film 13 after sticking to the semiconductor wafer 9 is irradiated with ultraviolet rays, and as shown in FIG. 8 (b), the semiconductor A protective film 13'is formed on the wafer 9. At this time, the ultraviolet rays irradiate the protective film forming film 13 via the support sheet 10.
Here, the protective film forming composite sheet after the protective film forming film 13 becomes the protective film 13'is indicated by reference numeral 1A'. This also applies to the following figures.

After the sticking 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, and FIG. 8 (c) shows. As shown in, a plurality of semiconductor chips 9'are obtained. At this time, the protective film 13'is cut (divided) at a position along the peripheral edge of the semiconductor chip 9'to become the protective film 130'.
As described above, the target semiconductor chip 9'can be obtained as a semiconductor chip with a protective film.

In the manufacturing method (2), the dividing step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the dividing step is performed without performing the protective film forming step, and the protective film is performed after the dividing step. The forming step may be performed.

Up to this point, a method for manufacturing a semiconductor chip has been described when the protective film forming film 13 shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the protective film forming composite sheet 1A shown in FIG. 2 are used. The method for manufacturing a semiconductor chip of the present invention is not limited thereto.
For example, when a protective film-forming composite sheet is used, the protective film-forming composite sheets 1B to 1E shown in FIGS. 3 to 6 and the protective film-forming composite sheet further provided with the intermediate layer are shown in FIG. A semiconductor chip can be similarly manufactured by using a material other than the protective film forming composite sheet 1A shown.
As the support sheet, a semiconductor chip can be similarly manufactured by using a support sheet other than the support sheet 10 shown in FIG. 2, such as a support sheet made of only a base material or a laminated intermediate layer as described above. it can.
As described above, when the composite sheet for forming a protective film or the support sheet of another embodiment is used, in the above-mentioned manufacturing method, addition, modification, deletion, etc. of steps are appropriately performed based on the difference in the structure of these sheets. To manufacture a semiconductor chip.

◇ Manufacturing method of semiconductor device After obtaining a semiconductor chip by the above-mentioned manufacturing method, the semiconductor chip is supported with the divided protective film still attached (that is, as a semiconductor chip with a protective film). Pick up by pulling away from (not shown).
After arranging the semiconductor chip of the obtained semiconductor chip with a protective film on the circuit surface of the substrate by a face-down method and flip-chip connecting the surface on which the protective film of the semiconductor chip is formed by heating at 100 to 280 ° C. , Semiconductor package. Then, the target semiconductor device may be manufactured using this semiconductor package (not shown).

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 protective film forming composition>
The raw materials used for producing the protective film forming composition are shown below.
[Energy ray curable component (a1-1)]
(A1-1) -1: 2 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). Side chain obtained by reacting 100 mol of a hydroxyl group derived from -hydroxyethyl acrylate with 2-methacryloyloxyethyl isocyanate ("Carens MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.) in an amount corresponding to 10 mol. An adduct-type acrylic polymer having an ultraviolet curable group introduced therein (weight average molecular weight 350,000, glass transition temperature 6 ° C.).
(A1-1) -2: 30 mol with respect to 100 mol of hydroxyl groups derived from 2-hydroxyethyl acrylate of an acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass). Adduct-type acrylic polymer (weight average molecular weight 350,000, glass transition temperature) in which an ultraviolet curable group was introduced into the side chain, which was obtained by reacting an amount of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko) corresponding to 6 ° C).
[Energy ray curable component (a2)]
(A2) -1: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (“A-9300-1CL” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a trifunctional UV curable compound).
[Polymer without energy ray-curable group (b)]
(B) -1: An acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight 350,000, glass transition temperature 6 ° C.).
[Photopolymerization Initiator (c)]
(C) -1: 2- (Dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (BASF's "Irgacure® 369").
[Filler (d)]
(D) -1: Silica filler (fused quartz filler, average particle size 8 μm).
[Coupling agent]
(E) -1: 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent).
[Colorant (g)]
(G) -1: 32 parts by mass of phthalocyanine blue dye (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow dye (Pigment Yellow 139), and 50 parts by mass of anthraquinone red dye (Pigment Red 177). A pigment obtained by mixing and pigmenting so that the total amount of the above three dyes / the amount of styrene acrylic resin = 1/3 (mass ratio).

The weight average molecular weights of the adduct-type acrylic polymer (a1-1) -1, (a1-1) -2, and the polymer (b) -1 having no energy ray-curable group can be obtained by the following methods. It was. Tetrahydrofuran was used as the solvent, and 1 mL of a sample sample containing 0.005 g of the polymer (a1-1) -1, (a1-1) -2, or (b) -1 was used, and tetrahydrofuran was used as the mobile phase at room temperature. It was measured by the gel permeation chromatography method used, and the weight average molecular weight was obtained as a polystyrene-equivalent value from the obtained data.

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

(Manufacturing of Adhesive Composition (I-4))
Acrylic polymer (100 parts by mass, solid content) and isocyanate-based cross-linking agent ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd., trimethylolpropane trimerizing isocyanate trimer adduct) (5 parts by mass, solid content) A non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing 30% by mass of a solid content and further containing methyl ethyl ketone as a solvent was prepared. The acrylic polymer is a copolymer of -2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass) and has a weight average molecular weight of 600,000.

(Manufacturing of support sheet)
The pressure-sensitive adhesive composition (I-4) obtained above is applied to the peel-treated surface of a release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film is peeled by a silicone treatment. ) Was applied and dried by heating at 120 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm.
Next, by laminating a polypropylene film (thickness 80 μm) as a base material on the exposed surface of the pressure-sensitive adhesive layer, the base material, the pressure-sensitive adhesive layer and the release film are laminated in this order in these thickness directions. I got a support sheet.

(Manufacturing of composite sheet for forming protective film)
The protective film obtained above is formed on the peeled surface of the peeled film (second peeling film, "SP-PET382150" manufactured by Lintec Corporation, thickness 38 μm) in which one side of the polyethylene terephthalate film is peeled by silicone treatment. The composition for use (IV-1) was applied and dried at 100 ° C. for 2 minutes to produce an energy ray-curable protective film forming film having a thickness of 25 μm.
Further, the exposed surface of the obtained protective film forming film on the side not provided with the second release film is subjected to a release treatment of the release film (first release film, "SP-PET38131" manufactured by Lintec Co., Ltd., thickness 38 μm). By laminating the surfaces, a laminated film having a first release film on one surface of the protective film forming film and a second release film on the other surface was obtained.

Then, the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. The first release film was removed from the laminated film obtained above. Then, by adhering the exposed surface of the pressure-sensitive adhesive layer formed by removing the release film and the exposed surface of the protective film forming film formed by removing the first release film, the base material and the adhesive are adhered. A protective film-forming composite sheet was prepared in which the agent layer, the protective film-forming film, and the second release film were laminated in this order in these thickness directions.

<Evaluation of protective film>
(Measurement of gloss value (glossiness) of protective film)
The first release film was removed from the laminated film obtained above, and the exposed surface of the protective film forming film thus formed was attached to the # 2000 polished surface of an 8-inch silicon wafer (thickness 300 μm).
Next, the second release film was removed from the protective film-forming film to expose the protective film-forming film. 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, the exposed surface of the pressure-sensitive adhesive layer is bonded to the exposed surface of the protective film-forming film, and the base material, the pressure-sensitive adhesive layer, the protective film-forming film, and the silicon wafer are attached in this order by sticking to the ring frame. The laminates laminated in these thickness directions were fixed to a ring frame and allowed to stand for 30 minutes.

Next, using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation), a protective film forming film was formed via the base material and the pressure-sensitive adhesive layer under the conditions of an illuminance of 195 mW / cm ² and a light intensity of 170 mJ / cm ^2. By irradiating with ultraviolet rays, the protective film-forming film was cured to obtain a protective film.

The gloss value (gloss value before heating) of the formed protective film surface was measured using a gloss meter (“VG7000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the condition of an incident angle of 60 °. The measured gloss value (gloss value before heating) is shown in Table 1.

Next, the silicon wafer on which the protective film was formed was heated at 260 ° C. for 5 minutes using an oven. Then, 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. When the rate of decrease of the gloss value after heating from the gloss value before heating was 30% or less, it was judged to be good. Table 1 shows the measured gross value before heating, the gloss value after heating, and the reduction rate of the gloss value after heating.

[Example 2]
Examples except that the adduct-type acrylic polymer (a1-1) -1 at the time of producing the protective film-forming composition (IV-1) was changed to the adduct-type acrylic polymer (a1-1) -2. A protective film-forming film and a protective film-forming composite sheet were produced in the same manner as in 1, and the protective film was evaluated. The results are shown in Table 1.

[Comparative Example 1]
Except for the fact that the adduct-type acrylic polymer (a1-1) -1 at the time of producing the protective film forming composition (IV-1) was changed to the polymer (b) -1 having no energy ray-curable group. A protective film-forming film and a protective film-forming composite sheet were produced in the same manner as in Example 1, and the protective film was evaluated. The results are shown in Table 1.

As is clear from the above results, in Example 1, the gloss value before heating and the gloss value after heating of the protective film surface were both as high as 80 and 65, and the reduction rate of the gloss value after heating was also 19%. It was low. In Example 2, the gloss value before heating and the gloss value after heating of the protective film surface were both high at 80 and 72, and the reduction rate of the gloss value after heating was also low at 10%. This is because the adduct-type acrylic polymer was polymerized by irradiation with ultraviolet rays, so that the protective film contained almost no low molecular weight polymer, and even if the protective film was heated, the low molecular weight polymer segregated on the surface of the protective film. It is probable that it was not.

On the other hand, in Comparative Example 1, the gloss value of the protective film surface before heating was as high as 80, while the gloss value after heating decreased to 9. This is because, as compared with the cases of Examples 1 and 2, in Comparative Example 1, a large amount of the polymer (b) having no low molecular weight energy ray-curable group is contained in the protective film, and the protective film is heated. It is considered that the low molecular weight polymer segregated on the surface of the protective film, resulting in a decrease in the gloss value.

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

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

1A, 1A', 1B, 1C, 1D, 1E ... Protective film forming composite sheet, 10 ... Support sheet, 10a ... Surface of support sheet (first surface), 11 ... Base material, 11a ... Surface of base material (first surface), 12 ... Adhesive layer, 12a ... Surface of adhesive layer (first surface), 13, 23 ... Protective film forming film, 13a , 23a ... Surface of protective film forming film (first surface), 13b ... Surface of protective film forming film (second surface), 13'... protective film, 130'... after cutting Protective film, 15 ... release film, 151 ... first release film, 152 ... second release film, 16 ... jig adhesive layer, 16a ... jig adhesive layer Front surface, 9 ... Semiconductor wafer, 9b ... Back surface of semiconductor wafer, 9'... Semiconductor chip

Claims (3)

An energy ray-curable protective film forming film
The protective film forming film is attached to the semiconductor wafer, and the gloss value measured after irradiation with energy rays is obtained. The protective film forming film is attached to the semiconductor wafer, irradiated with energy rays, and further at 260 ° C. for 5 minutes. A protective film forming film in which the reduction rate of the gloss value measured after heating is 30% or less. A composite sheet for forming a protective film, comprising a support sheet and having the protective film forming film according to claim 1 on the support sheet. A step of attaching the protective film forming film according to claim 1 or the protective film forming film in the protective film forming composite sheet according to claim 2 to a semiconductor wafer.
The semiconductor is formed by irradiating the protective film forming film after being attached to the semiconductor wafer with ultraviolet rays to form a protective film, and cutting the semiconductor wafer together with the protective film or the protective film forming film. A method for manufacturing a semiconductor chip, comprising a step of dividing a wafer to obtain a plurality of semiconductor chips.

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