JPWO2019082974A1 - A method for manufacturing a protective film forming film, a protective film forming composite sheet, and a semiconductor chip. - Google Patents

Abstract

The protective film forming film contains an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, a light transmittance of 25% or less at a wavelength of 550 nm, and a light transmittance of 25% at a wavelength of 1600 nm. That is all.

Description

The present invention relates to a protective film forming film, a protective film forming composite sheet, and a method for manufacturing a semiconductor chip.
The present application claims priority based on Japanese Patent Application No. 2017-208438 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 electrodes such as bumps on the circuit surface is used, and the electrodes are 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. Further, 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 an integrated protective film-forming film and dicing sheet.

As such a protective film-forming composite sheet, 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 so far. 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 (ultraviolet curable) that can be cured by irradiation with ultraviolet rays for forming the protective film.

Patent Document 1 discloses an ultraviolet curable pressure-sensitive adhesive sheet. This ultraviolet curable pressure-sensitive adhesive sheet is colored so that the maximum value of the transmittance in the wavelength light of 300 to 400 nm is 30% or more, and the minimum value of the transmittance in the wavelength light of 400 nm to 750 nm is 50% or less. There is.

Patent Document 2 describes (A) a polymer component composed of an acrylic copolymer having no double bond, (B) an ultraviolet curable component, (C) a dye and / or a pigment, (D) an inorganic filler, and (E) An ultraviolet curable chip protective film having an ultraviolet curable protective film forming layer containing a photopolymerization initiator that absorbs light in a long wavelength region of 350 nm or more is disclosed. Since such an ultraviolet curable chip protective film is cured mainly by ultraviolet irradiation in a short time, a protective film can be easily formed and can contribute to improvement of production efficiency.

Japanese Unexamined Patent Publication No. 2004-51736 Japanese Unexamined Patent Publication No. 2009-138026

As in Patent Document 1, when the transmittance in wavelength light of 300 to 400 nm is high, the ultraviolet curable adhesive sheet can be sufficiently cured by ultraviolet rays, but it is included in the light of a fluorescent lamp when the ultraviolet curable adhesive sheet is stored. Storage stability is lacking because curing proceeds even with ultraviolet rays.

The component (C) used in the examples of Patent Document 2 is a black pigment. The chip protection film containing a black pigment has low infrared light transmittance, and infrared inspection cannot be performed through the chip protection film.

Further, on the back surface of the semiconductor chip, grinding marks usually left by back grind processing applied to the semiconductor wafer remain. From the viewpoint of the appearance of the semiconductor chip, it is desirable that the grinding marks are covered with a protective film so that they cannot be visually seen.

Therefore, the present invention is a composite sheet for forming a protective film, which has good storage stability, has a good appearance of the semiconductor chip, and can form a protective film capable of infrared inspection via the protective film of the semiconductor chip. , And to provide a method for manufacturing the semiconductor chip.

In order to solve the above problems, the present invention contains an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, a light transmittance of 25% or less at a wavelength of 550 nm, and a light transmittance at a wavelength of 1600 nm. A film for forming a protective film having a ratio of 25% or more is provided.

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

Further, the present invention comprises a step of attaching the protective film forming film or the protective film forming film in the protective film forming composite sheet to the semiconductor wafer, and forming the protective film after the protective film is attached to the semiconductor wafer. The semiconductor wafer is divided by irradiating the film with ultraviolet rays to form a protective film and cutting the semiconductor wafer together with the protective film or the film for forming the protective film to obtain a plurality of semiconductor chips. Provided is a method for manufacturing a semiconductor chip, which comprises a process.

The protective film-forming film of the present invention can form a protective film that has good storage stability, has a good appearance of the semiconductor chip, and can be inspected by infrared rays through the protective film of the semiconductor chip. 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 the semiconductor chip.

It is sectional drawing which shows typically the protective film formation 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 in the case of using a film for forming a protective film. 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 the embodiment of the present invention contains an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a light transmittance of 25 at a wavelength of 550 nm. % Or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

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 ultraviolet rays to become a protective film. This protective film is for protecting the back surface (the surface opposite to the electrode forming surface) of the semiconductor wafer or the semiconductor chip. The protective film-forming film is soft and can be easily attached to an object to be attached.
Since the protective film-forming film is ultraviolet-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.

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, "ultraviolet curable" means a property of being cured by irradiating with ultraviolet rays, and "non-ultraviolet curable" means a property of not being cured by irradiating with ultraviolet rays.

As described above, the protective film forming film according to the present embodiment contains an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a light transmittance of 25% or less at a wavelength of 550 nm. The light transmittance at a wavelength of 1600 nm is 25% or more. The light transmittance in the present specification is a value measured using an integrating sphere, and a spectrophotometer is used as the measuring instrument.

The protective film forming film according to the present embodiment contains an ultraviolet curable component. The light transmittance of the protective film forming film at a wavelength of 350 nm is 20% or less, preferably 15% or less, more preferably 8% or less, and particularly preferably 5% or less. When the light transmittance of the protective film forming film at a wavelength of 350 nm is 20% or less, when the protective film forming film is stored, the ultraviolet light contained in the light of a fluorescent lamp or the like causes a curing reaction of the ultraviolet curable component. It can be suppressed from progressing. The light transmittance of the protective film forming film at a wavelength of 350 nm is preferably 0% or more. When the light transmittance of the protective film forming film at a wavelength of 350 nm is 0%, the protective film forming film may absorb all the light, or the protective film forming film may reflect all the light. obtain. The upper limit value and the lower limit value of the light transmittance of the protective film forming film at a wavelength of 350 nm can be arbitrarily combined. For example, the light transmittance of the protective film forming film at a wavelength of 350 nm is 0% or more and 20% or less, preferably 0% or more and 15% or less, and more preferably 0% or more and 8% or less. It is particularly preferable that it is 0% or more and 5% or less.

On the other hand, for example, on the back surface of the semiconductor chip, grinding marks due to back grind processing usually applied to the semiconductor wafer remain. When the light transmittance at a wavelength of 550 nm is 25% or less as described above, the protective film-forming film is difficult to transmit visible light. Therefore, the above-mentioned grinding marks are hidden by the protective film forming film (protective film) and are almost invisible to the naked eye. As a result, the appearance of the processed product such as a semiconductor chip becomes excellent.

From the viewpoint of hiding the grinding marks, the light transmittance of the protective film forming film at a wavelength of 550 nm is preferably 20% or less, more preferably 11% or less, and further preferably 8% or less. It is preferably 5% or less, and particularly preferably 5% or less. The lower limit of the light transmittance at a wavelength of 550 nm is not particularly limited, but it is naturally determined by setting the light transmittance at a wavelength of 350 nm to 20% or less. Specifically, the light transmittance of the protective film forming film at a wavelength of 550 nm is preferably 0% or more. The upper limit value and the lower limit value of the light transmittance of the protective film forming film at a wavelength of 550 nm can be arbitrarily combined. For example, the light transmittance of the protective film forming film at a wavelength of 550 nm is preferably 0% or more and 20% or less, more preferably 0% or more and 11% or less, and 0% or more and 8% or less. Is more preferable, and 0% or more and 5% or less is particularly preferable.

Further, the protective film forming film according to the present embodiment preferably has a light transmittance of 25% or more, more preferably 40% or more, and particularly preferably 45% or more at a wavelength of 1600 nm. Further, it is preferably 50% or more. In a semiconductor chip or the like obtained by dicing a semiconductor wafer, cracks or the like may occur due to stress generated during processing. When the light transmittance at a wavelength of 1600 nm is 25% or more as described above, the transmittance of infrared rays becomes good, and infrared rays are emitted from the protective film forming film (or the protective film formed by the protective film forming film) side. Can perform infrared inspection to obtain.
As a result, cracks or the like in a work piece such as a semiconductor chip can be found through the protective film forming film (protective film), and the product yield can be improved.

The upper limit of the light transmittance at a wavelength of 1600 nm is not particularly limited, but it is naturally determined by setting the light transmittance at a wavelength of 550 nm to 25% or less. Specifically, the light transmittance of the protective film forming film at a wavelength of 1600 nm is preferably 90% or more. When using a work piece (semiconductor chip, etc.) on which a protective film is formed, the light transmittance of the protective film forming film at a wavelength of 1600 nm is set to 90% or less, so that the work piece is susceptible to infrared rays from the outside. The operation can be prevented. The upper limit value and the lower limit value of the light transmittance of the protective film forming film at a wavelength of 1600 nm can be arbitrarily combined. For example, the light transmittance of the protective film forming film at a wavelength of 1600 nm is preferably 25% or more and 90% or less, more preferably 40% or more and 90% or less, and particularly 45% or more and 90% or less. It is preferable, and more preferably 50% or more and 90% or less.

The protective film forming film may have only one layer (single layer), may have 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 the protective film forming film, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers". "The layers may be different, and only some of the layers may be the same", and "multiple layers are different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other". It means "different".

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. Further, when the thickness of the protective film forming film is not more than the upper limit value, it is possible to prevent the 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.
Further, the "thickness of the protective film forming film" can be measured as follows. The distance between the front surface and the back surface of the protective film forming film is measured using a contact-type thickness gauge at any five points of the protective film forming film. The average value of the five measured points is taken as the thickness of the protective film forming film.
The thickness of the film, layer, semiconductor wafer, base material, etc. described below is also measured by the above method.

The curing conditions when the protective film forming 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 protective film forming film can be used. It may be appropriately selected accordingly.
For example, the illuminance of ultraviolet rays at the time of curing the protective film forming film is preferably ⁴ to 280 mW / cm ² . The amount of ultraviolet light 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 addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio and the like of each component are the same as the actual ones. Is not always the case.

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 a protective film forming composition described later. The protective film forming film 13 is ultraviolet curable.

Both the first release film 151 and the second release film 152 may be known. The light transmittance of the first release film 151 and the second release film 152 at 375 nm is not particularly limited as long as it has the effect of the present invention. In the embodiment of the present invention, the protective film forming film 13 is cured by ultraviolet light contained in light such as a fluorescent lamp, regardless of the light transmittance of the first release film 151 and the second release film 152 at 375 nm. It has the effect that the curing reaction of the sex component does not proceed easily.
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 addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

Here, the light transmittance of the protective film forming film hardly changes before or after curing. Therefore, if the light transmittance of the protective film forming film before curing is 20% or less and the light transmittance at a wavelength of 550 nm is 25% or less, the wavelength of the protective film forming film (protective film) after curing is The light transmittance at 350 nm is 20% or less, and the light transmittance at a wavelength of 550 nm is 25% or less.

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. Examples thereof include a method using various coaters such as a screen coater, a Meyer bar coater, and a knife coater.

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)>
[Ultraviolet curable component (a)]
The composition for forming a protective film contains an ultraviolet curable component (a). The ultraviolet curable component (a) is a component that is cured by irradiation with ultraviolet rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
Examples of the ultraviolet curable component (a) include a polymer (a1) having an ultraviolet curable group and having a weight average molecular weight of 80,000 to 2000000, and a compound (a2) having an ultraviolet curable group and having a molecular weight of 100 to 80,000. ). 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 ultraviolet curable group and having a weight average molecular weight of 80,000 to 2000000)
Examples of the polymer (a1) having an ultraviolet curable group and having a weight average molecular weight of 80,000 to 2000000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and the above-mentioned functional group. An acrylic resin (a1-1) obtained by polymerizing a group that reacts with a group and an ultraviolet curable compound (a12) having an ultraviolet curable group such as an ultraviolet curable double bond can be mentioned.

Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom. Group), epoxy group and the like. 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 the 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.
Further, 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, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Examples thereof include system-unsaturated alcohols (unsaturated alcohols having no (meth) acrylic skeleton).

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

Examples of the carboxy group-containing monomer include (meth) acrylic acid and ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as crotonic acid; fumaric acid, itaconic acid, maleic acid, and the like. And ethylenically unsaturated dicarboxylic acids such as citraconic acid (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. Can be mentioned.

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, and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate). Examples thereof include a (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms.

Examples of the acrylic monomer having no functional group include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkoxyalkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid; non-crosslinkable (meth) acrylamide. And derivatives thereof; (meth) acrylic acid esters having non-crosslinkable tertiary amino groups such as (meth) acrylic acid N, N-dimethylaminoethyl, and (meth) acrylic acid N, N-dimethylaminopropyl, etc. Can 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 ethylene and olefins such as norbornene; vinyl acetate; styrene and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) 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 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 units constituting the polymer 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 acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the ultraviolet curable compound (a12) is ultraviolet-curable. The content of the sex group can be easily adjusted to a preferable range for the degree of curing of the protective film.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) 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 may be arbitrary. You can choose.

In the protective film forming composition (IV-1), the content of the acrylic resin (a1-1) is 1 to 40% by mass with respect to the total mass of the protective film forming composition (IV-1). It is preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

-UV curable compound (a12)
The ultraviolet curable compound (a12) is one or more 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). Is preferable, and those having an isocyanate group as the group are more preferable. When the ultraviolet 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 UV curable compound (a12) preferably has 1 to 5 UV curable groups in one molecule, and more preferably 1 to 3 groups.

Examples of the ultraviolet 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 reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; by reacting a diisocyanate compound or polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate. Examples thereof include the obtained acryloyl monoisocyanate compound. Among these, the ultraviolet curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The ultraviolet curable compound (a12) constituting the acrylic resin (a1-1) 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 may be arbitrary. You can choose.

In the acrylic resin (a1-1), the ratio of the content of the ultraviolet curable group derived from the ultraviolet curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11). Is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is in such a range, the adhesive force of the protective film formed by curing becomes larger. When the ultraviolet 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 ultraviolet rays. 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 ultraviolet 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 only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

(Compound (a2) having an ultraviolet curable group and having a molecular weight of 100 to 80,000)
Examples of the ultraviolet curable group in the compound (a2) having an ultraviolet curable group and having a molecular weight of 100 to 80,000 include a group containing an ultraviolet curable double bond, and a (meth) acryloyl group is preferable. , And vinyl groups and the like.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, but is a low molecular weight compound having an ultraviolet curable group, an epoxy resin having an ultraviolet curable group, and a phenol resin having an ultraviolet curable group. And so on.

Among the compounds (a2), examples of the low molecular weight compound having an ultraviolet curable group include polyfunctional monomers and 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, di Propropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2 -Bifunctional (meth) acrylates such as hydroxy-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, and dipentaerythritol hexa. Polyfunctional (meth) acrylates such as (meth) acrylates;
Examples thereof include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), examples of the epoxy resin having an ultraviolet curable group and the phenol resin having an ultraviolet curable group are described in paragraph 0043 of "Japanese Unexamined Patent Publication 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.

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.

[Polymer without UV curable group (b)]
When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the ultraviolet curable component (a), the polymer (b) further having no ultraviolet curable group. ) Is also preferably contained.
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 ultraviolet 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, and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate), etc. 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 (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 ester 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; and styrene.

As the polymer (b) having no ultraviolet 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). The one that reacted with.
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, carboxy having a high reactivity with an epoxy group. Groups are preferred. However, from the viewpoint 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 ultraviolet 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 mass%. When the ratio is in such a range, the degree of cross-linking in the polymer (b) becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) having no ultraviolet curable group is 1000 to 2000000 from the viewpoint of improving the film-forming property of the protective film-forming composition (IV-1). Is preferable, and more preferably 100,000 to 1500,000.

The polymer (b) having no ultraviolet curable group 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 two kinds. In the above cases, the combination and ratio thereof can be arbitrarily selected.

Examples of the protective film-forming composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). When the protective film forming composition (IV-1) contains the compound (a2), it preferably also contains a polymer (b) having no ultraviolet curable group. In this case, the composition further contains the above. It is also preferable to contain (a1). Further, the protective film forming composition (IV-1) does not contain the compound (a2), but contains both the polymer (a1) and the polymer (b) having no ultraviolet curable group. You may.

When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no ultraviolet curable group, the protective film-forming composition (IV-1) In IV-1), the content of the compound (a2) is 10 to 400 mass by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no ultraviolet curable group. It is preferably parts, and more preferably 30 to 350 parts by mass.

In the protective film forming composition (IV-1), the ratio of the total content of the ultraviolet curable component (a) and the polymer (b) having no ultraviolet curable group to the total content of the components other than the solvent. (That is, the total content of the UV-curable component (a) and the polymer (b) having no UV-curable group with respect to the total mass of the protective film-forming film) is 5 to 90. It is preferably 10 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 15 to 70% by mass, and for example, in any of 20 to 60% by mass and 25 to 50% by mass. There may be. When the ratio of the total content is in such a range, the ultraviolet curability of the protective film forming film becomes better.

When the protective film-forming composition (IV-1) contains the ultraviolet-curable component (a) and the polymer (b) having no ultraviolet-curable group, the protective film-forming composition (IV-1) and In the film for forming a protective film, the content of the polymer (b) is preferably 50 to 400 parts by mass, preferably 100 to 350 parts by mass with respect to 100 parts by mass of the content of the ultraviolet curable component (a). It is more preferably parts, and particularly preferably 150 to 300 parts by mass. When the content of the polymer (b) is in such a range, the ultraviolet curability of the protective film-forming film becomes better.

The composition for forming a protective film (IV-1) is filled with a photopolymerization initiator (c) other than the ultraviolet curable component (a) and the polymer (b) having no ultraviolet curable group, depending on the purpose. From the group consisting of the material (d), the coupling agent (e), the cross-linking agent (f), the colorant (g), the thermosetting component (h), the curing accelerator (i), and the general-purpose additive (z). It may contain one or more selected species.
For example, the protective film-forming film formed by using the protective film-forming composition (IV-1) containing the ultraviolet curable component (a) and the thermosetting component (h) is covered by heating. The adhesive force to the body 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, Acetphenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) ) Acylphosphine oxide compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; 1-hydroxycyclohexylphenylketone and the like. α-Ketol compound; azo compound such as azobisisobutyronitrile; titanosen compound such as titanosen; thioxanthone compound such as thioxanthone; benzophenone, and 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl Benzoyl compounds such as -1-butanone, 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; and 2-chloro Anthraquinone and the like can be mentioned.
Further, as the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; and 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 ultraviolet curable compound (a). On the other hand, it 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)]
When the protective film-forming film contains the filler (d), the light transmittance of the protective film-forming film can be adjusted. Further, 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. 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. Further, 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 powders such as, for example, silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Quality products; 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. 3 to 10 μm is more preferable. 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 to the object to be formed of the protective film.
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. Further, 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 the functional group of the ultraviolet curable component (a), the polymer (b) having no ultraviolet curable group, or the like, and is preferably a silane cup. More preferably, it is a ring 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) tetrasulfan, 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 ultraviolet curable component (a) and the ultraviolet curing. The total content of the polymer (b) having no sex group is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass. It is particularly preferably 1 to 5 parts by mass. When the content of the coupling agent (e) is equal to or higher than the lower limit, 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 not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (f)]
The protective film forming composition (IV-1) may contain a cross-linking agent (f). By cross-linking the above-mentioned ultraviolet curable component (a) and polymer (b) having no ultraviolet curable group using a cross-linking agent (f), the initial adhesive force and cohesive force of the protective film forming film can be increased. Can be adjusted.

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 (a cross-linking agent having a metal chelate structure), and an aziridine-based cross-linking agent (a cross-linking agent having an aziridine group). And so on.

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" is a low content of the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound or the alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. 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. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion 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 Examples thereof include compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of polyol such as propane; and lysine diisocyanate.

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 and N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine.

When an organic polyhydric isocyanate compound is used as the cross-linking agent (f), it is preferable to use a hydroxyl group-containing polymer as the ultraviolet-curable component (a) or the polymer (b) having no ultraviolet-curable group. When the cross-linking agent (f) has an isocyanate group and the ultraviolet-curable component (a) or the polymer (b) having no ultraviolet-curable group has a hydroxyl group, the cross-linking agent (f) and the ultraviolet-curable component (a) ) Or the crosslinked structure can be easily introduced into the protective film-forming film by the reaction with the polymer (b) having no ultraviolet curable group.

The protective film-forming composition (IV-1) and the cross-linking agent (f) contained in the protective film-forming film 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.

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 the polymer having no ultraviolet curable component (a) and an ultraviolet curable group ( b) The total content of 100 parts by mass 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. Is particularly preferable. 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. Further, 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 type, two or more types, or a combination thereof when two or more types are used. And the ratio is that the light transmittance of the protective film forming composition (IV-1) and the protective film forming film at a wavelength of 350 nm is 20% or less, the light transmittance at a wavelength of 550 nm is 25% or less, and the light transmittance at a wavelength of 1600 nm. Is adjusted to be 25% or more. The colorant (g) preferably contains at least a blue pigment, and more preferably contains a blue pigment, a yellow pigment, and a red pigment. Here, as the blue dye, for example, a phthalocyanine dye is preferable, as the yellow dye, for example, an isoindolinone dye is preferable, and as the red dye, for example, an anthraquinone dye is preferable.

The content of the protective film-forming composition (IV-1) and the colorant (g) of the protective film-forming film is such that the protective film-forming composition (IV-1) and the protective film-forming film have a wavelength of 350 nm. The transmittance is adjusted to be 20% or less, the light transmittance at a wavelength of 550 nm is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

The protective film-forming composition (IV-1) and the protective film-forming film so that the light transmittance of the protective film-forming composition (IV-1) and the protective film-forming film at a wavelength of 350 nm is 20% or less. The content of the blue-based dye in the above is preferably 25 to 50 parts by mass with respect to 100 parts by mass of the total content of the colorant (g).

In the protective film-forming composition (IV-1), the ratio of the content of the colorant (g) to the total content of all the components other than the solvent (that is, the content of the colorant (g) of the protective film-forming film). The amount) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass. When the content of the colorant (g) is at least the lower limit, the light transmittance of the protective film forming composition (IV-1) and the protective film forming film at a wavelength of 350 nm is 20% or less, and the wavelength is 550 nm. The light transmittance of the film is adjusted to 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more. Further, when the content of the colorant (g) is not more than the upper limit value, the excessive use of the colorant (g) is suppressed.

[Thermosetting component (h)]
The protective film-forming composition (IV-1) and the protective film-forming film may contain a 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 can be arbitrarily selected.

Examples of the thermosetting component (h) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy-based thermosetting resins are 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. Examples thereof include bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. 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.
Further, 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. , And (meth) 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. More preferably, it is particularly preferably 500 to 3000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.

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, and a group in which an acid group is annealed, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, and 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.
Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, and an aromatic ring of the phenol resin. Examples thereof include compounds in which a group having an unsaturated 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. ..

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 ultraviolet curable group.

[Curing Accelerator (i)]
The protective film-forming composition (IV-1) and the protective film-forming film may contain a 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, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenyl. Imidazoles such as imidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, and tri. Organic phosphines such as phenylphosphine; tetraphenylphosphonium tetraphenylborate, tetraphenylboron salt 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 protective film-forming composition (IV-1) and the protective film-forming film may contain a 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 (2-methylpropan-1-ol), 1-butanol and the like. Examples thereof include 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).
The solvent contained in the protective film forming composition (IV-1) may be only one type, two or more types, and when two or more types are used, 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.

<< 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 a 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 in a state where release films are 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 The protective film-forming film can be provided on a support sheet as described above to form a protective film-forming composite sheet. 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, a protective film-forming film is attached to the back surface of the semiconductor wafer, and then a 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 ultraviolet rays and cured to form a protective film, and then on the exposed surface of the protective film (the surface opposite to the side attached to the semiconductor wafer). The support sheets are bonded together to form a composite sheet for forming 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 a protective film will be described in detail.

◎ Support sheet The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When 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 a 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 explained figures are designated by the same reference numerals as in the case of the already explained 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 the present 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). Further, 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 has an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a light transmittance of 25% or less at a wavelength of 550 nm. The light transmittance at a wavelength of 1600 nm is 25% or more.

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 the jig adhesive layer 16 is not provided. 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 has an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a light transmittance of 25% or less at a wavelength of 550 nm. The light transmittance at a wavelength of 1600 nm is 25% or more.

The protective film-forming composite sheet 1B shown in FIG. 3 has a semiconductor wafer (not shown) 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 attached, and the area near the peripheral edge is attached 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 jig adhesive layer 16 is laminated in the vicinity, and the region of the first surface 13a of the protective film forming film 13 where the jig adhesive layer 16 is not laminated and the jig adhesive layer 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 has an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a wavelength of 550 nm. The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

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 a jig 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 has an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a wavelength of 550 nm. The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

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 region 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 the base material 11, the pressure-sensitive adhesive layer 12 on the base material 11, and the 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. Further, 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 has an ultraviolet curable component, has a light transmittance of 20% or less at a wavelength of 350 nm, and has a wavelength of 550 nm. The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

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 with the release film 15 removed, and further, the pressure-sensitive adhesive layer is attached. 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, those shown in FIGS. 2 and 4 are 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. The jig adhesive layer may be laminated in the same manner as in (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 protective film-forming composite sheet provided with a jig adhesive layer, a jig adhesive layer is provided 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.
Further, 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.
Further, in the protective film forming composite sheet shown in FIGS. 2 to 6, a layer other than the intermediate layer may be provided at an arbitrary position.
Further, in the protective film forming composite sheet, a partial gap may be formed between the release film and the layer in direct contact with the release film.
Further, 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-ultraviolet 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 ultraviolet curability, the support sheet preferably transmits ultraviolet rays.

For example, in the support sheet, the transmittance of light having a wavelength of 350 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 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 350 nm is not particularly limited. For example, the light transmittance may be 95% or less.
The lower limit value and the upper limit value of the transmittance of light having a wavelength of 350 nm of the support sheet can be arbitrarily combined. For example, the transmittance of light having a wavelength of 350 nm of the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less. preferable.

Further, 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.
The lower limit value and the upper limit value of the transmittance of light having a wavelength of 532 nm of the support sheet can be arbitrarily combined. For example, the transmittance of light having a wavelength of 532 nm of the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less. preferable.

Further, 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.
The lower limit value and the upper limit value of the light transmittance of the support sheet having a wavelength of 1064 nm can be arbitrarily combined. For example, the transmittance of light having a wavelength of 1064 nm of the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less. preferable.

Further, 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 to form a modified layer 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.
The lower and upper limits of the light transmittance of the support sheet having a wavelength of 1342 nm can be arbitrarily combined. For example, the transmittance of light having a wavelength of 1342 nm on the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less. preferable.
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); polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene other than: Polyethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and ethylene-norbornene copolymer ( Copolymer obtained using polyethylene as a monomer); Vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and polyesters such as all aromatic polyesters in which all constituent units have an aromatic cyclic group; two or more. Poly (meth) acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; and polyether ketone and the like.
Further, 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.
Further, as the resin, for example, a crosslinked resin obtained by cross-linking one or more of the resins exemplified above; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

The resin constituting the base material 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 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, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.

It is preferable that the base material has high thickness accuracy, that is, a base material in which variation in thickness is suppressed regardless of the site. Among the above-mentioned constituent materials, as materials that can be used to compose such a highly accurate base material of thickness, for example, polyethylene, polyolefins 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). You may.

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 ultraviolet curability, the base material preferably transmits ultraviolet rays.

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

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

○ Adhesive layer The pressure-sensitive adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, and polycarbonates and ester-based resins. 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 has adhesiveness but also the resin itself has adhesiveness. It also includes a resin that exhibits adhesiveness when used in combination with other components such as additives, 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.

The optical properties of the pressure-sensitive adhesive layer preferably satisfy the optical properties 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 ultraviolet curability, the pressure-sensitive adhesive layer preferably transmits ultraviolet rays.

The pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive other than ultraviolet rays, or may be formed by using a non-energy ray-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer formed by using an energy ray-curable pressure-sensitive adhesive other than ultraviolet rays can easily adjust the physical properties before and after curing. Here, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include radiation and an electron beam. "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.

<< 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, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. , Meyer bar coater, and a method using various coaters such as 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 at 70 to 130 ° C. for 10 seconds to 5 minutes, for example.

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)"). Adhesive composition (I-2) containing (may be abbreviated); adhesive composition (I-3) containing the adhesive 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 , And icosyl (meth) 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 alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms, from the viewpoint of further improving the adhesive force of the pressure-sensitive adhesive layer. Further, 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. By doing so, it is possible to introduce 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, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Examples thereof include system-unsaturated alcohols (unsaturated alcohols having no (meth) acrylic skeleton).

Examples of the carboxy group-containing monomer include (meth) acrylic acid and ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as crotonic acid; fumaric acid, itaconic acid, maleic acid, and the like. And ethylenically unsaturated dicarboxylic acids such as citraconic acid (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. Can be mentioned.

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 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 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 amount of the structural units. It is 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, two or more kinds, or two or more kinds, and 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, the above-mentioned energy ray-curable adhesive resin obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (ultraviolet polymerizable group) is obtained. It can be used as (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 resin (I-1a) is preferably 5 to 99% by mass, preferably 10 to 95% by mass, based on the total content of the components other than the solvent. Is more preferable, and 15 to 90% by mass is particularly preferable.

[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 and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; and Examples thereof include epoxy (meth) acrylate.
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 1 to 95% by mass with respect to the total content of the components other than the solvent of the pressure-sensitive adhesive composition (I-1). It is preferably 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; epoxy-based cross-linking agents such as ethylene glycol glycidyl ether. (Crosslinking agent having a glycidyl group); Aziridine-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (cross-linking agent having an aziridinyl group); Metal chelate-based cross-linking agent such as aluminum chelate ( Crosslinking agent having a metal chelate structure); Isocyanurate-based crosslinking agent (crosslinking agent having an isocyanate skeleton) and the like can be mentioned.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoint 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, 2- Acetphenone compounds such as hydroxy-2-methyl-1-phenyl-propane-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α- such as 1-hydroxycyclohexylphenylketone. Ketol compounds; azo compounds such as azobisisobutyronitrile; titanosen 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; and 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can 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 antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, and tackifiers. , Reaction retarders, and known additives such as cross-linking accelerators (catalysts).
The reaction retarder means, for example, that an unintended cross-linking reaction occurs in the pressure-sensitive adhesive composition (I-1) during storage due to the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses the progress. 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.

In the pressure-sensitive adhesive composition (I-1), the content of other additives is not particularly limited, and may be appropriately selected depending on the type 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 the organic solvent includes, for example, a ketone such as methyl ethyl ketone and acetone; an ester such as ethyl acetate (carboxylic acid ester); an ether such as tetrahydrofuran and dioxane; cyclohexane, and n. -Adipose hydrocarbons such as hexane; 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 bond with 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 (meth) acryloyl group. 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 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 resin (I-2a) is preferably 5 to 99% by mass, preferably 10 to 95% by mass, based on the total mass of the components other than the solvent. It is more preferable, and it is particularly preferable that it is 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 additives 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, the combination and ratio thereof 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 resin (I-2a) is preferably 5 to 99% by mass, preferably 10 to 95% by mass, based on the total mass of the components other than the solvent. More preferably, it is particularly 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.

In the pressure-sensitive adhesive composition (I-3), the content of other additives is not particularly limited, and may be appropriately selected depending on the type 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 the present 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 rays such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. Examples thereof include a pressure-sensitive adhesive composition (I-4) containing a curable pressure-sensitive adhesive 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 resin (I-1a) is preferably 5 to 99% by mass, preferably 10 to 95% by mass, based on the total mass of the components other than the solvent. It is more preferable to have it, and it is particularly preferable that it is 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 protective film forming composite sheet, the pressure-sensitive adhesive layer is preferably non-ultraviolet curable. This is because if the pressure-sensitive adhesive layer is ultraviolet-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 ultraviolet 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-ultraviolet 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-ultraviolet 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, this layer If is non-UV curable, the same effect can be achieved.

<< Manufacturing method of adhesive composition >>
Adhesive compositions other than the adhesive compositions (I-1) to (I-3) and the adhesive compositions (I-1) to (I-3) such as the 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 known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; and a method of adding ultrasonic waves to mix. It may be selected appropriately from.
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 of manufacturing a protective film-forming composite sheet The protective film-forming composite sheet 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 onto 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, a 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. Layers other than the protective film-forming film can also 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). In the case of producing a protective film-forming composite sheet), an adhesive composition is applied onto a base material and dried if 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 as 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. A composite sheet for use is obtained.

When the pressure-sensitive adhesive layer is laminated on the base material, the pressure-sensitive adhesive composition is applied on the release film instead of the method of applying the pressure-sensitive adhesive composition on the base material as described above. An adhesive layer is formed on the release film by drying as necessary, and the exposed surface of this layer is bonded to one surface of the base material to form an adhesive layer on the base material. It may be laminated.
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 that employs such a process may be appropriately selected to produce a protective film-forming composite sheet.

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") (hereinafter, "divided"). (Sometimes 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. Further, 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. Is.

<< 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 pasting step of the manufacturing method (1), as shown in FIG. 7A, the protective film forming film 13 is pasted 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. Further, in the semiconductor wafer 9, the illustration of bumps and the like on the circuit surface is omitted here.

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. 7 (b), A protective film 13'is formed on the semiconductor wafer 9. 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). In the document, 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"). To do. 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. To obtain the 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'.

Note that 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), since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into semiconductor chips 9'in the dividing step, the protective film 13'or after cutting is used. The floating of the semiconductor chip 9'from the protective film 130' can be suppressed.

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 using a protective film-forming composite sheet in which a protective film-forming film is integrated with a support sheet in advance >>
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), A protective film 13'is formed on the semiconductor 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.

Further, 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. As shown in c), 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'is obtained as a semiconductor chip with a protective film.

In the manufacturing method (2), since the protective film forming film 13 is used, when the semiconductor wafer 9 is divided into semiconductor chips 9'in the dividing step, the protective film 13'or after cutting is used. The floating of the semiconductor chip 9'from the protective film 130' can be suppressed.

In the manufacturing method (2), 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.

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 to these.
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.
Further, as the support sheet, a semiconductor chip can be similarly used 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. Can be manufactured.
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 that, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate by the same method as the conventional method, and then the semiconductor package is formed. Then, the target semiconductor device may be manufactured using this semiconductor package (not shown).

As one aspect of the present invention, the protective film forming film contains an ultraviolet curable component, has a light transmittance of 0% or more and 15% or less at a wavelength of 350 nm, and has a light transmittance of 0% or more and 20 at a wavelength of 550 nm. % Or less, and the light transmittance at a wavelength of 1600 nm is 50% or more and 90% or less.
The protective film-forming film may further contain a colorant containing a blue-based dye, a yellow-based dye, and a red-based dye. The blue dye may be a phthalocyanine dye, the yellow dye may be an isoindolinone dye, and the red dye may be an anthraquinone dye.
In the protective film forming film, the content of the colorant with respect to the total mass of the protective film forming film may be 0.4 to 7.5% by mass.
The protective film-forming film may further contain an inorganic filler having an average particle size of 3 to 10 μm.
The protective film-forming film may further contain a polymer having no energy ray-curable group.
In the protective film forming film, the total of the ultraviolet curable component and the polymer having no energy ray curable group may be 25 to 50% by mass with respect to the total mass of the protective film forming film.
In the protective film forming film, the content of the polymer having no energy ray-curable group may be 150 to 300 parts by mass with respect to 100 parts by mass of the content of the ultraviolet curable component.

As one aspect of the present invention, the protective film forming film contains an ultraviolet curable component, has a light transmittance of 0% or more and 5% or less at a wavelength of 350 nm, and has a light transmittance of 0% or more and 5% at a wavelength of 550 nm. % Or less, and the light transmittance at a wavelength of 1600 nm is 50% or more and 90% or less.
The protective film-forming film may further contain a colorant containing a blue-based dye, a yellow-based dye, and a red-based dye. The blue dye may be a phthalocyanine dye, the yellow dye may be an isoindolinone dye, and the red dye may be an anthraquinone dye.
In the protective film forming film, the content of the colorant with respect to the total mass of the protective film forming film may be 0.4 to 7.5% by mass.
The protective film-forming film may further contain an inorganic filler having an average particle size of 3 to 10 μm.
The protective film-forming film may further contain a polymer having no energy ray-curable group.
In the protective film forming film, the total of the ultraviolet curable component and the polymer having no energy ray curable group may be 25 to 50% by mass with respect to the total mass of the protective film forming film.
In the protective film forming film, the content of the polymer having no energy ray-curable group may be 150 to 300 parts by mass with respect to 100 parts by mass of the content of the ultraviolet curable component.

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.

<Raw material for manufacturing protective film forming composition>
The raw materials used for producing the protective film forming composition are shown below.
[UV 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) [with UV curable group Polymer (b) that does not.
(B) -1: Acrylic polymer (weight average molecular weight) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass). 300,000, 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).

[Example 1]
<Manufacturing of protective film forming film>
(Production of composition for forming a protective film (IV-1))
UV curable component (a2) -1, polymer (b) -1, photopolymerization initiator (c) -1, filler (d) -1, coupling agent (e) -1, and colorant (g) ) -1 and are dissolved or dispersed in methyl ethyl ketone so that their contents (solid content, parts by mass) are as shown in Table 1, and the mixture is stirred at 23 ° C. to bring the solid content concentration to 50% by mass. The composition for forming a protective film (IV-1) was prepared.

A first release sheet (Lintec Corporation: SP-PET381130, thickness 38 μm) in which a silicone-based release agent layer is formed on one side of a polyethylene terephthalate (PET) film, and a silicone-based release agent on one side of the PET film. A second release sheet (manufactured by Lintec Corporation: SP-PET381031, thickness 38 μm) on which a layer was formed was prepared.

The above-mentioned protective film forming composition (IV-1) is applied on the peeling surface of the first release sheet with a knife coater, and then dried in an oven at 120 ° C. for 2 minutes to form a protective film forming film. Was formed. The thickness of the obtained protective film forming film was 25 μm. Next, the release surface of the second release sheet is overlapped with the protective film forming film and the two are bonded to each other, and the first release sheet (release sheet 151 in FIG. 1) and the protective film forming film (protection film in FIG. 1) are laminated. A protective film-forming film composed of a forming film 13) (thickness: 25 μm) and a second release sheet (release sheet 152 in FIG. 1) was obtained.

<Manufacturing of composite sheet for forming protective film>
(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 Industry 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 a release film (second release film, "SP-PET382150" manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film is peeled by a silicone treatment. The composition (IV-1) for use 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 for 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. Moreover, the first release film was removed from the laminated film obtained above. Then, by adhering the exposed surface of the pressure-sensitive adhesive layer generated by removing the above-mentioned release film and the exposed surface of the protective film forming film generated by removing the above-mentioned first release film, the base material and the adhesive 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 light transmittance)
The first release sheet and the second release sheet were peeled from the protective film forming film obtained in Examples and Comparative Examples, and these were used as measurement samples.

Using a spectrophotometer (UV-VIS-NIR SPECTROPHOTOMETER UV-3600, manufactured by SHIMADZU), the light transmittance of the above measurement sample was measured, and the wavelengths were 350 nm (ultraviolet light), 550 nm (visible light) and 1600 nm (red). The light transmittance (%) of (external light) was extracted. A built-in integrating sphere was used for the measurement. The results are shown in Table 1.

(Measurement of shear strength reduction rate)
The protective film-forming composite sheet obtained above was stored for 30 days under 30 cm of a 27 watt fluorescent lamp (1). The first release film of the protective film-forming composite sheet was removed, and the exposed surface of the protective film-forming film thus formed was attached to the # 2000 polished surface of a 6-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. Further, 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 laminated body laminated in these thickness directions was 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 form a protective film, and a silicon wafer with a protective film was obtained.
Next, using a dicing blade, the silicon wafer is diced together with the protective film (dicing the silicon wafer with the protective film) to individualize the silicon wafer, and the size is 3 mm × 3 mm, and the silicon chip with the protective film (silicon with the protective film). Multiple chips) were obtained.

Next, using a universal bond tester (“DAGE4000” manufactured by Nordson Advanced Technology Co., Ltd.), only the protective film of the silicon chip with protective film is used at a speed of 200 μm / s by a share tool under the condition of 23 ° C. A force was applied toward the surface of the protective film. Then, the maximum value of the force applied until the protective film was broken was confirmed, and this was defined as the shear strength (N / 3 mm □).

The shear strength of the protective film formed by the protective film-forming composite sheet stored in the dark room was measured in the same manner. The rate of decrease in the shear strength of the protective film formed by the protective film-forming composite sheet stored in a fluorescent lamp for 30 days with respect to the shear strength of the protective film formed by the protective film-forming composite sheet stored in a dark room. Was less than 20%, it was judged that the rate of decrease in shear strength was low. The results are shown in Table 1.

<Manufacturing of composite sheet for forming protective film and evaluation of protective film>
[Example 2, Comparative Examples 1 and 2]
The protective film-forming film and the protective film-forming composite were obtained in the same manner as in Example 1 except that the amounts of the compounding components at the time of producing the protective film-forming composition (IV-1) were as shown in Table 1. Sheets were manufactured and protective films were evaluated. The results are shown in Table 1.

As is clear from the above results, in Examples 1 and 2, since the light transmittance at 350 nm is 20% or less, the shear strength reduction rate is high even when the protective film forming composite sheet is stored under a fluorescent lamp. It was as low as 11% or less. On the other hand, in Comparative Examples 1 and 2, the rate of decrease in shear strength when the protective film-forming composite sheet was stored under fluorescent light was as high as 24% or more, and the storage stability of the protective film-forming composite sheet was low.

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, 130 ... Protective film forming film after cutting, 13a, 23a ... Surface of protective film forming film (first surface), 13b ... Surface of protective film forming film (second surface), 13' ... Protective film, 130'... Protective film after cutting, 15 ... Release film, 151 ... First release film, 152 ... Second release film, 16 ... Adhesion for jigs Agent layer, 16a ... front surface of adhesive layer for jigs, 9 ... semiconductor wafer, 9b ... back surface of semiconductor wafer, 9'... semiconductor chip

Claims (3)

Contains UV curable ingredients,
The light transmittance at a wavelength of 350 nm is 20% or less,
The light transmittance at a wavelength of 550 nm is 25% or less,
A film for forming a protective film having a light transmittance of 25% or more at a wavelength of 1600 nm. 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, and after attaching the protective film to the semiconductor wafer. The semiconductor wafer is divided into a plurality of steps by irradiating the protective film forming film with ultraviolet rays to form the 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 obtaining a semiconductor chip.

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