WO2017188229A1

WO2017188229A1 - Film for forming protective coating, composite sheet for forming protective coating, and method for manufacturing semiconductor chip

Info

Publication number: WO2017188229A1
Application number: PCT/JP2017/016328
Authority: WO
Inventors: 健太古野; 洋一稲男
Original assignee: リンテック株式会社
Priority date: 2016-04-28
Filing date: 2017-04-25
Publication date: 2017-11-02
Also published as: KR102303923B1; JP6854811B2; CN108713248B; JPWO2017188229A1; TWI719200B; CN108713248A; TW201802156A; KR20190003463A

Abstract

This film for forming a protective coating satisfies both condition (1): the transmittance therethrough of laser light having a 1342-nm wavelength is 45% or more, and condition (2): the transmittance therethrough of laser light having a 1250-nm wavelength is 35% or more. This composite sheet for forming a protective coating comprises: a support sheet; and said film for forming a protective coating provided on the support sheet.

Description

Protective film forming film, protective film forming composite sheet, and semiconductor chip manufacturing method

The present invention relates to a protective film forming film, a protective film forming composite sheet, and a method of manufacturing a semiconductor chip.
This application claims priority based on Japanese Patent Application No. 2016-092016 filed in Japan on April 28, 2016, the contents of which are incorporated herein by reference.

In recent years, a semiconductor device using a mounting method called a so-called face-down method has been manufactured. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the back surface opposite to the circuit surface of the semiconductor chip may be exposed.

A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip and may be taken into the 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 comprising a protective film-forming film for forming a protective film on a support sheet is used. In the protective film forming composite sheet, the protective film forming film can form a protective film by curing, and the support sheet can be used as a dicing sheet, and the protective film forming film and the dicing sheet are integrated. It is possible that

As such a composite sheet for forming a protective film, for example, a sheet provided with a thermosetting protective film forming film that forms a protective film by being cured by heating has been mainly used so far. However, since heat curing of a thermosetting protective film-forming film usually takes a long time of about several hours, it is desired to shorten the curing time. On the other hand, use of a protective film-forming film that can be cured by irradiation with energy rays such as ultraviolet rays has been studied. For example, an energy ray curable protective film (see Patent Document 1) formed on a release film, and an energy ray curable chip protective film that can form a protective film having high hardness and excellent adhesion to a semiconductor chip (Patent Document) 2).

When using a composite sheet for forming a protective film provided with such an energy ray-curable protective film-forming film, for example, for forming a protective film on the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) After affixing the protective film-forming composite sheet with the film, the semiconductor wafer is divided into the protective film-forming film by dicing to form a semiconductor chip, and the protective film-forming film is cured by irradiation with energy rays to form a protective film. There is. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is stuck.

However, when the protective film forming film is cured after dicing, the protective film forming film divided together with the semiconductor wafer by dicing is exposed to the air until the divided surface is cured. Become. Then, this divided surface is also exposed to oxygen contained in the air, but the protective film-forming film exposed to such oxygen undergoes a curing reaction by oxygen even when irradiated with energy rays. Since it is inhibited, curing becomes insufficient. As a result, the semiconductor chip with the protective film cannot be picked up, the protection effect of the back surface of the semiconductor chip is reduced, and when the semiconductor chip with the protective film is stored, the semiconductor chip with the protective film is provided by a protective film at a location other than the intended location Will cause problems such as sticking.

In the manufacturing process of a semiconductor device, the state of a semiconductor wafer or a semiconductor chip having a protective film forming film or a protective film may be inspected by an infrared camera or the like through the protective film forming film or the protective film. Therefore, a composite sheet for forming a protective film is desired to have good infrared transmittance. In general, if the infrared ray permeability of the protective film-forming film is good, the infrared ray permeability of the protective film is also good.

On the other hand, the energy beam curable protective film disclosed in Patent Document 1 and the energy beam curable chip protective film disclosed in Patent Document 2 are both poorly cured on the divided surfaces as described above. It is not intended to achieve both the suppression of the occurrence of defects associated with the above and having good infrared transparency.

Japanese Patent No. 5144433 JP 2010-031183 A

The present invention is for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip, can suppress the occurrence of problems associated with poor curing of the divided surface, and has energy ray curable protection with good infrared transparency. It aims at providing the film for film formation, and the composite sheet for protective film formation provided with the said film.

In order to solve the above problems, the present invention provides a protective film-forming film having energy ray curability and satisfying both of the following conditions (1) and (2).
(1) The transmittance of laser light having a wavelength of 1342 nm is 45% or more.
(2) The transmittance of laser light having a wavelength of 1250 nm is 35% or more.

Moreover, this invention provides the composite sheet for protective film formation provided with the support sheet and providing the said film for protective film formation on the said support sheet.
The present invention also includes a step of attaching the protective film forming film in the protective film forming film or the protective film forming composite sheet to a semiconductor wafer, and the protective film forming film attached to the semiconductor wafer. Irradiating energy rays to the semiconductor wafer, forming a protective film on the semiconductor wafer, and passing through the protective film or the protective film forming film so as to focus on a focal point set inside the semiconductor wafer. Irradiating a laser beam in the outer region to form a modified layer inside the semiconductor wafer, and applying force to the semiconductor wafer on which the modified layer has been formed, so that the semiconductor is formed at the modified layer. A method of manufacturing a semiconductor chip, comprising: dividing a wafer to obtain a plurality of semiconductor chips.

By using the protective film-forming film and the protective film-forming composite sheet of the present invention, a protective film can be formed on the back surface of the semiconductor wafer or semiconductor chip, resulting in problems associated with poor curing of the dividing surface of the protective film-forming film. Can be suppressed. In the manufacturing process of the semiconductor device, the state of the semiconductor wafer or the semiconductor chip provided with the protective film forming film or the protective film can be satisfactorily inspected by an infrared camera or the like through the protective film forming film or the protective film.

It is sectional drawing which shows typically one Embodiment of the film for protective film formation of this invention. It is sectional drawing which shows typically one Embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip when using the film for protective film formation of this invention independently. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip when using the film for protective film formation of this invention independently. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip when using the film for protective film formation of this invention independently. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip when using the film for protective film formation of this invention independently. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip when using the film for protective film formation of this invention independently. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip in the case of integrating and using the film for protective film formation of this invention previously with a support sheet. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip in the case of integrating and using the film for protective film formation of this invention previously with a support sheet. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip in the case of integrating and using the film for protective film formation of this invention previously with a support sheet. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of a semiconductor chip in the case of integrating and using the film for protective film formation of this invention previously with a support sheet.

◇ Protective film-forming film The protective film-forming film of the present invention has energy ray curability and satisfies both the following conditions (1) and (2).
(1) The transmittance of laser light having a wavelength of 1342 nm (hereinafter sometimes abbreviated as “transmittance (1342 nm)”) is 45% or more.
(2) The transmittance of laser light having a wavelength of 1250 nm (hereinafter sometimes abbreviated as “transmittance (1250 nm)”) is 35% or more.
As will be described later, a protective film-forming composite sheet can be formed by providing the protective film-forming film on a support sheet.

The protective film-forming film is cured by irradiation with energy rays and becomes a protective film. This protective film is for protecting the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer or 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 energy ray curable, the protective film can be formed by curing in a shorter time than a thermosetting protective film-forming film.

In this specification, “protective film forming film” means a film before curing, and “protective film” means a film obtained by curing a protective film forming film.

Examples of the protective film-forming film include those containing an energy ray-curable component (a) and a colorant (g) described later.
The energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.

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

The laser beam having a wavelength of 1342 nm under the condition (1) is suitable for irradiating a semiconductor wafer and forming a modified layer therein by a method described later. And when the transmittance | permeability (1342 nm) of the film for protective film formation is high, the transmittance | permeability (1342 nm) of the protective film formed by hardening | curing this film is also high. Therefore, the protective film-forming film satisfying the condition (1) is suitable for forming a modified layer by irradiating the semiconductor wafer with laser light having a wavelength of 1342 nm through or through the protective film. is there.

On the other hand, the semiconductor wafer on which the modified layer is formed is divided at the portion where the modified layer is formed by applying a force to form a semiconductor chip. At this time, the semiconductor wafer is usually divided together with the protective film stuck on the back surface thereof, and is not divided in the state of the protective film forming film, so that the divided surface of the protective film forming film may be exposed to the air. There is no exposure to oxygen. Therefore, since the curing reaction due to oxygen is not inhibited during irradiation with energy rays, the entire protective film-forming film is sufficiently cured. As a result, for example, a semiconductor chip with a protective film cannot be picked up, and the protective effect of the back surface of the semiconductor chip is reduced. It is possible to avoid the occurrence of problems such as the semiconductor chip adhering.
Thus, the film for protective film formation of this invention can avoid generation | occurrence | production of the malfunction resulting from the hardening in the division | segmentation surface becoming inadequate by satisfy | filling conditions (1).

The transmittance (1342 nm) of the protective film-forming film is preferably 50% or more, and more preferably 55% or more. When the transmittance (1342 nm) is equal to or higher than the lower limit, the effect of the present invention can be obtained more remarkably.
The upper limit value of the transmittance (1342 nm) is not particularly limited, and may be 100%, for example.

On the other hand, the laser beam having a wavelength of 1250 nm in the condition (2) is suitable for inspecting the state of the semiconductor wafer or the semiconductor chip with an infrared camera or the like by a method described later. And when the transmittance | permeability (1250 nm) of the film for protective film formation is high, the transmittance | permeability (1250 nm) is similarly high also in the protective film formed by hardening | curing this film.
As described above, the protective film-forming film of the present invention is suitable for inspecting the state of the semiconductor wafer or the semiconductor chip through the condition (2) or through the protective film.

The transmittance (1250 nm) of the protective film-forming film is preferably 40% or more, and more preferably 45% or more. When the transmittance (1250 nm) is equal to or higher than the lower limit, the effects of the present invention can be obtained more remarkably.
The upper limit value of the transmittance (1250 nm) is not particularly limited, and may be 100%, for example.

The film for forming the protective film after curing, that is, the protective film, has a transmittance of laser light having a wavelength of 1342 nm (hereinafter sometimes abbreviated as “protective film transmittance (1342 nm)”) of 45% or more. Preferably, it is 50% or more, more preferably 55% or more. When the protective film transmittance (1342 nm) is equal to or higher than the lower limit, the effect of the present invention can be obtained more remarkably.
The upper limit value of the protective film transmittance (1342 nm) is not particularly limited, and may be, for example, 100%.

The transmittance of laser light having a wavelength of the protective film of 1250 nm (hereinafter sometimes abbreviated as “protective film transmittance (1250 nm)”) is preferably 35% or more, and preferably 40% or more. Is more preferable, and 45% or more is particularly preferable. When the protective film transmittance (1250 nm) is equal to or higher than the lower limit, the effect of the present invention can be obtained more remarkably.
The upper limit value of the protective film transmittance (1250 nm) is not particularly limited, and may be 100%, for example.

Hereinafter, in the present specification, the simple descriptions of “transmittance (1342 nm)” and “transmittance (1250 nm)” mean the transmittance of the protective film-forming film, respectively.

The transmittance (1342 nm) and transmittance (1250 nm), and the protective film transmittance (1342 nm) and the protective film transmittance (1250 nm) of the protective film-forming film are, for example, the types of components contained in the protective film-forming film and It can adjust suitably by adjusting quantity etc.

For example, the type and amount of the component contained in the protective film-forming film can be adjusted by the type and amount of the component contained in the protective film-forming composition described below. And among the components of the protective film forming composition, for example, by adjusting the type and content of the colorant (g), the transmittance (1342 nm) and the transmittance (1250 nm) of the protective film forming film, In addition, the protective film transmittance (1342 nm) and the protective film transmittance (1250 nm) can be adjusted more easily.

The protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
In the present specification, not only in the case of a 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 may be the same. The layers may be different, and only some of the layers may be the same, and “a plurality of layers are different from each other” means “at least one of the constituent materials and thicknesses of each layer is mutually different. Means different.

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the protective film-forming film is equal to or more than the lower limit value, a protective film having higher protective ability can be formed. Moreover, when the thickness of the protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, the “thickness of the protective film-forming film” means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of a plurality of layers means the protective film-forming film. Means the total thickness of all the layers that make up.

The curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the protective film has a degree of curing that sufficiently exhibits its function, and the type of the protective film-forming film is not limited. Accordingly, it may be appropriately selected.
For example, the illuminance of the energy rays when the protective film-forming film is cured is preferably 4 to 280 mW / cm ² . The amount of energy rays during the curing is preferably 3 to 1000 mJ / cm ² .

FIG. 1 is a cross-sectional view schematically showing one embodiment of a protective film-forming film of the present invention. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The protective film-forming film 13 shown here includes a first release film 151 on one surface 13a, and a second release film 152 on the other surface 13b opposite to the surface 13a.
Such a protective film-forming film 13 is suitable for storage as, for example, a roll.

The protective film-forming film 13 can be formed using a protective film-forming composition described later.
The protective film-forming film 13 satisfies both the conditions (1) and (2).

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

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 resulting exposed surface. And the remaining other of the 1st peeling film 151 and the 2nd peeling film 152 is removed, and the produced exposed surface turns into a sticking surface of a support sheet.

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

Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.

The drying conditions of the protective film-forming composition are not particularly limited, but when the protective film-forming composition contains a solvent to be described later, it is preferable to dry by heating. 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 protective film (IV-1)>
Examples of the protective film forming composition include a protective film forming composition (IV-1) containing the energy ray curable component (a).

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000. A compound (a2) is mentioned. The polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
In the present specification, the weight average molecular weight means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) obtained by polymerizing a group that reacts with a functional group and an energy ray curable compound (a12) having an energy ray curable group such as an energy ray curable double bond. .

Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). Group), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
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 an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.

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

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

Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate 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 (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester such as octadecyl (meth) acrylate (stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms.

Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid aryl ester such as (meth) acrylic acid phenyl ester, etc .; (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide and Derivatives thereof: (meth) acrylic acid esters having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate .

The acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene.
The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the protective film-forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. A content of ˜20% by weight is particularly preferred.

Energy beam curable compound (a12)
The energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

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

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

In the acrylic resin (a1-1), the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect 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 within such a range, the adhesive force of the protective film formed by curing is further increased. In addition, when the energy ray curable compound (a12) is a monofunctional compound (having one of the groups per molecule), the upper limit of the content ratio is 100 mol%, When the energy ray 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 2,000,000, and more preferably 300,000 to 1500,000.

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

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

(Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond. ) An acryloyl group, a vinyl group, etc. are mentioned.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and an energy ray curable group. A phenol resin etc. are mentioned.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate 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 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di (meth) acrylate (tri Cyclodecane dimethylol di (meth) a Relate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2 , 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydro Difunctional (meth) acrylates such as shea 1,3-di (meth) acryloxy propane;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as (meth) acrylate;
Examples include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used. Such a resin corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.

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

The protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds. The ratio can be arbitrarily selected.

[Polymer (b) having no energy ray curable group]
When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the energy ray curable component (a), the polymer further does not have an energy ray curable group. It is also preferable to contain (b).
The polymer (b) may be at least partially crosslinked by the crosslinking agent (f) or may not be crosslinked.

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

The acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more 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, glycidyl group-containing (meth) acrylic acid ester, Examples include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters. Here, the “substituted amino group” is as described above.

Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. 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, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester such as octadecyl (meth) acrylate (stearyl (meth) acrylate) 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 isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

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

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

As the polymer (b) at least partially crosslinked by the crosslinking agent (f) and not having the energy ray curable group, for example, the reactive functional group in the polymer (b) is a crosslinking agent (f ).
The reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred. Further, when the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, etc. Among them, a carboxy group having high reactivity with an epoxy group. Groups are preferred. However, the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.

Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomers constituting the polymer (b-1). Use it. 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. Examples thereof include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group in a non-acrylic monomer or a non-acrylic monomer.

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 unit constituting the polymer (b) is 1 to 25. The mass is preferably 2, and more preferably 2 to 20 mass%. When the ratio is within such a range, the degree of cross-linking becomes a more preferable range in the polymer (b).

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferably 100000 to 1500,000.

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

Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). When the protective film-forming composition (IV-1) contains the compound (a2), it preferably contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.

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

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

When the protective film forming composition (IV-1) contains the energy beam curable component (a) and the polymer (b) having no energy beam curable group, the protective film forming composition (IV-1) ) And the protective film-forming film, the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). More preferably, it is ˜130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray curability of the protective film-forming film becomes better.

In addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) comprises a photopolymerization initiator (c) depending on the purpose. , A filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component (h), and a general-purpose additive (z). Or you may contain 2 or more types.
For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the protective film-forming film formed is heated. Adhesive strength to the adherend is improved, and the strength of the protective film formed from this protective film-forming film is also improved.
Further, by using the colorant (g) as a component of the protective film forming composition (IV-1), the transmittance (1342 nm) is adjusted so as to satisfy the condition (1), and the condition It becomes easy to adjust the transmittance (1250 nm) so as to satisfy (2).

[Photoinitiator (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, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one, 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; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide Compound; α-ketol compound such as 1-hydroxycyclohexyl phenyl ketone; azo compound such as azobisisobutyronitrile; titanocene compound such as titanocene; thioxanthone compound such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime Benzophenone compounds such as); diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methyl Vinyl) phenyl] propanone; 2-chloroanthraquino Or the like.
As the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be only one type, or 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, in the protective film-forming composition (IV-1), the content of the photopolymerization initiator (c) is 100 parts by mass of the energy ray-curable compound (a). The amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Filler (d)]
When the protective film-forming film contains the filler (d), the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient. And the reliability of the package obtained using the composite sheet for protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a protective film. Moreover, the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for protective film formation contains a filler (d).
Examples of the filler (d) include those made of a heat conductive material.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers 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. . When the average particle diameter 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 adhesion to the object to be formed of the protective film.
In the present specification, “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, and combinations of two or more types. The ratio can be arbitrarily selected.

When the filler (d) is used, in the protective film forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming the protective film) The content of the filler (d) in the film) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass, such as 10 to 78% by mass, 20 to 78% by mass, It may be any of 30 to 78 mass%, 40 to 78 mass%, and 50 to 78 mass%. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

[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 adhesion 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 the heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy beam curable component (a), the polymer (b) having no energy beam curable group, and the like. More preferably, it is a silane coupling agent.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.

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

When the coupling agent (e) is used, the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film includes the energy ray curable component (a) and the energy. It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total content of the polymer (b) having no linear curable group, The amount is particularly preferably 0.1 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 adhesion of the protective film-forming film to the adherend is improved. The effect by using a coupling agent (e) etc. is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

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

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

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as 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 include a xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.

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

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group. When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable property. A cross-linked structure can be easily introduced into the protective film-forming film by reaction with the component (a) or the polymer (b) having no energy ray-curable group.

The crosslinking agent (f) 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 of two or more types. The ratio can be arbitrarily selected.

In the case where the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray-curable component (a) and the energy ray-curable group having no energy ray-curable group are contained. The total content of the combined (b) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight. It is particularly preferred. When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. Moreover, the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

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

Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazo B Systems dyes, pyranthrone pigments and threne dyes.

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

The protective film-forming composition (IV-1) and the colorant (g) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds. The ratio can be arbitrarily selected.

The transmittance (1342 nm) of the protective film-forming film is adjusted so as to satisfy the condition (1), and the transmittance (1250 nm) of the protective film-forming film is adjusted so as to satisfy the condition (2). It is preferable that the colorant (g) is an organic pigment or an organic dye from the viewpoint that each becomes easier.

When the colorant (g) is used, the content of the colorant (g) in the protective film-forming film is appropriately adjusted so that the protective film-forming film satisfies both the conditions (1) and (2). Good. For example, in the protective film forming composition (IV-1), the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the colorant (g) of the protective film forming film) 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. By adjusting the ratio in such a range, the transmittance (1342 nm) of the protective film-forming film is adjusted so as to satisfy the above condition (1) while not damaging the function of the protective film. And it is easy to adjust the transmittance (1250 nm) of the protective film-forming film so as to satisfy the condition (2). Moreover, making the said ratio into such a range is especially suitable when the colorant (g) is an organic pigment or an organic dye.

[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 kinds or more, and if two or more kinds, These combinations and ratios can be arbitrarily selected.

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

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2).
The epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.

・ Epoxy resin (h1)
Examples of the epoxy resin (h1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of curability of the protective film-forming film and strength and heat resistance of the protective film, and is preferably 400 to 10,000. More preferably, it is more preferably 500 to 3000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.

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

・ Thermosetting agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
As a thermosetting agent (h2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. .

Of the thermosetting agent (h2), for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
Among the thermosetting agents (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

A thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

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

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, the epoxy resin (h1) and the 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 polymer (b) having no energy ray curable group.

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. Is 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 there are two or more kinds, Combinations and ratios can be arbitrarily selected.
When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected according to the purpose. do it.

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

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

<< Method for producing protective film-forming composition >>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

Similar to the protective sheet-forming composite sheet of the present invention to be described later, it is affixed to the back surface of the semiconductor wafer or semiconductor chip opposite to the circuit surface, and is a composite having an adhesive layer on the support sheet. As the sheet, there is a dicing die bonding sheet.
However, the adhesive layer provided in the dicing die bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip and then attached to the substrate, the lead frame, or another semiconductor chip. On the other hand, the protective film-forming film in the protective film-forming composite sheet of the present invention is the same as the adhesive layer in that it is picked up from the support sheet together with the semiconductor chip, but eventually becomes a protective film by curing, It has a function of protecting the back surface of the semiconductor chip that is affixed. Thus, the protective film-forming film in the present invention has a different use from the adhesive layer in the dicing die bonding sheet, and naturally the required performance is also different. And reflecting the difference of this use, the film for protective film formation has the tendency of being harder compared with the adhesive bond layer in a dicing die bonding sheet normally. It is usually difficult to divert the adhesive layer in the dicing die bonding sheet as it is as the protective film-forming film in the protective film-forming composite sheet.

◇ Method for producing protective film-forming film The protective film-forming film of the present invention is obtained by coating a protective film-forming composition on a release film (preferably its release-treated surface) and drying it as necessary. Can be manufactured.
In addition, as shown in FIG. 1, the film for protective film formation is normally stored in the state by which the peeling film was bonded together on both surfaces, for example. For that purpose, a release film (preferably its release-treated surface) is further formed on the exposed surface of the protective film-forming film formed on the release film as described above (the surface opposite to the side provided with the release film). Can be pasted together.

◇ Method of using protective film-forming film The protective film-forming film of the present invention can constitute a protective film-forming composite sheet by providing it on a support sheet as described above. The protective film-forming composite sheet is used by being attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer by the protective film-forming film. Thereafter, in the same manner as the protective film forming composite sheet described later, the protective film is formed by curing the protective film forming film, dicing, picking up the semiconductor chip with the protective film, etc. What is necessary is just to manufacture.

On the other hand, the protective film-forming film of the present invention may be provided first on the back surface of the semiconductor wafer instead of the support sheet. That is, the protective film-forming film is attached to the back surface of the semiconductor wafer. Next, the protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Next, a protective film is formed in a state in which the protective film-forming film becomes a protective film by attaching a support sheet to the exposed surface of this protective film (the surface opposite to the side attached to the semiconductor wafer) Composite sheet. Thereafter, in the same manner as described above, dicing, picking up a semiconductor chip with a protective film, and the like may be performed to manufacture a target semiconductor device.

Here, the case where the protective film-forming film is cured to form a protective film and then this protective film is bonded to the support sheet has been described, but when the protective film-forming film of the present invention is used, these steps are performed. The order of performing may be reversed. That is, after affixing the protective film-forming film to the back surface of the semiconductor wafer, the support sheet is adhered to the exposed surface of the protective film-forming film (the side opposite to the side that is affixed to the semiconductor wafer). The protective film-forming film is an uncured protective film-forming composite sheet. Next, the protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Thereafter, in the same manner as described above, dicing, picking up a semiconductor chip with a protective film, and the like may be performed to manufacture a target semiconductor device.

◇ Composite sheet for protective film formation The composite sheet for protective film formation of the present invention includes a support sheet, and the protective film-forming film is provided on the support sheet.
The composite sheet for forming a protective film of the present invention is provided with a function as a dicing sheet in advance.

The protective sheet-forming composite sheet is provided with the protective film-forming film, so that it is possible to suppress the occurrence of defects due to insufficient curing on the dividing surface of the protective film-forming film, Infrared inspection of the semiconductor wafer or the semiconductor chip through the protective film forming film or through the protective film is facilitated.

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 film 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 or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present invention is not particularly limited, but is preferably 30 to 1000 μm because the effects of the present invention can be obtained more remarkably. 100 to 300 μm is more preferable.
Hereinafter, the structure of the composite sheet for protective film formation is demonstrated in detail.

Support sheet The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When a support sheet consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer, and only the substrate. And the like.
Examples of the composite sheet for forming a protective film of the present invention will be described below with reference to the drawings for each kind of the support sheet.

FIG. 2 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention.
In FIG. 2 and subsequent figures, the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.

The protective film-forming composite sheet 1 A shown here includes a pressure-sensitive adhesive layer 12 on a substrate 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. In other words, the protective film-forming composite sheet 1 A has a protective film-forming film 13 laminated on one surface 10 a of the support sheet 10. Have a configuration. The protective film-forming composite sheet 1 A further includes a release film 15 on the protective film-forming film 13.

In the protective sheet-forming composite sheet 1A, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film-forming film 13 is laminated on the entire surface of the one surface 12a of the pressure-sensitive adhesive layer 12. A jig adhesive layer 16 is laminated on a part of one surface 13 a of the film forming film 13, that is, in a region near the peripheral edge, and the jig adhesive among the surfaces 13 a of the protective film forming film 13. A release film 15 is laminated on the surface where the layer 16 is not laminated and on the surface 16 a (upper surface and side surface) of the jig adhesive layer 16.

In the protective film-forming composite sheet 1A, the protective film-forming film 13 satisfies both the conditions (1) and (2).

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 surfaces of a core sheet. It may be of a structure.

The composite sheet 1A for forming a protective film shown in FIG. 2 has a back surface of a semiconductor wafer (not shown) attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed. The upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that the adhesive sheet 16 for jig is not provided. That is, in the protective sheet-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film-forming film 13 is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12. A release film 15 is laminated on the entire surface 13 a of the film forming film 13.

The protective sheet-forming composite sheet 1B shown in FIG. 3 has a semiconductor wafer (not shown) in a partial region on the center side of the surface 13a of the protective film-forming film 13 with the release film 15 removed. The back surface is affixed, and the region near the peripheral edge is affixed to a jig such as a ring frame and used.

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

In the protective film-forming composite sheet 1C, the protective film-forming film 13 satisfies both of the conditions (1) and (2).

As in the protective film forming composite sheet 1A shown in FIG. 2, the protective film forming composite sheet 1C is formed on the surface 13a of the protective film forming film 13 with the release film 15 removed. The back surface of (not shown) is attached, and the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
The protective sheet-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 sheet-forming composite sheet 1D, the protective film-forming film 13 is laminated on one surface 11a of the substrate 11, and the release film 15 is laminated on the entire surface 13a of the protective film-forming film 13. Yes.

The protective film-forming composite sheet 1D shown in FIG. 5 is the same as the protective film-forming composite sheet 1B shown in FIG. 3, with the release film 15 being removed, of the surface 13a of the protective film-forming film 13, The back surface of a semiconductor wafer (not shown) is affixed to a partial area on the center side, and the area near the peripheral edge is affixed to a jig such as a ring frame for use.

FIG. 6 is a cross-sectional view schematically showing still another embodiment of the protective sheet-forming composite sheet 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 1 E includes 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 is formed by laminating the protective film-forming film 23 on one surface 10a of the support sheet 10. Have a configuration. The protective film-forming composite sheet 1 E further includes a release film 15 on the protective film-forming film 23.

In the protective sheet-forming composite sheet 1E, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a protective film-forming film is formed in the central region. 23 are stacked. And the peeling film 15 is laminated | stacked on the area | region where the film 23 for protective film formation is not laminated | stacked among the surface 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the film 23 for protective film formation. ing.

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

In the protective film-forming composite sheet 1E, the protective film-forming film 23 satisfies both the conditions (1) and (2).

In the protective film-forming composite sheet 1E shown in FIG. 6, the back surface of the semiconductor wafer (not shown) is pasted on the front surface 23a of the protective film-forming film 23 with the release film 15 removed. The area | region where the film 23 for protective film formation is not laminated | stacked among the surface 12a of 12 is stuck and used for jig | tools, such as a ring frame.

In the protective film-forming composite sheet 1E shown in FIG. 6, the surface 12a of the pressure-sensitive adhesive layer 12 is formed in the region where the protective film-forming film 23 is not laminated in the same manner as that shown in FIGS. An adhesive layer for jigs may be laminated (not shown). The protective film-forming composite sheet 1E provided with such a jig adhesive layer has a jig frame whose surface has a ring frame or the like, similar to the protective film-forming composite sheet shown in FIGS. Affixed to the jig and used.

Thus, the protective sheet-forming composite sheet of the present invention may have any form of the support sheet and the protective film-forming film, or may be provided with an adhesive layer for jigs. However, usually, as shown in FIGS. 2 and 4, the protective film-forming composite sheet of the present invention having a jig adhesive layer is provided with a jig adhesive layer on the protective film-forming film. Are preferred.

The composite sheet for forming a protective film of the present invention is not limited to the one shown in FIGS. 2 to 6, and a part of the structure shown in FIGS. 2 to 6 is changed or deleted within a range not impairing the effect of the present invention. In addition, another configuration may be added to what has been described so far.

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. Any intermediate layer can be selected according to the purpose.
In the composite sheet for forming a protective film shown in FIGS. 2, 3 and 6, an intermediate layer may be 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. 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.
In the composite sheet for forming a protective film shown in FIGS. 2 to 6, a layer other than the intermediate layer may be provided at an arbitrary position.
In the composite sheet for forming a protective film of the present invention, a gap may be partially formed between the release film and the layer that is in direct contact with the release film.
In the composite sheet for forming a protective film of the present invention, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

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

The support sheet may be transparent, opaque, or colored depending on the purpose.
Among them, in the present invention in which the protective film-forming film has energy ray curability, the support sheet is preferably capable of transmitting energy rays.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is within such a range, when the protective film-forming film is irradiated with energy rays (ultraviolet rays) via the support sheet, the degree of curing of the protective film-forming film is further improved.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the light transmittance may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet and printed on these, printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value 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.

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 within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet and printed on these, printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value 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.
Next, each layer which comprises a support sheet is demonstrated in detail.

-Base material The base material is in the form of a sheet or film, and examples of the constituent material include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyolefins; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer) A copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have an aromatic cyclic group; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.

The resin constituting the substrate may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

The thickness of the substrate is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or semiconductor chip are further improved.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.

The base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.

The base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.

The optical characteristics of the base material only need to satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
And in this invention in which the film for protective film formation has energy-beam sclerosis | hardenability, what a base material permeate | transmits an energy beam is preferable.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer provided on the substrate, the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment. The surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
The base material may have a surface subjected to primer treatment.
In addition, the base material prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coating layer and the protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
Among these, the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.

The base material can be manufactured 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 said adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferable. .

In the present invention, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has an adhesive property, Also included are resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit 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, these layers may be the same or different from each other. The combination of the 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 whole pressure-sensitive adhesive layer. For example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness.

The optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose.
In the present invention in which the protective film-forming film has energy ray curability, the pressure-sensitive adhesive layer is preferably capable of transmitting energy rays.

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

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site | part by applying an adhesive composition to the formation object surface of an adhesive layer, and making it dry as needed. A more specific method for forming the pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers. The ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer. Here, “normal temperature” is as described above.

The adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater and a kiss coater.

Although the drying conditions of an adhesive composition are not specifically limited, When the adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. The pressure-sensitive adhesive composition containing the solvent is preferably dried, for example, at 70 to 130 ° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive A pressure-sensitive adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; Energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) (hereinafter referred to as “adhesive resin (I-2a)”) A pressure-sensitive adhesive composition (I-2) containing the pressure-sensitive adhesive resin (I-2a) and an energy ray curable compound, etc. Is 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.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The acrylic resin may have only one type of structural unit, two or more types, and in the case of 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 preferred.
More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (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, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, 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 in which the alkyl group has 4 or more carbon atoms. In view of further improving the adhesive strength of the pressure-sensitive adhesive layer, the alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms. In addition, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic 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 an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow introduction of an unsaturated group into the side chain of the acrylic polymer.

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

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

The functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of 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, and more preferably 2 to 32% by mass with respect to the total amount of the structural unit. It is particularly preferably 3 to 30% by mass.

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 acrylic polymer may further have a structural unit derived from another monomer.
The other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, their combination and ratio 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 functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).

The pressure-sensitive adhesive composition (I-1) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or 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, more preferably 10 to 95% by mass, and 15 to 90%. It is particularly preferable that the content is% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4. Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.

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

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

[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 (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-1) preferably further contains a crosslinking agent.

For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
As a crosslinking agent, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Cross-linking agent having a glycidyl group); Aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton) and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer, and being easily available.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a). The amount 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 proceeds with a curing reaction even when irradiated with a relatively low energy beam 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-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. Α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of 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 energy ray curable compound. The amount is 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-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
Incidentally, the reaction retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C (═O) —) in one molecule. Can be mentioned.

The other additive contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio 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 according to the type.

[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. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane and n-hexane and the like. Aliphatic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

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

The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of 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 adjusted as appropriate.

<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.

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, 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. Etc.

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

The pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or 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, more preferably 10 to 95% by mass. It is particularly preferable that the content is% 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, an adhesive composition ( I-2) may further contain a crosslinking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of 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 crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). The amount 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 the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as 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, or two or more types, and in the case of 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 weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that 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, or two or more types, and in the case of 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 adjusted as appropriate.

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive 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, more preferably 10 to 95% by mass, and 15 to 90%. It is particularly preferable that the content is% 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. Examples thereof include the same energy ray curable compounds contained in the product (I-1).
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and in the case of 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 adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, more 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 energy rays of relatively low energy such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as 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, or two or more types, and in the case of 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 about 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 within a range not impairing the effects of the present invention.
Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof 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 according to the type.

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that 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, or two or more types, and in the case of 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 adjusted as appropriate.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive composition (I-3) have been mainly described. General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to herein as “pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)”) But it can be used similarly.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. An adhesive composition (I-4) containing an adhesive resin (I-1a) is preferable, and an adhesive composition containing an acrylic resin is preferred.

The pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more kinds of crosslinking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. It can be the same as in the case of (I-1).

<Adhesive composition (I-4)>
Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the pressure-sensitive adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or 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, more preferably 10 to 95% by mass, and 15 to 90%. It is particularly preferable that the content is% 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 (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same crosslinking agents as those in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of 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 crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a). The amount 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 within a range not impairing the effects of the present invention.
Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that 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, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.

In the composite sheet for forming a protective film of the present invention, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy ray curable, it is sometimes impossible to suppress the pressure-sensitive adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to the interface so as not to be peeled off. In that case, it becomes difficult to peel the film for forming a protective film after curing, that is, the semiconductor chip provided with the protective film on the back surface (semiconductor chip with protective film) from the support sheet provided with the adhesive layer after curing, The semiconductor chip with the protective film cannot be picked up normally. By making the pressure-sensitive adhesive layer non-energy ray curable with the support sheet in the present invention, such a problem can be reliably avoided and a semiconductor chip with a protective film can be picked up more easily.

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

<< Method for producing pressure-sensitive adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if necessary.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◇ Method for Producing Protective Film-Forming Composite Sheet The protective film-forming composite sheet of the present invention can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.
For example, when a pressure-sensitive adhesive layer is laminated on a substrate when producing a support sheet, the above-described pressure-sensitive adhesive composition may be applied on the substrate and dried as necessary.

On the other hand, for example, when a protective film-forming film is further laminated on the adhesive layer laminated on the substrate, the protective film-forming composition is applied on the adhesive layer, It is possible to form the forming film directly. Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after forming the laminated structure.

For example, a protective film-forming composite sheet in which a pressure-sensitive 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 the base material and the pressure-sensitive adhesive layer) In the case of producing a protective sheet-forming composite sheet), a pressure-sensitive adhesive composition is coated on a base material and dried as necessary, whereby a pressure-sensitive adhesive layer is laminated on the base material, The protective film-forming composition is coated on 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 adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer, thereby forming a protective film. A composite sheet is obtained.

In addition, when laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition is applied on the release film. The pressure-sensitive 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 so that the pressure-sensitive adhesive layer is placed on the base material. You may laminate.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.

In this way, all layers other than the base material constituting the protective film-forming composite sheet can be formed in advance on the release film and laminated on the surface of the target layer. A layer that employs such a process may be appropriately selected to produce a protective sheet-forming composite sheet.

In addition, the composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is applied on this release film (preferably its release-treated surface) and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the methods described above. And the composite sheet for protective film formation is obtained also by leaving it in the state bonded together, without removing a peeling film.

◇ Method for Manufacturing Semiconductor Chip The protective film-forming film and the protective film-forming composite sheet of the present invention can be used for manufacturing semiconductor chips.
As a manufacturing method of the semiconductor chip at this time, for example, a process of attaching the protective film forming film or the protective film forming film in the protective film forming composite sheet to a semiconductor wafer (hereinafter referred to as “applying process”) And a process of forming a protective film on the semiconductor wafer by irradiating the film for forming the protective film affixed to the semiconductor wafer with energy rays (hereinafter abbreviated as “protective film forming process”). And irradiating laser light in the infrared region through the protective film or film for forming a protective film so as to be focused on a focal point set inside the semiconductor wafer. A step of forming a modified layer therein (hereinafter sometimes abbreviated as “modified layer forming step”), and applying the force to the semiconductor wafer on which the modified layer has been formed; Wherein at the site of dividing the semiconductor wafer to obtain a plurality of semiconductor chips (hereinafter, sometimes abbreviated as "split step"), those having a.

Hereinafter, the above manufacturing method will be described with reference to the drawings. 7A to 7E are cross-sectional views for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a protective film-forming film is used alone. 8A to 8D are cross-sectional views for schematically explaining one embodiment of a method for manufacturing a semiconductor chip when a protective film-forming film is used in advance integrated with a support sheet.

<< Method of Manufacturing Semiconductor Chip When Using Protective Film Forming Film >>
First, the manufacturing method in the case of using the protective film-forming film alone will be described by taking as an example the case where the protective film-forming film is as shown in FIG.
In the attaching step, as shown in FIG. 7A, a protective film forming film 13 is attached to the back surface (surface opposite to the electrode forming surface) 9b of the semiconductor wafer 9. Here, the case where the 1st peeling film 151 was removed from the film 13 for protective film formation, and the one surface 13a of the film 13 for protective film formation was bonded together to the back surface 9b of the semiconductor wafer 9 is shown.

After the attaching step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with energy rays in the protective film forming step to form a protective film 13 ′ on the semiconductor wafer 9 as shown in FIG. 7B. . The irradiation with energy rays may be performed after the second release film 152 is removed from the protective film-forming film 13.

Further, after the pasting step, in the modified layer forming step, the laser beam in the infrared region is irradiated through the protective film 13 ′ so as to be focused on the focal point set inside the semiconductor wafer 9. As shown in FIG. 7C, the modified layer 91 is formed inside the semiconductor wafer 9. Irradiation with infrared laser light is performed after the second release film 152 is removed from the protective film 13 '.

In the modified layer forming step, the transmittance (1342 nm) of the protective film 13 ′ is high, so that the modified layer 91 can be stably and sufficiently formed inside the semiconductor wafer 9.

Here, although the case where the modified layer forming step is performed after the protective film forming step has been described, the protective film forming step may be performed after the modified layer forming step (not shown). In this case, when the modified layer 91 is formed inside the semiconductor wafer 9, the second release film 152 is removed from the protective film forming film 13, and infrared laser light is irradiated through the protective film forming film 13. To do. In this case as well, since the transmittance (1342 nm) of the protective film forming film 13 is high, the modified layer 91 can be stably and sufficiently formed inside the semiconductor wafer 9.

After the modified layer forming step, prior to the dividing step, as shown in FIG. 7D, the protective film 13 ′ on the side opposite to the (one) surface 13a ′ on which the semiconductor wafer 9 is stuck ( The support sheet 10 is affixed to the other surface 13b ′. The support sheet 10 is shown in FIG. 3 and the like, and is attached to the protective film 13 ′ by the adhesive layer 12.

Next, in the dividing step, a force is applied to the semiconductor wafer 9 on which the modified layer 91 is formed, so that the semiconductor wafer 9 is divided at a site of the modified layer 91 as shown in FIG. Get 9 '. At the same time, the protective film 13 ′ is also divided (cut) at a position along the peripheral edge of the semiconductor chip 9 ′. The protective film 13 ′ after the cutting is denoted by reference numeral 130 ′.
In the dividing step, the semiconductor wafer 9 and the protective film to which a force (tensile force) is applied in this direction by expanding the semiconductor wafer 9 and the protective film 13 ′ in the direction indicated by the arrow I in FIG. 7D. 13 'is divided.

In this manufacturing method, the protective film-forming film is cured to form a protective film, and the protective film is divided. Therefore, the divided surface of the protective film-forming film is not exposed to the air (oxygen), and the protective film Occurrence of problems associated with poor curing of the dividing surface of the forming film can be avoided.

<< Semiconductor chip manufacturing method in the case where the protective film-forming film is integrated with a support sheet in advance >>
Next, a manufacturing method in the case where the protective film-forming film is used by being integrated with a support sheet in advance will be described by taking the case where the protective film-forming composite sheet is as shown in FIG.
8A, the protective film forming film 13 in the protective film forming composite sheet 1A is attached to the back surface 9b of the semiconductor wafer 9. The protective film-forming composite sheet 1A is used with the release film 15 removed.

After the attaching step, in the protective film forming step, the protective film forming film 13 attached to the semiconductor wafer 9 is irradiated with energy rays to form a protective film 13 ′ on the semiconductor wafer 9 as shown in FIG. 8B. .

In addition, after the pasting step, in the modified layer forming step, the infrared region is passed through the protective film 13 ′ (the protective film forming composite sheet 1A) so as to be focused on the focal point set inside the semiconductor wafer 9. The modified layer 91 is formed inside the semiconductor wafer 9, as shown in FIG. 8C.

In the modified layer forming step, the transmittance (1342 nm) between the protective film 13 ′ and the support sheet 10 is high, so that the modified layer 91 can be stably and sufficiently formed inside the semiconductor wafer 9.

Here, although the case where the modified layer forming step is performed after the protective film forming step has been described, the protective film forming step may be performed after the modified layer forming step (not shown). In this case, when the modified layer 91 is formed in the semiconductor wafer 9, the laser beam in the infrared region is irradiated through the protective film forming composite sheet 1A in which the protective film forming film 13 is uncured. Also in this case, since the transmittance (1342 nm) between the protective film-forming film 13 and the support sheet 10 is high, the modified layer 91 can be stably and sufficiently formed inside the semiconductor wafer 9.

In the dividing step, a force is applied to the semiconductor wafer 9 on which the modified layer 91 is formed, so that the semiconductor wafer 9 is divided at the site of the modified layer 91 as shown in FIG. 'Get. At the same time, the protective film 13 ′ is also divided (cut) at a position along the peripheral edge of the semiconductor chip 9 ′. The protective film 13 ′ after the cutting is denoted by reference numeral 130 ′.
In the dividing step, the semiconductor wafer 9 and the protective film to which a force (tensile force) is applied in this direction by expanding the semiconductor wafer 9 and the protective film 13 ′ in the direction indicated by the arrow I in FIG. 8C. 13 'is divided.

Even in this manufacturing method, the protective film-forming film is cured to form a protective film, and this protective film is divided, so that the divided surface of the protective film-forming film is not exposed to the air (oxygen), Occurrence of problems associated with poor curing of the dividing surface of the forming film can be avoided.

◇ Method for Manufacturing Semiconductor Device After obtaining the semiconductor chip 9 ′ by the above-described manufacturing method, the semiconductor chip 9 ′ is left in a state where the divided protective film 130 ′ is adhered (that is, a semiconductor with a protective film). As a chip), the pickup is pulled away from the support sheet 10 (not shown).
Thereafter, the semiconductor chip 9 ′ of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then a semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package (not shown).

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

The components used for the production of the protective film-forming composition are shown below.
Energy ray curable component (a2) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684”, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Kayaku Co., Ltd.)
Polymer having no energy ray-curable group (b) -1: butyl acrylate (hereinafter abbreviated as “BA”) (10 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) ( 70 parts by mass), glycidyl methacrylate (hereinafter abbreviated as “GMA”) (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) Acrylic polymer (weight average molecular weight 300000, glass transition temperature -1 ° C).
Photopolymerization initiator (c) -1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF)
(C) -2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure (registered by BASF)) Trademark) OXE02 ")
Filler (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) -1: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and anthraquinone red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and pigmenting the mixture so that the total amount of the three kinds of dyes / the amount of styrene acrylic resin = 1/3 (mass ratio).
(G) -2: Carbon black (“# MA650” manufactured by Mitsubishi Chemical Corporation, average particle size 28 nm)

[Example 1]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (IV-1))
Energy ray curable component (a2) -1, polymer (b) -1, photopolymerization initiator (c) -1, photopolymerization initiator (c) -2, filler (d) -1, coupling agent (E) -1 and the colorant (g) -1 are dissolved or dispersed in methyl ethyl ketone so that the content (solid content, parts by mass) thereof is the value shown in Table 1, and stirred at 23 ° C. Thus, a protective film-forming composition (IV-1) having a solid content concentration of 50% by mass was prepared. In addition, the description of “-” in the column of the contained component in Table 1 means that the protective film-forming composition (IV-1) does not contain the component.

(Production of pressure-sensitive adhesive composition (I-4))
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing methyl ethyl ketone and having a solid content concentration of 30% by mass was prepared. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass). The weight average molecular weight is 600,000.

(Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. ) 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.
Subsequently, the pressure-sensitive adhesive layer was provided on one surface of the base material by bonding a polyvinyl chloride film (Young's modulus 280 MPa, thickness 80 μm) as a base material to the exposed surface of the pressure-sensitive adhesive layer. A support sheet (10) -1 was obtained.

(Manufacture of composite sheet for protective film formation)
The protective film-forming composition (IV) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 μm) from which one side of a polyethylene terephthalate film was released by silicone treatment. -1) was applied with a knife coater and dried at 100 ° C. for 2 minutes to produce an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 μm.

Next, the release film is removed from the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above, and the protective film-forming film (13) -1 obtained above is exposed on the exposed surface of the pressure-sensitive adhesive layer. The surfaces were bonded together to prepare a composite sheet for forming a protective film, in which a base material, an adhesive layer, a protective film-forming film (13) -1 and a release film were laminated in this order in the thickness direction. Table 2 shows the structure of the obtained protective sheet-forming composite sheet.

<Evaluation of protective film-forming film and protective film>
(Laser transmittance of protective film-forming film)
Using a spectrophotometer (“UV-VIS-NIR SPECTROTOPOMETER UV-3600” manufactured by SHIMADZU), the transmittance (1342 nm) and the transmittance (1250 nm) of the protective film-forming film (13) -1 obtained above were used. ) Was measured. The measurement was performed using the attached large sample chamber MPC-3100 without using the built-in integrating sphere. The results are shown in Table 2. In Table 2, “−” in the evaluation result column means that the item has not been evaluated.

(Dividability of semiconductor wafer)
The protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of an 8-inch silicon wafer (thickness 300 μm) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed and allowed to stand for 30 minutes.
Next, a protective film-forming film (13) is formed from the support sheet (10) -1 side under the conditions of an illuminance of 195 mW / cm ² and a light amount of 170 mJ / cm ² using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film.
Next, a protective film-forming composite sheet having the protective film-forming film (13) -1 as a protective film is affixed, and the silicon wafer fixed to the ring frame is interposed through the protective film-forming composite sheet. The silicon wafer and the ring frame were placed on a laser saw (“DFL 7361” manufactured by Disco Corporation) while adjusting the position so that the laser beam could be irradiated.
Next, a modified layer was formed inside the silicon wafer by irradiating a laser beam having a wavelength of 1342 nm through the protective film-forming composite sheet so as to focus on the focal point set inside the silicon wafer. .
Next, the silicon wafer, the protective film forming composite sheet, and the ring frame are placed on a die separator (Disco 2300 “DDS2300”). By expanding in the direction along the surface, the silicon wafer was divided together with the protective film to obtain a silicon chip having a size of 3 mm × 3 mm.
Next, the divided state of the silicon wafer is visually observed, and when the silicon wafer is completely divided together with the protective film at the target location, the division property is determined as “A”, and at least a part of the target location is silicon. When the wafer was not divided, the division property was determined as “B”. The results are shown in Table 2.

(Laser transmittance of protective film)
About the protective film obtained above, the protective film transmittance | permeability (1342 nm) and the protective film transmittance | permeability (1250 nm) were measured by the same method as the case of said film for protective film formation. The results are shown in Table 2.

(Infrared inspection of semiconductor chips)
When the silicon chip obtained above is inspected by irradiating a laser beam having a wavelength of 1250 nm through the protective film after the division, and the presence or absence of abnormality of the silicon chip can be confirmed, the infrared inspection property is improved. When it was determined as “A” and the presence or absence of abnormality of the silicon chip could not be confirmed, the infrared inspection property was determined as “B”. The results are shown in Table 2.

(Hardening degree of protective film)
Using a Fourier transform infrared spectrometer (“Spectrum One” manufactured by Perkin Elmer), the splitting surface of the protective film after splitting obtained above has a peak with a wave number of 1410 cm ⁻¹ peculiar to the energy ray-curable component. The presence or absence was confirmed. And when there is no peak, it is determined that the protective film is sufficiently cured, and the curing degree is determined as “A”, and when there is a peak, the protective film is not sufficiently cured, Was determined to be “B”. The results are shown in Table 2.

<Manufacture of Composite Sheet for Forming Protective Film, and Evaluation of Film for Forming Protective Film and Protective Film>
[Example 2]
Table 2 shows the amounts of compounding ingredients at the time of production of the protective film-forming composition (IV-1). Instead of the protective film-forming film (13) -1, the energy ray-curable composition having a thickness of 25 μm is used. A protective film-forming film and a protective film-forming composite sheet were produced in the same manner as in Example 1 except that the protective film-forming film (13) -2 was produced. evaluated. The results are shown in Table 2.

[Reference Example 1]
<Manufacture of composite sheet for forming protective film>
In the same manner as in Example 1, a composite sheet for forming a protective film was produced.

<Evaluation of protective film-forming film and protective film>
(Dividability of semiconductor wafer)
The protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of an 8-inch silicon wafer (thickness 300 μm) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed and allowed to stand for 30 minutes.
Next, the silicon wafer was diced and divided together with the protective film-forming film (13) -1 using a blade dicer (“DFD651” manufactured by Disco Corporation) to obtain a silicon chip having a size of 3 mm × 3 mm.
Next, the division state of the silicon wafer was visually observed, and the division property in the case where the silicon wafer was all divided together with the protective film forming film (13) -1 at the target location was determined as “A”. The division property when the silicon wafer was not divided at at least a part of the portion to be processed was determined as “B”. The results are shown in Table 2.

(Infrared inspection of semiconductor chips)
After obtaining the silicon chip as described above, the support sheet (10) -1 was used under the conditions of illuminance of 195 mW / cm ² and light amount of 170 mJ / cm ² using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). The protective film forming film (13) -1 after being divided from the side was irradiated with ultraviolet rays to cure the protective film forming film (13) -1 to obtain a protective film.
Subsequently, the infrared inspection property of the obtained silicon chip was evaluated by the same method as in Example 1. The results are shown in Table 2.

(Hardening degree of protective film)
With respect to the divided surface of the protective film after the division obtained above, the presence or absence of a peak at a wave number of 1410 cm ⁻¹ was confirmed, and the degree of curing of the protective film was evaluated by the same method as in Example 1. The results are shown in Table 2.

<Manufacture of Composite Sheet for Forming Protective Film, and Evaluation of Film for Forming Protective Film and Protective Film>
[Reference Example 2]
The protective film was prepared in the same manner as in Reference Example 1 except that instead of the protective film-forming film (13) -1, an energy ray-curable protective film-forming film (13) -2 having a thickness of 25 μm was produced. A film for forming and a composite sheet for forming a protective film were produced, and the film for forming a protective film and the protective film were evaluated. The results are shown in Table 2.

[Comparative Example 1]
Table 2 shows the amounts of compounding ingredients at the time of production of the protective film-forming composition (IV-1). Instead of the protective film-forming film (13) -1, the energy ray-curable composition having a thickness of 25 μm is used. A protective film-forming film and a protective film-forming composite sheet were produced in the same manner as in Example 1 except that the protective film-forming film (93) -1 was produced. evaluated. The results are shown in Table 2.

[Comparative Example 2]
Instead of the protective film-forming film (13) -1, an energy ray-curable protective film-forming film (93) -1 having a thickness of 25 μm was prepared in the same manner as in Reference Example 1, except that a protective film was formed. A film for forming and a composite sheet for forming a protective film were produced, and the film for forming a protective film and the protective film were evaluated. The results are shown in Table 2.

[Comparative Example 3]
Table 2 shows the amounts of compounding ingredients at the time of production of the protective film-forming composition (IV-1). Instead of the protective film-forming film (13) -1, the energy ray-curable composition having a thickness of 25 μm is used. A protective film-forming film and a protective film-forming composite sheet were produced in the same manner as in Example 1 except that the protective film-forming film (93) -2 was produced. evaluated. The results are shown in Table 2.

As is clear from the above results, in Examples 1 and 2, the transmittance (1342 nm) of the protective film-forming film is 60%, and the silicon wafer can be divided well by forming a modified layer on the silicon wafer. did it. Further, the transmittance (1250 nm) of the protective film-forming film was 50%, and the infrared inspection property of the silicon chip was also good. The peak of wave number 1410 cm ⁻¹ was not recognized on the divided surface of the protective film, and the protective film was sufficiently cured.

On the other hand, in Reference Examples 1 and 2, although the same protective film forming composition as in Examples 1 and 2 was used, blade dicing was performed before the protective film forming film was cured. The divided surface of the protective film was not sufficiently cured due to the effect that the divided surface of the protective film-forming film was exposed to oxygen during ultraviolet irradiation. It was considered that the silicon chip with protective film obtained in these reference examples could not suppress the occurrence of defects due to the pickup, the protective effect of the protective film, storage, and the like.

In Comparative Example 1, since the transmittance (1342 nm) of the protective film-forming film was low, the modified layer could not be sufficiently formed on the silicon wafer, and as a result, many silicon wafers that could not be divided remained. As described above, in this comparative example, the silicon wafer was not sufficiently divided, and thus the infrared testability of the silicon chip was not evaluated. However, the transmittance (1250 nm) of the protective film-forming film was low. It was thought that the infrared inspection property of the silicon chip was also poor.

In Comparative Example 2, since the blade dicing was employed for dividing the silicon wafer, it was not affected by the low transmittance (1342 nm) of the protective film-forming film, but the protective film-forming film had a transmittance (1250 nm). By being low, the infrared testability of the silicon chip was poor. As in Reference Example 1, blade dicing was performed before the protective film-forming film was cured. As a result, the divided surface of the protective film was not sufficiently cured.

In Comparative Example 3, since the transmittance (1342 nm) of the protective film-forming film is lower than that of Comparative Example 1, the modified layer cannot be sufficiently formed on the silicon wafer. Many more remained than in the case of Comparative Example 1. In this comparative example, as in Comparative Example 1, the infrared testability of the silicon chip was not evaluated. However, the transmittance (1250 nm) of the protective film-forming film was remarkably low. It was considered very bad.

The present invention can be used for manufacturing semiconductor devices.

1A, 1B, 1C, 1D, 1E ... Composite sheet for protective film formation, 10 ... Support sheet, 10a ... Surface of support sheet, 11 ... Base material, 11a ... Surface of base material , 12 ... adhesive layer, 12a ... surface of the adhesive layer, 13, 23 ... protective film forming film, 13a, 23a ... surface of the protective film forming film (one surface), 13b: surface of the protective film-forming film (the other surface), 13 '... protective film, 130' ... protective film after cutting, 15 ... release film, 151 ... first release Film, 152 ... second release film, 16 ... adhesive layer for jig, 16a ... surface of adhesive layer for jig, 9 ... semiconductor wafer, 9b ... back surface of semiconductor wafer 91 ... Modified layer of semiconductor wafer, 9 '... Semiconductor chip

Claims

A protective film-forming film having energy ray curability and satisfying the following conditions (1) and (2).
(1) The transmittance of laser light having a wavelength of 1342 nm is 45% or more.
(2) The transmittance of laser light having a wavelength of 1250 nm is 35% or more.
A composite sheet for forming a protective film, comprising a support sheet, the protective film-forming film according to claim 1 being provided on the support sheet.
Applying 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;
Irradiating the protective film-forming film attached to the semiconductor wafer with energy rays to form a protective film on the semiconductor wafer;
Irradiate laser light in the infrared region through the protective film or film for forming a protective film so as to focus on a focal point set inside the semiconductor wafer, thereby forming a modified layer inside the semiconductor wafer. And a process of
A method of manufacturing a semiconductor chip, comprising: applying a force to the semiconductor wafer on which the modified layer is formed to divide the semiconductor wafer at a portion of the modified layer to obtain a plurality of semiconductor chips.