WO2019082974A1

WO2019082974A1 - Film for forming protective coating, composite sheet for forming protective coating, and method for manufacturing semiconductor chip

Info

Publication number: WO2019082974A1
Application number: PCT/JP2018/039694
Authority: WO
Inventors: 力也小橋; 洋一稲男
Original assignee: リンテック株式会社
Priority date: 2017-10-27
Filing date: 2018-10-25
Publication date: 2019-05-02
Also published as: TW201936824A; JP6979081B2; TWI847963B; JPWO2019082974A1

Abstract

This film for forming a protective coating contains an ultraviolet-curable component, the light transmittance at a wavelength of 350 nm being 20% or less, the light transmittance at a wavelength of 550 nm being 25% or less, and the light transmittance at wavelength 1600 nm being 25% or greater.

Description

Film for protective film formation, composite sheet for protective film formation, and method of manufacturing semiconductor chip

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, and a method of manufacturing a semiconductor chip.
Priority is claimed on Japanese Patent Application No. 2017-208438, filed Oct. 27, 2017, the content of which is incorporated herein by reference.

In recent years, semiconductor devices have been manufactured to which a mounting method called a so-called face down method is applied. 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. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.

A resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and may be taken into a semiconductor device as a semiconductor chip with a protective film.
The protective film is used to prevent the occurrence of cracks in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film comprising a protective film-forming film for forming a protective film on a support sheet is used. The film for protective film formation can form a protective film by hardening. In addition, the support sheet can be used to fix the semiconductor wafer when dividing the semiconductor wafer provided with the protective film-forming film or the protective film on the back surface into semiconductor chips. Furthermore, the support sheet can also be used as a dicing sheet, and the composite sheet for protective film formation can also be used as an integrated film of the protective film formation film and the dicing sheet.

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

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

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

JP 2004-51736 A JP, 2009-138026, A

As in Patent Document 1, when the transmittance at wavelength light of 300 to 400 nm is high, the ultraviolet ray curable adhesive sheet can be sufficiently cured by ultraviolet rays, but is included in the light of a fluorescent lamp during storage of the ultraviolet ray curable adhesive sheet. Since the curing proceeds even by ultraviolet light, the storage stability is lacking.

The component (C) used in the example of Patent Document 2 is a black pigment. In the chip protection film containing a black pigment, the transmittance of infrared light is low, and an infrared inspection can not be performed via the chip protection film.

In addition, on the back surface of the semiconductor chip, usually, a grinding mark by back grinding processing applied to a semiconductor wafer remains. From the viewpoint of the appearance of the semiconductor chip, it is desirable that such grinding marks be covered with a protective film so that they can not be seen visually.

Therefore, the present invention is a composite sheet for forming a protective film, which has good storage stability, and can form a protective film which makes the appearance of the semiconductor chip good and enables infrared inspection through the protective film of the semiconductor chip. And providing a method of manufacturing the semiconductor chip.

In order to solve the above problems, the present invention contains an ultraviolet ray curable component, the light transmittance of a wavelength 350 nm is 20% or less, the light transmittance of a wavelength 550 nm is 25% or less, and a light transmission of a wavelength 1600 nm The film for protective film formation whose rate is 25% or more.

The present invention also provides a composite sheet for forming a protective film, which comprises a support sheet, and the film for forming a protective film on the support sheet.

Further, according to the present invention, a step of sticking the film for forming a protective film or the film for forming a protective film in the composite sheet for forming a protective film on a semiconductor wafer, and forming the protective film after being attached to the semiconductor wafer Film is irradiated with ultraviolet light to form a protective film, and the semiconductor wafer is cut together with the protective film or the protective film-forming film to divide the semiconductor wafer and obtain a plurality of semiconductor chips. And providing a method of manufacturing a semiconductor chip.

The film for protective film formation of the present invention has good storage stability, and can form a protective film which makes the appearance of the semiconductor chip good and enables infrared inspection through the protective film of the semiconductor chip. Further, according to the present invention, a composite sheet for forming a protective film provided with the film for forming a protective film, and a method for manufacturing the semiconductor chip are provided.

It is sectional drawing which shows typically the film for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip in the case of using the film for protective film formation. It is sectional drawing for describing typically one Embodiment of the manufacturing method of a semiconductor chip in the case of using the composite sheet for protective film formation.

フィルム Film for Protective Film Formation The film for protective film formation according to one embodiment of the present invention contains an ultraviolet ray curable component, has a light transmittance of wavelength 350 nm of 20% or less, and a light transmittance of wavelength 550 nm of 25. %, And the light transmittance at a wavelength of 1600 nm is 25% or more.

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

The film for protective film formation is cured by irradiation with ultraviolet light to be a protective film. This protective film is for protecting the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer or the semiconductor chip. The protective film-forming film is soft and can be easily attached to an object to be attached.
Since the film for protective film formation is ultraviolet curable, the protective film can be formed by curing in a shorter time than a thermosetting film for protective film formation.

In the present specification, the “protective film-forming film” means one before curing, and the “protective film” means one obtained by curing the protective film-forming film.

The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet light source. The electron beam can irradiate what was generated by the electron beam accelerator or the like.
In the present invention, "ultraviolet-curable" means the property of curing by irradiation with ultraviolet light, and "non-ultraviolet-curable" means the property of not curing even when irradiated with ultraviolet light.

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

The film for protective film formation which concerns on this embodiment contains an ultraviolet curable component. The light transmittance at a wavelength of 350 nm of the protective film-forming film is 20% or less, preferably 15% or less, more preferably 8% or less, and particularly preferably 5% or less. When the light transmittance of 350 nm wavelength of the film for protective film formation is 20% or less, when storing the film for protective film formation, the curing reaction of the ultraviolet curable component is caused by the ultraviolet light contained in the light of the fluorescent lamp etc. It is possible to suppress progress. It is preferable that the light transmittance of wavelength 350 nm of the film for protective film formation is 0% or more. In addition, when the light transmittance of wavelength 350 nm of the film for protective film formation is 0%, the film for protective film formation may absorb all light, or the film for protective film formation may reflect all light. obtain. The upper limit value and the lower limit value of the light transmittance at a wavelength of 350 nm of the protective film-forming film can be arbitrarily combined. For example, the light transmittance at a wavelength of 350 nm of the film for protective film formation is 0% or more and 20% or less, preferably 0% or more and 15% or less, and more preferably 0% or more and 8% or less. It is particularly preferable that it is 0% or more and 5% or less.

On the other hand, for example, on the back surface of a semiconductor chip, grinding marks by back grinding processing applied to a semiconductor wafer usually remain. When the light transmittance at a wavelength of 550 nm is 25% or less as described above, the protective film-forming film hardly transmits visible light. Therefore, the above-mentioned grinding marks are concealed by the protective film-forming film (protective film) and hardly visible visually. As a result, the appearance of a workpiece such as a semiconductor chip becomes excellent.

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

The protective film-forming film according to this embodiment preferably has a light transmittance of 25% or more, more preferably 40% or more, and particularly preferably 45% or more, at a wavelength of 1600 nm. Furthermore, it is preferable that it is 50% or more. In a semiconductor chip or the like obtained by dicing a semiconductor wafer, a crack or the like may be generated due to a stress generated during processing. As described above, when the light transmittance at a wavelength of 1600 nm is 25% or more, the transmittance of infrared rays becomes good, and the infrared rays from the protective film-forming film (or the protective film formed by the protective film-forming film) side You can do an infrared inspection to get.
Thus, cracks and the like in the processed product such as a semiconductor chip can be found through the protective film-forming film (protective film), and the product yield can be improved.

The upper limit of the light transmittance at a wavelength of 1600 nm is not particularly limited, but it is naturally determined by setting the light transmittance at a wavelength of 550 nm to 25% or less. Specifically, the light transmittance of the film for forming a protective film at a wavelength of 1600 nm is preferably 90% or more. When using a workpiece (such as a semiconductor chip) on which a protective film has been formed, by setting the light transmittance of the film for protective film formation at a wavelength of 1600 nm to 90% or less, false errors in workpieces susceptible to external infrared rays It can prevent operation. The upper limit value and the lower limit value of the light transmittance at a wavelength of 1600 nm of the protective film-forming film can be arbitrarily combined. For example, the light transmittance at a wavelength of 1600 nm of the film for protective film formation is preferably 25% to 90%, more preferably 40% to 90%, and particularly 45% to 90%. And more preferably 50% or more and 90% or less.

The film for protective film formation may be only one layer (single layer), or two or more layers, and in the case of multiple layers, these multiple layers may be the same or different from one another. The combination is not particularly limited.
In addition, in this specification, not only in the case of the film for protective film formation, "all layers may be the same, and all layers may be the same" It means that the layers may be different, and only some of the layers may be the same. Further, “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is mutually different. It means "different".

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the film for protective film formation is more than the said lower limit, a protective film with higher protective ability can be formed. In addition, when the thickness of the protective film-forming film is equal to or less than the upper limit value, excessive thickness can be suppressed.
Here, "the thickness of the film for protective film formation" means the thickness of the whole film for protective film formation, for example, the thickness of the film for protective film formation which consists of multiple layers is a film for protective film formation. Means the total thickness of all the layers that make up.
Moreover, "the thickness of the film for protective film formation" can be measured as follows. The distance between the front surface and the back surface of the film for protective film formation is measured using a contact-type thickness meter at any five points of the film for protective film formation. Let the average value of five measured points be the thickness of the film for protective film formation.
The thicknesses of the films, layers, semiconductor wafers, substrates and the like described below are also measured by the above-described method.

The curing conditions for curing the protective film-forming film to form a protective film are not particularly limited as long as the protective film has a curing degree sufficient to exhibit its function, and the type of protective film-forming film Depending on the situation, it may be selected appropriately.
For example, the illuminance of ultraviolet light at the time of curing of the protective film-forming film is preferably 4 to 280 mW / cm ² . The light quantity of the ultraviolet light at the time of curing is preferably 3 to 1000 mJ / cm ² .

FIG. 1 is a cross-sectional view schematically showing a protective film-forming film according to an embodiment of the present invention. Note that the drawings used in the following description may be enlarged for convenience, in order to make the features of the present invention intelligible. Not necessarily.

The film 13 for protective film formation shown here is provided with the 1st peeling film 151 on one surface (it may be called a "1st surface" in this specification) 13a, and the said 1st surface 13a A second release film 152 is provided on the other surface (which may be referred to herein as the “second surface”) 13b of the opposite side.
Such a protective film-forming film 13 is suitable, for example, for storage as a roll.

The film 13 for protective film formation can be formed using the composition for protective film formation mentioned later. The protective film-forming film 13 is ultraviolet curable.

Both the first release film 151 and the second release film 152 may be known ones. The light transmittance of 375 nm of the first release film 151 and the second release film 152 is not particularly limited as long as the effects of the present invention are obtained. In the embodiment of the present invention, regardless of the light transmittance of 375 nm of the first peeling film 151 and the second peeling film 152, the protective film-forming film 13 is UV-cured by the ultraviolet light contained in the light of a fluorescent lamp or the like. It has the effect that the curing reaction of the sex component hardly progresses.
The first release film 151 and the second release film 152 may be identical to each other, or may be different from each other, for example, the release forces necessary for releasing from the protective film-forming film 13 may be different from each other. May be

In the protective film-forming film 13 shown in FIG. 1, 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 other of the remaining of the 1st exfoliation film 151 and the 2nd exfoliation film 152 is removed, and the generated exposed side turns into the sticking side of a support sheet.

<< Composition for protective film formation >>
The film for protective film formation can be formed using the composition for protective film formation containing the constituent material. For example, the composition for protective film formation may be coated on the formation target surface of the film for protective film formation, and dried as needed, so that the film for protective film formation can be formed on the target site.
The ratio of the content of components which do not vaporize at normal temperature in the composition for forming a protective film is usually the same as the ratio of the content of the components of the film for forming a protective film. In the present specification, “normal temperature” means a temperature which is not particularly cooled or heated, ie, a normal temperature, and includes, for example, a temperature of 15 to 25 ° C. and the like.

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

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

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

<Composition for forming protective film (IV-1)>
[UV-curable component (a)]
The composition for forming a protective film contains an ultraviolet ray curable component (a). The ultraviolet ray curable component (a) is a component which is cured by irradiation of ultraviolet rays, and is also a component for imparting film forming property, flexibility and the like to the protective film forming film.
As the ultraviolet ray curable component (a), for example, a polymer (a1) having an ultraviolet ray curable group, a weight average molecular weight of 80000 to 2,000,000 and an ultraviolet ray curable group, a compound having a molecular weight of 100 to 80000 (a2) Can be mentioned. At least a part of the polymer (a1) may or may not be crosslinked by a crosslinking agent (f) described later.
In the present specification, weight-average molecular weight means polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise noted.

(Polymer having a UV-curable group and having a weight average molecular weight of 80,000 to 2,000,000 (a1))
Examples of the polymer (a1) having a UV-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 possessed by another compound, An acrylic resin (a1-1) formed by polymerization of an ultraviolet-curable compound (a12) having a group that reacts with a group and an ultraviolet-curable group such as an ultraviolet-curable double bond can be mentioned.

Examples of the functional group capable of reacting with a group possessed by another compound include, for example, 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 Groups), epoxy groups and the like. However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably a hydroxyl group.

. Acrylic polymers having functional groups (a11)
Examples of the acrylic polymer (a11) having a 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 the monomers, monomers (non-acrylic monomers) other than acrylic monomers may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.

As an acryl-type monomer which has the said functional group, a hydroxyl-containing monomer, a carboxy-group containing monomer, an amino-group containing monomer, a substituted amino-group containing monomer, an epoxy-group containing monomer etc. are mentioned, for example.

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) acrylics such as vinyl alcohol and allyl alcohol And unsaturated alcohols (unsaturated alcohols having no (meth) acryloyl skeleton) and the like.

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.

As the carboxy group-containing monomer, for example, 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, And ethylenically unsaturated dicarboxylic acids such as citraconic acid (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like Can be mentioned.

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

Examples of the acrylic monomer having no functional group include 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 ( 2-ethylhexyl 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) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), The alkyl group constituting the alkyl ester such as heptadecyl (meth) acrylate and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms (meth And acrylic acid alkyl esters and the like.

Further, examples of the acrylic monomer having no functional group include, for example, methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkoxyalkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate etc., (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide And derivatives thereof; (meth) acrylates having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate It can be mentioned.

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

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) 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 (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the same is 0.1 to 50 mass % Is preferable, 1 to 40% by mass is more preferable, and 3 to 30% by mass is particularly preferable. In the acrylic resin (a1-1) obtained by the copolymerization of the acrylic polymer (a11) and the ultraviolet curable compound (a12) with the ratio being in such a range, the ultraviolet curing is performed. The content of the nature group can be easily adjusted to the 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 in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the composition (IV-1) for forming a protective film, the content of the acrylic resin (a1-1) is 1 to 40% by mass based on the total mass of the composition (IV-1) for forming a protective film Is preferable, 2 to 30% by mass is more preferable, and 3 to 20% by mass is particularly preferable.

・ UV-curable compound (a12)
The said ultraviolet curable compound (a12) is 1 type, or 2 or more types selected from the group which consists of an isocyanate group, an epoxy group, and a carboxy group as a group which can react with the functional group which the said acryl-type polymer (a11) has. Are preferred, and those having an isocyanate group as the group are more preferred. For example, when the ultraviolet 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 ultraviolet curable compound (a12) preferably has 1 to 5, and more preferably 1 to 3 of the ultraviolet curable groups in one molecule.

Examples of the ultraviolet curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl). Ethyl isocyanate; Acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; reaction of diisocyanate compound or polyisocyanate compound with polyol compound and hydroxyethyl (meth) acrylate The acryloyl monoisocyanate compound etc. which are obtained are mentioned. Among these, the ultraviolet curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The ultraviolet curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the acrylic resin (a1-1), the ratio of the content of the ultraviolet curable group derived from the ultraviolet curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) Is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. The adhesive force of the protective film formed by hardening becomes larger because the ratio of the said content is such a range. In addition, when the said ultraviolet curable compound (a12) is a monofunctional (it has one said group in 1 molecule) compound, although the upper limit of the ratio of the said content will be 100 mol%, In the case where the curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

When the polymer (a1) is at least a part of which is crosslinked by the crosslinking agent (f), the polymer (a1) has been described as constituting the acrylic polymer (a11) And a monomer which does not correspond to any of the above-mentioned monomers and which has a group reactive with the crosslinking agent (f) may be polymerized and crosslinked in the group reactive with the crosslinking agent (f) The group derived from the ultraviolet ray curable compound (a12) and reactive to the functional group may be crosslinked.

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

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

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

As a low molecular weight compound which has an ultraviolet curable group among the said compounds (a2), a polyfunctional monomer, an oligomer, etc. are mentioned, for example, The acrylate type compound which has 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, tricyclodecanedimethanol di (meth) acrylate (tri) Cyclodecane dimethylol di (meth) a 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, and 2-hydroxy-1,3-di (meth) acryloxy bifunctional (meth) acrylates such as 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, and dipentaerythritol hexa (hexa) Multifunctional (meth) acrylates such as (meth) acrylates;
Polyfunctional (meth) acrylate oligomers, such as a urethane (meth) acrylate oligomer, etc. are mentioned.

As an epoxy resin which has an ultraviolet curable group among said compounds (a2), and a phenol resin which has an ultraviolet curable group, it is described, for example, in paragraph 0043 of "JP-A-2013-194102" and the like. Can be used. Such a resin also corresponds to a resin constituting a thermosetting component (h) described later, but in the present invention, it is handled as the compound (a2).

The molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.

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

[Polymer (b) having no UV-curable group]
When the composition for forming a protective film (IV-1) and the film for forming a protective film contain the compound (a2) as the ultraviolet ray curable component (a), a polymer (b) further having no ultraviolet ray curable group It is preferable to also contain.
The polymer (b) may be at least a part of which is crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.

As a polymer (b) which does not have an ultraviolet curable group, for example, acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, acrylic urethane resin, polyvinyl alcohol (PVA), butyral resin, and polyester urethane Resin etc. are mentioned.
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, may be a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers, It may also be a copolymer of one or more acrylic monomers and a monomer (non-acrylic monomer) other than one 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 thereof 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 methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 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) acrylate ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Acid undecyl, dodecyl (meth) acrylate (lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), The alkyl group constituting the alkyl ester such as heptadecyl (meth) acrylate and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms (meth And acrylic acid alkyl esters and the like.

Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyl oxyethyl ester and the like.

As said glycidyl group containing (meth) acrylic acid ester, glycidyl (meth) acrylate etc. are mentioned, for example.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (meth) acrylate And 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 and the like.

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

As the polymer (b) having no UV curable group and at least partially crosslinked by the crosslinking agent (f), for example, the reactive functional group in the polymer (b) is the crosslinking agent (f) The thing which reacted with is mentioned.
The reactive functional group may be appropriately selected depending on 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, an amino group and the like, and among these, a hydroxyl group having high reactivity with the isocyanate group. Is preferred. When the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amido group and the like, among which a carboxy having a high reactivity with the epoxy group Groups are preferred. However, it is preferable that the reactive functional group is a group other than a carboxy group in terms of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip.

As a polymer (b) which does not have an ultraviolet curable group which has the said reactive functional group, the thing obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. 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 monomer constituting the polymer It may be used. As said polymer (b) which has a hydroxyl group as a reactive functional group, what was obtained by polymerizing a hydroxyl-containing (meth) acrylic acid ester is mentioned, for example, In addition to this, the said acrylics mentioned above What is obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted by the reactive functional group among the system monomer or the non-acrylic monomer is mentioned.

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

The weight average molecular weight (Mw) of the polymer (b) having no UV-curable group is from 10000 to 2000000, from the viewpoint that the film forming property of the composition for forming a protective film (IV-1) becomes better. Is preferable, and 100000 to 1.500000 is more preferable.

The composition for forming a protective film (IV-1) and the film for forming a protective film may contain only one type of polymer (b) having no ultraviolet curable group, or two or more types of polymers (b). When it is above, the combination and ratio of them can be selected arbitrarily.

The composition for forming a protective film (IV-1) includes one containing either one or both of the polymer (a1) and the compound (a2). And when the composition (IV-1) for protective film formation contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an ultraviolet curable group further, In this case, It is also preferable to contain (a1). In addition, the composition for forming a protective film (IV-1) contains neither the compound (a2) but the polymer (a1) and the polymer (b) having no ultraviolet curable group. May be

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

In the composition for forming a protective film (IV-1), the ratio of the total content of the ultraviolet ray curable component (a) and the polymer (b) having no ultraviolet ray curable group to the total content of components other than the solvent (That is, the total content of the ultraviolet ray curable component (a) and the polymer (b) having no ultraviolet ray curable group in the film for protective film formation relative to the total mass of the film for protective film formation) is from 5 to 90 It is preferably mass%, more preferably 10 to 80 mass%, particularly preferably 15 to 70 mass%, and for example, 20 to 60 mass% and 25 to 50 mass%. It may be. By the ratio of the said total content being such a range, the ultraviolet curability of the film for protective film formation becomes more favorable.

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

The composition for forming a protective film (IV-1) comprises, according to the purpose, a UV curable component (a), a photopolymerization initiator (c) other than a polymer (b) having no UV curable group, and a filling Materials (d), coupling agents (e), crosslinking agents (f), colorants (g), thermosetting components (h), curing accelerators (i), and general purpose additives (z) You may contain 1 type, or 2 or more types selected.
For example, by using the composition for forming a protective film (IV-1) containing the ultraviolet ray curable component (a) and the thermosetting component (h), the film for forming a protective film formed is heated by heating. The adhesion to the adherend is improved, and the strength of the protective film formed from the protective film-forming film is also improved.

[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, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) ) Acyl phosphine oxide compounds such as phenyl phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; benzyl phenyl sulfide, and tetramethylthiuram monosulphie Sulfide compounds such as 1; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobis isobutyro nitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, and 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O Benzophenone compounds such as -acetyl oxime; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone; and And 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as an amine or the like can be used.

The composition (IV-1) for forming a protective film may contain only one type of photoinitiator, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.

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

[Filler (d)]
When the film for protective film formation contains a filler (d), the light transmittance of the film for protective film formation can be adjusted. Moreover, when the film for protective film formation contains a filler (d), adjustment of a thermal expansion coefficient of the protective film obtained by hardening the film for protective film formation becomes easy. 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, when the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced and heat dissipation can also be improved.
As a filler (d), what consists of heat conductive materials is mentioned, for example.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, iron oxide, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; and surface modification of these inorganic fillers Articles; single crystal fibers of these inorganic fillers; and glass fibers.
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. And 3 to 10 μm are more preferable. When the average particle diameter of the filler (d) is in such a range, it is possible to suppress the decrease in the light transmittance of the protective film while maintaining the adhesiveness to the object on which the protective film is to be formed.
In the present specification, “average particle size” means the value of particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve determined by the laser diffraction scattering method, unless otherwise specified. .

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

When the filler (d) is used, in the composition (IV-1) for forming a protective film, the ratio of the content of the filler (d) to the total content of all the components other than the solvent (that is, for forming a protective film) The content of the filler (d) in the film is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass, for example, It may be 40 to 70% by mass, and 45 to 65% by 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 adhesiveness 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 is improved in water resistance without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group possessed by the ultraviolet ray curable component (a), the polymer (b) having no ultraviolet ray curable group, etc., and a silane cup It is more preferable that it is a ring 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-mercaptopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. It can be mentioned.

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

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 is the ultraviolet curable component (a) and the ultraviolet curing The amount 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 functional group. Particularly preferred is 1 to 5 parts by mass. When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the film for protective film formation to the adherend is improved. The effect of using the coupling agent (e) can be obtained more remarkably. 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)]
The composition for forming a protective film (IV-1) may contain a crosslinking agent (f). By crosslinking the above-mentioned ultraviolet ray curable component (a) and the polymer (b) having no ultraviolet ray curable group using the crosslinking agent (f), the initial adhesion and cohesion of the protective film-forming film can be obtained. It can be adjusted.

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

As the organic polyvalent isocyanate compound, for example, 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 etc.” Abbreviated in some cases); trimers such as the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds and the like with a polyol compound Etc. The “adduct” includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and low contents such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil It means a reactant with a molecule active hydrogen-containing compound. Examples of the adduct include xylylene diisocyanate adduct of trimethylolpropane as described later, and the like. Also, "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at the terminal 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 Diphenylmethane-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 in the hydroxyl groups of all or part of a polyol such as propane Or two or more compounds are added; and lysine diisocyanate.

Examples of the organic polyhydric imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. -Tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridine carboxamide) triethylene melamine and the like.

When using an organic polyvalent isocyanate compound as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the ultraviolet ray curable component (a) or the polymer (b) having no ultraviolet ray curable group. When the crosslinking agent (f) has an isocyanate group and the ultraviolet ray curable component (a) or the polymer (b) not having an ultraviolet ray curable group has a hydroxyl group, the crosslinking agent (f) and the ultraviolet ray curable component (a) Or a reaction with the polymer (b) having no ultraviolet curable group, a crosslinked structure can be easily introduced into the protective film-forming film.

The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof And the ratio can be selected arbitrarily.

When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the composition (IV-1) for forming a protective film is a polymer having no ultraviolet ray curable component (a) and no ultraviolet ray curable group ( 0.01 to 20 parts by mass is preferable, and 0.1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the total content of b) Is particularly preferred. When the content of the crosslinking agent (f) is equal to or more than the lower limit value, the effect of using the crosslinking agent (f) can be more remarkably obtained. Moreover, the excess 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)]
As a coloring agent (g), well-known things, such as an inorganic type pigment, an organic type pigment, and an organic type dye, are mentioned, for example.

Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrilium 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 The Systems dyes, pyranthrone pigments and threne dyes.

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

The composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, a combination thereof The ratio of the composition for forming a protective film (IV-1) and the film for forming a protective film is 20% or less at 20 nm wavelength light transmittance, 25% or less at 550 nm wavelength light transmittance, and 1600 nm wavelength light transmittance Is adjusted to be 25% or more. The colorant (g) preferably contains at least a blue pigment, and more preferably contains a blue pigment, a yellow pigment, and a red pigment. Here, as the blue dye, for example, a phthalocyanine dye is preferable, and as the yellow dye, for example, an isoindolinone dye is preferable, and as the red dye, for example, an anthraquinone dye is preferable.

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

Composition for protective film formation (IV-1) and film for protective film formation such that the light transmittance at a wavelength of 350 nm of the film for protective film formation is 20% or less Preferably, the content of the blue dye in the above is 25 to 50 parts by mass with respect to 100 parts by mass of the total content of the coloring agent (g).

In the composition (IV-1) for forming a protective film, the ratio of the content of the colorant (g) to the total content of all the components other than the solvent (that is, the content of the colorant (g) in the film for forming a protective film) The amount is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass. When the content of the coloring agent (g) is at least the lower limit value, the light transmittance of the protective film-forming composition (IV-1) and the protective film-forming film at a wavelength of 350 nm is 20% or less, and the wavelength of 550 nm The light transmittance of the light source is adjusted to 25% or less, and the light transmittance of the wavelength 1600 nm is 25% or more. Moreover, the excess use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.

[Thermosetting component (h)]
The composition for forming a protective film (IV-1) and the film for forming a protective film may contain a thermosetting component (h). The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, The combination and ratio of can be selected arbitrarily.

As a thermosetting component (h), an epoxy-type thermosetting resin, a thermosetting polyimide, polyurethane, unsaturated polyester, a silicone resin etc. are mentioned, for example, An epoxy-type thermosetting resin is preferable.

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

・ Epoxy resin (h1)
As an epoxy resin (h1), a well-known thing is mentioned, For example, a polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, an ortho cresol novolak epoxy resin, a dicyclopentadiene type epoxy resin, Examples thereof include bifunctional or higher epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.

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

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by converting a part of epoxy group of polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example. 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 which comprises an epoxy resin, etc. are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (also referred to as vinyl group), 2-propenyl group (also referred to as allyl group) and (meth) acryloyl group And (meth) acrylamide groups etc. are mentioned, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000, and is 400 to 10000, from the viewpoint of the curability of the film for protective film formation and the strength and heat resistance of the protective film. And more preferably 500 to 3,000.
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, the combination and ratio thereof can be optionally selected.

・ Heat curing agent (h2)
The heat curing 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, and a group in which an acid group is anhydrated, and the phenolic hydroxyl group, an amino group or an acid group is anastabilized. It is preferably a hydroxyl group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), as a phenol-based curing agent having a phenolic hydroxyl group, for example, polyfunctional phenol resin, biphenol, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkyl phenol resin and the like can be mentioned. .
Among the thermosetting agents (h2), examples of amine-based curing agents having an amino group include dicyandiamide.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound obtained by substituting a part of hydroxyl groups of a phenol resin with a group having an unsaturated hydrocarbon group, and an aromatic ring of a phenol resin, The compound etc. which a group which has an unsaturated hydrocarbon group directly couple | bonds are mentioned.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenol-based curing agent is used as the heat-curing agent (h2), the heat-curing agent (h2) preferably has a high softening point or glass transition temperature, from the viewpoint that the removability of the protective film from the support sheet is improved. .

Among thermosetting agents (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl phenol resin and the like is preferably 300 to 30,000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
Among the thermosetting agents (h2), for example, the molecular weight of the non-resin component 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 combination and ratio can be selected arbitrarily.

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

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, epoxy resin (h1) and heat) in the composition for forming a protective film (IV-1) and the film for forming a protective 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 ultraviolet curable group.

[Hardening accelerator (i)]
The composition for forming a protective film (IV-1) and the film for forming a protective film may contain a curing accelerator (i). A hardening accelerator (i) is a component for adjusting the hardening speed of the film for protective film formation.
Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenyl Imidazoles such as imidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributyl phosphine, diphenyl phosphine, tri Organic phosphines such as phenyl phosphine; tetraphenyl phosphonium tetraphenyl borate; and tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate.

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

[General purpose additive (z)]
The composition for forming a protective film (IV-1) and the film for forming a protective film may contain a general-purpose additive (z). The general-purpose additive (z) may be a known one, can be selected arbitrarily according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, etc. Can be mentioned.

The composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective film may be only one type, or two or more types, and in the case of two or more types, Combinations and ratios can be selected arbitrarily.
When the general-purpose additive (z) is used, the content of the protective film-forming composition (IV-1) and the content of the general-purpose additive (z) of the protective film-forming film are not particularly limited, and may be appropriately selected depending on the purpose. do it.

[solvent]
The composition for forming a protective film (IV-1) preferably further contains a solvent. The composition for forming a protective film (IV-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol Alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition for forming a protective film (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 composition (IV-1) for forming a protective film is methyl ethyl ketone, toluene, ethyl acetate or the like in that the components contained in composition (IV-1) for forming a protective film can be mixed more uniformly. Is preferred.

<< Method of producing composition for forming protective film >>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending the respective components for constituting the composition.
There is no particular limitation on the order of addition of each component at the time of blending, 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 this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; a method of adding ultrasonic waves and mixing, etc. It may be selected as appropriate.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

製造 Method of Producing Protective Film-Forming Film The protective film-forming film can be produced by coating the protective film-forming composition on a release film (preferably the release-treated surface thereof) and drying it as required. . The manufacturing method at this time is as described above.
In addition, for example, as shown in FIG. 1, the film for protective film formation is normally stored in the state in which the peeling film was bonded together by the both surfaces. To that end, a release film (preferably a release-treated surface) is preferably formed on the exposed surface (surface opposite to the side provided with the release film) of the protective film-forming film formed on the release film as described above. You just need to paste

使用 Method of Use of Protective Film-Forming Film As described above, the protective film-forming film can be formed on a support sheet to form a protective film-forming composite sheet. The composite sheet for protective film formation is stuck on the back surface (surface on the opposite side to the electrode formation surface) of the semiconductor wafer by the protective film formation film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

On the other hand, the protective film-forming film may be provided first on the back surface of the semiconductor wafer, not on the support sheet. For example, first, a protective film-forming film is attached to the back surface of the semiconductor wafer, and a supporting sheet is attached to the exposed surface of the protective film-forming film (the surface opposite to the side attached to the semiconductor wafer) The film for protective film formation in the pasted state is irradiated with ultraviolet light and cured to form a protective film, and then the exposed surface of this protective film (the side opposite to the side pasted on the semiconductor wafer) The support sheet is bonded to form a composite sheet for forming a protective film. Thereafter, from this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method described later.

複合 Composite Sheet for Forming Protective Film The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and the film for forming a protective film is provided on the support sheet.

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

The thickness of the semiconductor wafer to be used for the composite sheet for protective film formation of the present invention is not particularly limited, but is preferably 30 to 1000 μm from the viewpoint of easier division into semiconductor chips described later. More preferably, it is 100 to 400 μm.
Hereinafter, the configuration of the protective film-forming composite sheet will be described in detail.

Support Sheet The support sheet may be formed of a single layer (single layer), or may be formed of two or more layers. When the support sheet comprises a plurality of layers, the plurality of layers may be identical to or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

As a preferable support sheet, for example, a substrate is provided, and an adhesive layer is directly laminated on the substrate and laminated (a substrate and an adhesive layer are laminated in direct contact in this order) A substrate, an intermediate layer and a pressure-sensitive adhesive layer laminated in this order in direct contact with each other in the thickness direction; and those consisting only of a substrate.
Examples of the composite sheet for protective film formation of the present invention will be described below for each type of such a support sheet, with reference to the drawings.

FIG. 2: is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
In the drawings after FIG. 2, the same components as those shown in the already described drawings are denoted by the same reference numerals as in the already explained drawings, and the detailed description thereof will be omitted.

The composite sheet 1A for protective film formation shown here is provided with the base material 11, the adhesive layer 12 is provided on the base material 11, and the protective film formation film 13 is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for protective film formation is, in other words, one surface of the support sheet 10 (in the present specification, "first surface" And a protective film-forming film 13 is laminated on the substrate 10a). In addition, the protective film-forming composite sheet 1A further includes a peeling film 15 on the protective film-forming film 13.

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

In the protective film-forming composite sheet 1A, the protective film-forming film 13 has an ultraviolet ray curable component, and the light transmittance of 350 nm wavelength is 20% or less, and the light transmittance of 550 nm wavelength is 25% or less And the light transmittance at a wavelength of 1600 nm is 25% or more.

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

The composite sheet 1A for protective film formation shown in FIG. 2 has the back surface of a semiconductor wafer (not shown) attached to the first surface 13a of the protective film formation film 13 with the release film 15 removed. The upper surface of the surface 16 a of the tool 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 a composite sheet for protective film formation according to another embodiment of the present invention.
The composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film-forming film 13 is laminated on the entire first surface 12a of the pressure-sensitive adhesive layer 12 The release film 15 is laminated on the entire surface of the first surface 13 a of the protective film-forming film 13.

In the protective film-forming composite sheet 1B, the protective film-forming film 13 has an ultraviolet ray curable component, and the light transmittance of 350 nm wavelength is 20% or less, and the light transmittance of 550 nm wavelength is 25% or less And the light transmittance at a wavelength of 1600 nm is 25% or more.

The composite sheet 1B for protective film formation shown in FIG. 3 is a semiconductor wafer (not shown) on the central region of the first surface 13a of the protective film formation film 13 with the release film 15 removed. And the area in the vicinity of the peripheral portion is used by being attached to a jig such as a ring frame.

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

In the protective film-forming composite sheet 1C, the protective film-forming film 13 has a UV-curable component and has a light transmittance of 20% or less at a wavelength of 350 nm and a light beam at a wavelength of 550 nm. The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

Similar to the composite sheet 1A for protective film formation shown in FIG. 2, the composite sheet 1C for protective film formation shown in FIG. 4 is on the first surface 13a of the film 13 for protective film formation with the release film 15 removed. The back surface of the semiconductor wafer (not shown) is attached, and the upper surface of the surface 16a of the adhesive layer 16 for jig is used by being adhered to a jig such as a ring frame.

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

In the protective film-forming composite sheet 1D, the protective film-forming film 13 has a UV-curable component and has a light transmittance of 20% or less at a wavelength of 350 nm and a light beam at a wavelength of 550 nm. The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

The composite sheet 1D for protective film formation shown in FIG. 5 is the same as the composite sheet 1B for protective film formation shown in FIG. 3 with the release film 15 removed, on the first surface 13a of the film 13 for protective film formation. Among them, the back surface of a semiconductor wafer (not shown) is attached to a partial region on the center side, and the region in the vicinity of the peripheral portion is attached to a jig such as a ring frame and used.

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

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

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

In the protective film-forming composite sheet 1E, the protective film-forming film 13 has a UV curable component, and the light transmittance of a wavelength 350 nm is 20% or less, and the light beam of a wavelength 550 nm The transmittance is 25% or less, and the light transmittance at a wavelength of 1600 nm is 25% or more.

The composite sheet 1E for protective film formation shown in FIG. 6 has the back surface of a semiconductor wafer (not shown) attached to the surface 23a of the protective film formation film 23 in a state where the release film 15 is removed. The area | region where the film 23 for protective film formation is not laminated | stacked among 12 1st surface 12a is stuck on jigs, such as a ring frame, and is used.

In addition, in the composite sheet 1E for protective film formation shown in FIG. 6, in the area | region where the film 23 for protective film formation is not laminated | stacked among the 1st surfaces 12a of the adhesive layer 12, what is shown in FIG. The adhesive layer for jig | tool may be laminated | stacked similarly to (not shown). Similar to the composite sheet for protective film formation shown in FIGS. 2 and 4, the composite sheet 1E for protective film formation provided with such an adhesive layer for jigs has a ring frame for the surface of the adhesive layer for jigs. It is stuck on a jig etc. and used.

Thus, the composite sheet for protective film formation may be provided with the adhesive layer for jigs, regardless of the form of the support sheet and the film for protective film formation. However, generally, as shown in FIGS. 2 and 4, as a composite sheet for protective film formation provided with a jig adhesive layer, one provided with a jig adhesive layer on a protective film formation film Is preferred.

The composite sheet for protective film formation which concerns on one Embodiment of this invention is not limited to what is shown in FIGS. 2-6, A part of what is shown in FIGS. 2-6 in the range which does not impair the effect of this invention The configuration of the above may be changed or deleted, or another configuration may be added to those described above.

For example, in the composite sheet for protective film formation shown in FIGS. 4 and 5, an intermediate layer may be provided between the substrate 11 and the protective film formation film 13. The intermediate layer can be selected arbitrarily according to the purpose.
Moreover, in the composite sheet for protective film formation shown in FIG.2, FIG3 and FIG.6, the intermediate | middle layer may be provided between the base material 11 and the adhesive layer 12. As shown in FIG. That is, in the composite sheet for protective film formation of the present invention, the support sheet may be formed by laminating the base material, the intermediate layer and the pressure-sensitive adhesive layer in this order in the thickness direction. Here, the intermediate layer is the same as the intermediate layer which may be provided in the composite sheet for protective film formation shown in FIGS. 4 and 5.
In the composite sheet for protective film formation shown in FIGS. 2 to 6, the layer other than the intermediate layer may be provided at an arbitrary place.
Moreover, in the composite sheet for protective film formation, a clearance may be partially generated between the release film and the layer in direct contact with the release film.
Moreover, in the composite sheet for protective film formation, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

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

The support sheet may be transparent or opaque, and may be colored according to the purpose.
Among them, in the present invention in which the protective film-forming film has ultraviolet curability, it is preferable that the support sheet transmits ultraviolet light.

For example, in the support sheet, the transmittance of light having a wavelength of 350 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, when the protective film-forming film is irradiated with ultraviolet light through 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 of the transmittance of light with a wavelength of 350 nm is not particularly limited. For example, the light transmittance may be 95% or less.
The lower limit value and the upper limit value of the light transmittance of the support sheet at a wavelength of 350 nm can be arbitrarily combined. For example, the transmittance of light with a wavelength of 350 nm of the support sheet is preferably 30% to 95%, more preferably 50% to 95%, and particularly preferably 70% to 95%. preferable.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
When the transmittance of light is in such a range, the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit of the transmittance of light of wavelength 532 nm is not particularly limited. For example, the light transmittance may be 95% or less.
The lower limit value and the upper limit value of the transmittance of light of wavelength 532 nm of the support sheet can be arbitrarily combined. For example, the transmittance of light of wavelength 532 nm of the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less preferable.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of light is in such a range, the protective film-forming film or the protective film is irradiated with a laser beam through the support sheet, and printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value of the transmittance of light with a wavelength of 1064 nm is not particularly limited. For example, the light transmittance may be 95% or less.
The lower limit value and the upper limit value of the light transmittance for the wavelength 1064 nm of the support sheet can be arbitrarily combined. For example, the transmittance of light with a wavelength of 1064 nm of the support sheet is preferably 30% or more and 95% or less, more preferably 50% or more and 95% or less, and particularly preferably 70% or more and 95% or less preferable.

In the support sheet, the transmittance of light with a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the semiconductor wafer is irradiated with laser light through the support sheet and the protective film-forming film or protective film, and the modified layer is formed on the semiconductor wafer. It can be easily formed.
On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 1342 nm is not particularly limited. For example, the light transmittance may be 95% or less.
The lower limit value and the upper limit value of the light transmittance of the wavelength 1342 nm of the support sheet can be arbitrarily combined. For example, the transmittance of light having a wavelength of 1342 nm of the support sheet is preferably 30% to 95%, more preferably 50% to 95%, and particularly preferably 70% to 95%. preferable.
Next, each layer constituting the support sheet will be described in more detail.

○ Base Material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin Ethylene-vinyl copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and ethylene-norbornene copolymer Copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); polystyrene; polycycloolefins; Polyethylene terephthalate, PO Polyesters such as ethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, and wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; two or more of the above-mentioned polyesters Copolymers of: poly (meth) acrylic acid ester, polyurethane, polyurethane acrylate, polyimide, polyamide, polycarbonate, fluorocarbon resin, polyacetal, modified polyphenylene oxide, polyphenylene sulfide, polysulfone, and polyether ketone.
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are also 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.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or more of the above-described resins exemplified so far; modification of an ionomer using one or more of the above-described resins exemplified so far Resin is also mentioned.

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

The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 100 μm. When the thickness of the substrate is in such a range, the flexibility of the composite sheet for protective film formation and the adhesion to a semiconductor wafer or a 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 comprising a plurality of layers means the total thickness of all the layers constituting the substrate means.

The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which the thickness variation is suppressed regardless of the part. Among the above-mentioned constituent materials, as materials which can be used to construct a substrate having such a high thickness accuracy, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc. Can be mentioned.

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

The optical properties of the substrate are preferably such as to satisfy the optical properties of the support sheet described above. For example, the substrate may be transparent or opaque, or may be colored according to the purpose, or other layers may be deposited.
And in this invention which the film for protective film formation has ultraviolet curability, as a base material, what permeate | transmits an ultraviolet-ray is preferable.

The substrate is roughened by sand blasting, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, etc., in order to improve the adhesion to other layers such as the pressure-sensitive adhesive layer provided thereon. The surface may be subjected to oxidation treatment such as ozone and ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
Moreover, the surface of the substrate may be subjected to primer treatment.
In addition, the base material prevents adhesion of the base material to another sheet and adhesion of the base material to the suction table when the antistatic coating layer and the composite sheet for protective film formation are stacked and stored. It may have a layer or the like.

The substrate can be produced by a known method. For example, the base material containing resin can be manufactured by shape | molding the resin composition containing the said resin.

○ Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is in the form of a sheet or a film, and contains a pressure-sensitive adhesive.
Examples of the pressure-sensitive adhesive include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, epoxy resins, polyvinyl ethers, and adhesive resins such as polycarbonates and ester resins. Acrylic resins are exemplified. preferable.

In the present invention, the term "adhesive resin" is a concept including both an adhesive resin and an adhesive resin, and for example, the resin itself is not limited to one having adhesiveness. It also includes a resin that exhibits tackiness when used in combination with other components such as additives, and a resin that exhibits adhesion due to the presence of a trigger such as heat or water.

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

The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, "the thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

The optical properties of the pressure-sensitive adhesive layer preferably satisfy the optical properties of the support sheet described above. For example, the pressure-sensitive adhesive layer may be transparent or opaque, or may be colored according to the purpose.
And in this invention which the film for protective film formation has ultraviolet curability, that to which an adhesive layer permeate | transmits an ultraviolet-ray is preferable.

The pressure-sensitive adhesive layer may be formed using an energy ray-curable adhesive other than ultraviolet light, or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer formed using an energy ray-curable pressure-sensitive adhesive other than ultraviolet light can easily adjust physical properties before and after curing. Here, the term "energy beam" means an electromagnetic wave or charged particle beam having energy quantum, and examples thereof include radiation and electron beam. "Energy ray curable" means a property of curing by irradiation with energy rays, and "non-energy ray curable" means a property of not curing even by irradiation of energy rays.

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target site by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying it as necessary. The more specific formation method of an adhesive layer is demonstrated in detail later with the formation method of another layer. The ratio of the contents of the components which do not vaporize at normal temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components of the pressure-sensitive adhesive layer.

The application of the pressure-sensitive adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater And methods using various coaters such as Meyer bar coater and kiss coater.

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

When the pressure-sensitive adhesive layer is energy ray-curable, a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive, that is, an energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable tackiness Pressure-sensitive adhesive composition (I-1) containing resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; non-energy Energy ray curable adhesive resin (I-2a) (hereinafter referred to as “adhesive resin (I-2a)”) wherein an unsaturated group is introduced into the side chain of the linear curable adhesive resin (I-1a) Pressure-sensitive adhesive composition (I-2) containing the abbreviation); pressure-sensitive adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound, etc. Can be mentioned.

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

[Adhesive resin (I-1a)]
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 structural unit which the said acrylic resin has may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combination and ratio can be selected arbitrarily.

Examples of the (meth) acrylic acid alkyl ester include ones 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, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylate ) Undecyl acrylate, dodecyl (meth) acrylate (also lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also referred to as palmityl (meth) acrylate), Examples include heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate), nonadecyl (meth) acrylate, and icosyl (meth) acrylate.

It is preferable that the said acryl-type polymer has a structural unit derived from the (meth) acrylic-acid alkylester whose carbon number of the said alkyl group is 4 or more from the point which the adhesive force of an adhesive layer improves. The carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8, in order to further improve the adhesion of the pressure-sensitive adhesive layer. Moreover, it is preferable that the (meth) acrylic-acid alkyl ester whose carbon number of the said alkyl group is 4 or more is methacrylic acid alkyl ester.

The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer, in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group reacts with a crosslinking agent described later to be a crosslinking origin, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later What makes it possible to introduce an unsaturated group into the side chain of an acrylic polymer by doing is mentioned.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. are mentioned, for example.
That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer and a carboxy group-containing monomer, and 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 units. And 3 to 30% by mass is particularly preferable.

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

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, the combination and ratio thereof can be arbitrarily selected.

The acrylic polymer can be used as the above-mentioned non-energy ray curable tackifying resin (I-1a).
On the other hand, those obtained by reacting the unsaturated group-containing compound having an energy ray polymerizable unsaturated group (ultraviolet polymerizable group) with the functional group in the acrylic polymer are the above-mentioned energy ray curable adhesive resin It can be used as (I-2a).

The adhesive resin (I-1a) contained in the 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 are optionally It can be selected.

In the pressure-sensitive adhesive composition (I-1), the content of the adhesive resin (I-1a) relative to the total content of the components other than the solvent is preferably 5 to 99% by mass, and 10 to 95% by mass Is more preferable, and 15 to 90% by mass is particularly preferable.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays.
Among the energy ray-curable compounds, as a monomer, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4 Polyvalent (meth) acrylates such as -butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; Epoxy (meth) acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomers include oligomers formed by polymerization of the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly reduced.

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 1 to 95% by mass with respect to the total content of components other than the solvent of the pressure-sensitive adhesive composition (I-1). Is preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.

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

The crosslinking agent, for example, reacts with the functional group to crosslink the adhesive resin (I-1a).
Crosslinking agents include, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isocyanate-based crosslinking agents such as adducts of these diisocyanates (crosslinking agents having an isocyanate group); epoxy-based crosslinking agents such as ethylene glycol glycidyl ether (Cross-linking agent having glycidyl group); Aziridine-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] trifosphatriazine (cross-linking agent having aziridinyl group); Metal chelate-based cross-linking agent such as aluminum chelate ( Crosslinkers having a metal chelate structure); isocyanurate crosslinkers (crosslinkers having an isocyanuric acid skeleton) and the like.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoint of improving the cohesion of the pressure-sensitive adhesive to improve the adhesion of the pressure-sensitive adhesive layer and being easy to obtain.

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, the combination and ratio thereof can be optionally selected.

In the pressure-sensitive adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the 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.

[Photoinitiator]
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 curing reaction even when irradiated with energy rays of relatively low energy 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- Acetophenone compounds such as hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acyl phosphine oxide compounds such as phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; benzyl phenyl sulfide and tetramethyl thiuram monosulfide Sulfide compounds; 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; Dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; and 2-chloroanthraquinone etc. Be
Further, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone and the like; photosensitizers such as amine and the like can also be used.

The photopolymerization initiator 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 photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound, and 0 The content is more preferably in the range of 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 which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agent, antioxidant, softener (plasticizer), filler (filler), rust inhibitor, coloring agent (pigment, dye), sensitizer, tackifier And known additives such as reaction retarders and crosslinking promoters (catalysts).
The reaction retarder means, for example, an unintended cross-linking reaction in the adhesive composition (I-1) during storage by the action of a catalyst mixed in the adhesive composition (I-1). It is to control progress. The reaction retarder includes, for example, those which form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule It can be mentioned.

The other additives 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 other additive is not particularly limited, and may be appropriately selected depending on the type.

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. The pressure-sensitive adhesive composition (I-1) contains a solvent, whereby the coating suitability to the surface to be coated is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

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

The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, 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 solvent is not particularly limited, and may be appropriately adjusted.

<Pressure-sensitive adhesive composition (I-2)>
The pressure-sensitive adhesive composition (I-2) is, as described above, an energy ray-curable adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy ray-curable 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 beam polymerizable unsaturated group.

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with the functional group in the adhesive resin (I-1a) in addition to the energy beam polymerizable unsaturated group It is a compound having a group.
Examples of the energy ray polymerizable unsaturated group include (meth) acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), etc., and (meth) acryloyl group is preferable.
Examples of the group capable of binding to a functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of binding to a hydroxyl group or an amino group, and a hydroxy group and amino group capable of binding to a carboxy group or an epoxy group. Etc.

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

The adhesive resin (I-2a) contained in the 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 are optionally It can be selected.

In the pressure-sensitive adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, and preferably 10 to 95% by mass, based on the total mass of components other than the solvent. And more preferably 10 to 90% by mass.

[Crosslinking agent]
When the above-mentioned 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, I-2) may further contain a crosslinking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same as the crosslinking agent 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 optionally selected.

In the pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the 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.

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

The photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) may be the same as the photopolymerization initiator 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 mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a) 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-2) may contain other additives which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
Examples of the other additives in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be optionally selected.

In the pressure-sensitive adhesive composition (I-2), the content of the 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 the pressure-sensitive adhesive composition (I-1).
The solvent in the pressure-sensitive adhesive composition (I-2) may be the same as the solvent 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 appropriately adjusted.

<Pressure-sensitive adhesive composition (I-3)>
The pressure-sensitive adhesive composition (I-3) contains, as described above, 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 adhesive resin (I-2a) is preferably 5 to 99% by mass, and preferably 10 to 95% by mass, based on the total mass of the components other than the solvent. And more preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers which have an energy ray-polymerizable unsaturated group and can be cured by irradiation of energy rays, and the pressure-sensitive adhesive composition The same as the energy ray-curable compound contained in the compound (I-1) can be mentioned.
The energy ray-curable compound 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 energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a) Is more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.

[Photoinitiator]
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 proceeds curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

The photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) may be the same as the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).
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 100 parts by mass relative to the total content of the 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 which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-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 optionally selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
The solvent in the pressure-sensitive adhesive composition (I-3) may be the same as the solvent 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 appropriately adjusted.

<Adhesive Composition Other than Adhesive Composition (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive composition (I-3) have been mainly described, but those described as the components thereof are General pressure-sensitive adhesive compositions other than these three pressure-sensitive adhesive compositions (herein referred to as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") But it can be used as well.

As the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, non-energy ray-curable pressure-sensitive adhesive compositions can also be mentioned.
As a non-energy ray curable adhesive composition, for example, non-energy rays such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin The pressure-sensitive adhesive composition (I-4) containing a curable adhesive resin (I-1a) is mentioned, and one containing an acrylic resin is preferable.

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

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

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same ones as the adhesive resin (I-1a) in the 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 in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

In the pressure-sensitive adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, and preferably 10 to 95% by mass, based on the total mass of the components other than the solvent. And more preferably 15 to 90% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from a (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( It is preferable that I-4) further contains a crosslinking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same as the crosslinking agents 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 optionally selected.

In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the 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 which do not correspond to any of the components described above, as long as the effects of the present invention are not impaired.
Examples of the other additives include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-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 optionally selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as the pressure-sensitive adhesive composition (I-1).
The solvent in the pressure-sensitive adhesive composition (I-4) may be the same as the solvent 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 protective film formation, the pressure-sensitive adhesive layer is preferably non-UV curable. This is because when the pressure-sensitive adhesive layer is ultraviolet-curable, it may not be possible to simultaneously cure the pressure-sensitive adhesive layer when the film for protective film formation is cured by irradiation of ultraviolet light. When the pressure-sensitive adhesive layer is cured simultaneously with the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to such an extent that they can not be peeled off at these interfaces. In that case, it becomes difficult to peel off the cured protective film-forming film, that is, the semiconductor chip (semiconductor chip with protective film) having the protective film on the back surface, from the supporting sheet provided with the adhesive layer after curing. It will become impossible to pick up the semiconductor chip with a protective film normally. By making the pressure-sensitive adhesive layer non-ultraviolet curable in the support sheet, such a defect can be reliably avoided, and the semiconductor chip with a protective film can be picked up more easily.

Although the effect when the pressure-sensitive adhesive layer is non-UV-curable is described here, even if the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, this layer If it is non-ultraviolet curable, the same effect is exhibited.

<< Method of producing pressure-sensitive adhesive composition >>
Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-1) to (I-3) such as pressure-sensitive adhesive composition (I-4) It is obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition, such as components other than the pressure-sensitive adhesive.
There is no particular limitation on the order of addition of each component at the time of blending, 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 this compounding component in advance, or by previously diluting any compounding component other than the solvent A solvent may be used by mixing with these compounding ingredients without storage.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer; and a method of adding and mixing ultrasonic waves, etc. It should just select from.
The temperature and time of addition and mixing of the respective components are not particularly limited as long as the respective blended components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

製造 Method of Producing Protective Film-Forming Composite Sheet The protective film-forming composite sheet can be produced by laminating the above-described respective layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, in the case of laminating a pressure-sensitive adhesive layer on a substrate when manufacturing a support sheet, the above-mentioned pressure-sensitive adhesive composition may be coated on the substrate and dried as necessary.

On the other hand, for example, when a film for protective film formation is further laminated on the pressure-sensitive adhesive layer laminated on the substrate, the composition for protective film formation is coated on the pressure-sensitive adhesive layer to form a protective film. It is possible to form the forming film directly. Layers other than the protective film-forming film can be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer. As described above, in the case of forming a continuous two-layer laminated structure using any of the compositions, the composition is further coated on the layer formed of the composition to form a new layer. It is possible to form
However, of these two layers, the layer to be laminated later is formed in advance using the composition on another release film, and the side of the formed layer in contact with the release film is It is preferable to form a continuous two-layered laminated structure by bonding the opposite exposed surface to the exposed surface of the remaining layer that has already been 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 the formation of the laminated structure.

For example, a composite sheet for protective film formation in which a pressure-sensitive adhesive layer is laminated on a substrate and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the substrate and the pressure-sensitive adhesive layer) In the case of producing a protective film-forming composite sheet), the pressure-sensitive adhesive composition is coated on a base material, and dried as needed to laminate the pressure-sensitive adhesive layer on the base material separately. The protective film-forming film is formed on the release film by applying the composition for forming a protective film on the release film and drying it as necessary. Then, the exposed surface of the protective film-forming film is attached to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the pressure-sensitive adhesive layer to form a protective film. Composite sheet is obtained.

In addition, when laminating an adhesive layer on a base material, it replaces with the method of coating an adhesive composition on a base material as mentioned above, and applies an adhesive composition on a peeling film. If necessary, the pressure-sensitive adhesive layer is formed on the release film, and the exposed surface of this layer is bonded to one surface of the substrate to form the pressure-sensitive adhesive layer on the substrate. It may be stacked.
In any of the methods, the release film may be removed at any timing after formation of the intended laminated structure.

As described above, any layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on the peelable film and laminated on the surface of the intended layer, as required. A layer adopting such a process may be appropriately selected to manufacture a composite sheet for forming a protective film.

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

Method of Manufacturing Semiconductor Chip The film for forming a protective film and the composite sheet for forming a protective film can be used for manufacturing a semiconductor chip.
As a method for manufacturing a semiconductor chip at this time, for example, a film for forming a protective film which does not constitute the composite sheet for forming a protective film, or a film for forming a protective film in the composite sheet for forming a protective film is used as a semiconductor wafer. And a step of forming a protective film by irradiating the film for forming a protective film after being attached to the semiconductor wafer with ultraviolet rays (hereinafter, referred to as a step of forming a protective film). A process for forming a plurality of semiconductor chips (hereinafter referred to as “division,” abbreviated as “protective film forming process”), and dividing the semiconductor wafer together with the protective film or a film for protective film formation And the like, which may be abbreviated as “process”.

Hereinafter, the above-mentioned manufacturing method will be described with reference to the drawings. FIG. 7 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing a semiconductor chip in the case of using a protective film-forming film which does not constitute a protective film-forming composite sheet. FIG. 8 is a cross-sectional view for schematically describing one embodiment of a method of manufacturing a semiconductor chip in the case of using a composite sheet for protective film formation in which a protective film-forming film is integrated with a support sheet in advance. It is.

<< Method of manufacturing semiconductor chip when using a film for forming a protective film which does not constitute a composite sheet for forming a protective film >>
First, with respect to an embodiment of a manufacturing method in the case of using a film for forming a protective film which does not constitute a composite sheet for forming a protective film, the case where the film for forming a protective film is as shown in FIG. It will be described (this embodiment may be referred to as “manufacturing method (1)”).

In the attaching step of the manufacturing method (1), as shown in FIG. 7A, the 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 first release film 151 is removed from the protective film formation film 13 and the first surface 13a of the protective film formation film 13 is bonded to the back surface 9b of the semiconductor wafer 9 is shown. Further, in the semiconductor wafer 9, illustration of bumps and the like on the circuit surface is omitted here.

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

After the protective film forming step of the manufacturing method (1), prior to the dividing step, as shown in (c) of FIG. , The support sheet 10 is attached to the surface (which may be referred to herein as the “second surface”) 13b ′ opposite to the “first surface” 13a ′. Do. The support sheet 10 is shown in FIG. 2 and the like, and is attached to the protective film 13 ′ by the pressure-sensitive adhesive layer 12.

Next, in the dividing step of the manufacturing method (1), the semiconductor wafer 9 is divided by dicing or the like together with the protective film 13 ′ to divide the semiconductor wafer 9, and as shown in (d) of FIG. The semiconductor chip 9 'is obtained. At this time, the protective film 13 'is cut (divided) at a position along the periphery of the semiconductor chip 9'. The protective film 13 'after this cutting is indicated by reference numeral 130'.

In addition, in FIG. 7, after performing a protective film formation process, it shows about the case where the support sheet 10 is stuck on protective film 13 '. However, in the production method (1), the protective film forming step may be performed after the support sheet 10 is attached to the protective film forming film 13.

In the manufacturing method (1), when the semiconductor wafer 9 is divided into semiconductor chips 9 ′ in the dividing step by using the film 13 for forming a protective film, the protective film 13 ′ or the film after being cut is used. The floating of the semiconductor chip 9 'from the protective film 130' can be suppressed.

In the manufacturing method (1), the dividing step is performed after the protective film forming step. However, in the manufacturing method of the semiconductor chip according to the present embodiment, the dividing step is performed without the protective film forming step, and the protective film is performed after the dividing step. You may perform a formation process.

<< Method of manufacturing semiconductor chip in the case of using a composite sheet for protective film formation in which a film for protective film formation is previously integrated with a support sheet >>
Next, a composite sheet for protective film formation is shown in Drawing 2 about one embodiment of a manufacturing method in the case of using a composite sheet for protective film formation which made a film for protective film formation unite with a support sheet beforehand. These will be described by way of example (this embodiment may be referred to as “manufacturing method (2)”).

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

After the sticking step of the manufacturing method (2), in the protective film forming step, the protective film-forming film 13 after being stuck to the semiconductor wafer 9 is irradiated with ultraviolet light, as shown in FIG. A protective film 13 ′ is formed on the semiconductor wafer 9. At this time, ultraviolet rays are applied to the protective film-forming film 13 through the support sheet 10.
In addition, the composite sheet for protective film formation after the film 13 for protective film formation becomes protective film 13 'is shown with code | symbol 1 A' here. This is the same in the following figures.

Further, after the attaching process of the manufacturing method (2), the semiconductor wafer 9 is divided together with the protective film 13 ′ by dicing or the like in the dividing step of the manufacturing method (2), thereby dividing the semiconductor wafer 9 As shown in c), a plurality of semiconductor chips 9 'are obtained. At this time, the protective film 13 'is cut (divided) at a position along the peripheral portion of the semiconductor chip 9' to form a protective film 130 '.
Thus, the target semiconductor chip 9 'is obtained as a semiconductor chip with a protective film.

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

In the manufacturing method (2), the dividing step is performed after the protective film forming step, but in the manufacturing method of the semiconductor chip according to the present embodiment, the dividing step is performed without the protective film forming step, and the protective film is performed after the dividing step. You may perform a formation process.

So far, the method of manufacturing a semiconductor chip has been described using the film 13 for forming a protective film shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for forming a protective film shown in FIG. The manufacturing method of the semiconductor chip of the present invention is not limited to these.
For example, in the case of using a composite sheet for protective film formation, composite sheets 1B to 1E for protective film formation shown in FIGS. 3 to 6, a composite sheet for protective film formation further including the intermediate layer, etc. A semiconductor chip can be manufactured similarly even if it uses things other than composite sheet 1A for protective film formation shown.
In addition, as the support sheet, as described above, the semiconductor chip can be used similarly even when using a support sheet other than the support sheet 10 shown in FIG. Can be manufactured.
Thus, when using the composite sheet for protective film formation of other embodiment and support sheet of other embodiments, based on the difference in the structure of these sheets, in the above-mentioned manufacturing method, addition, change, deletion of a process, etc. are carried out suitably. To manufacture a semiconductor chip.

Method of Manufacturing Semiconductor Device After a semiconductor chip is obtained by the above-described manufacturing method, the semiconductor chip is supported as it is with the protective film after division (ie, as a semiconductor chip with a protective film). Pull away from and pick up (not shown).
Thereafter, the obtained semiconductor chip of the semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate by a method similar to that of the conventional method to form a semiconductor package. Then, the target semiconductor device may be manufactured using this semiconductor package (not shown).

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

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

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

<Manufacturing raw material of composition for protective film formation>
The raw materials used for the production of the composition for forming a protective film are shown below.
[UV-curable component (a2)]
(A2) -1: ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate (“A-93001CL” manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional UV curable compound) [having UV curable group Not polymer (b)].
(B) -1: an acrylic polymer (weight average molecular weight copolymerized with methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) 300000, glass transition temperature 6 ° C.).
[Photoinitiator (c)]
(C) -1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF Corporation).
[Filler (d)]
(D) -1: silica filler (fused silica filler, average particle diameter 8 μm).
[Coupling agent]
(E) -1: 3-methacryloxypropyl trimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent).
[Colorant (g)]
(G) -1: 32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone-based red pigment (Pigment Red 177) And the pigment obtained by pigmenting so that the total amount of the three dyes / the styrene acrylic resin amount = 1/3 (mass ratio).

Example 1
<Manufacture of film for protective film formation>
(Production of composition for forming a protective film (IV-1))
UV curable component (a2) -1, polymer (b) -1, photopolymerization initiator (c) -1, filler (d) -1, coupling agent (e) -1, and colorant (g) The solid content concentration is 50 mass% by dissolving or dispersing it in methyl ethyl ketone so that the content (solid content, mass part) thereof becomes the value shown in Table 1 and stirring at 23.degree. The composition for forming a protective film (IV-1) was prepared.

A first release sheet (made by Lintec: SP-PET 381130, thickness 38 μm) having a silicone release agent layer formed on one side of a polyethylene terephthalate (PET) film, and a silicone release agent on one side of a PET film A second release sheet (manufactured by Lintec Corporation: SP-PET 381031, thickness 38 μm) having a layer formed was prepared.

The protective film-forming composition (IV-1) described above is applied on the release surface of the first release sheet with a knife coater and then dried in an oven at 120 ° C. for 2 minutes to form a protective film-forming film Formed. The thickness of the obtained film for protective film formation was 25 micrometers. Next, the release surface of the second release sheet is superimposed on the protective film-forming film, and both are attached to each other, and the first release sheet (release sheet 151 in FIG. 1) and the protective film-forming film (protective film in FIG. 1) The film for protective film formation which consists of the film 13 for formation (thickness: 25 micrometers) and the 2nd peeling sheet (peeling sheet 152 in FIG. 1) was obtained.

<Manufacture of composite sheet for protective film formation>
(Production of Pressure-Sensitive Adhesive Composition (I-4))
Acrylic polymer (100 parts by mass, solid content) and isocyanate crosslinking agent ("Coronato L" manufactured by Nippon Polyurethane Industry Co., Ltd., tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content) A non-energy ray curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30% by mass was prepared, which further contains methyl ethyl ketone as a solvent. The acrylic polymer is a copolymer having a weight average molecular weight of 600,000, which is obtained by copolymerizing 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass).

(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 Corporation, 38 μm thick) whose release treatment was performed on one side of a polyethylene terephthalate film by silicone treatment. C.) and heat-dried at 120.degree. C. for 2 minutes to form a 10 .mu.m-thick non-energy ray curable pressure-sensitive adhesive layer.
Then, a base material, an adhesive layer and a release film are laminated in this order in the thickness direction by laminating a polypropylene film (80 μm in thickness) as a substrate on the exposed surface of the adhesive layer. Support sheet was obtained.

(Manufacture of composite sheet for protective film formation)
The protective film obtained above is formed on the release-treated surface of a release film (second release film, "SP-PET 382150" manufactured by Lintec Corporation, thickness 38 μm) in which one surface of a polyethylene terephthalate film is release-treated by silicone treatment. The composition for preparation (IV-1) was applied and dried at 100 ° C. for 2 minutes to produce a 25 μm-thick energy ray-curable protective film-forming film.
Furthermore, the exfoliation process of the exfoliation film (the 1st exfoliation film, the lintec "SP-PET 38 1031", 38 micrometers in thickness) is carried out to the exposure side of the side which does not equip the 2nd exfoliation film of the film for protective film formation obtained By laminating the surfaces, a laminated film provided with a first peelable film on one surface of the protective film-forming film and a second peelable film on the other surface was obtained.

Next, the release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. Moreover, the 1st peeling film was removed from the laminated film obtained above. And a base material and adhesion are obtained by sticking together the exposed surface of the pressure-sensitive adhesive layer produced by removing the above-mentioned release film and the exposed surface of the film for protective film formation produced by removing the above-mentioned first release film. The composite sheet for protective film formation in which an agent layer, the film for protective film formation, and the 2nd exfoliation film are laminated in this thickness direction in this order was produced.

<Evaluation of protective film>
(Measurement of light transmittance)
The first release sheet and the second release sheet were released from the protective film-forming films obtained in Examples and Comparative Examples, and used as a measurement sample.

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

(Measurement of shear strength reduction rate)
The composite sheet for protective film formation obtained above was placed under 30 cm of a 27 watt fluorescent lamp (one) for 30 days and stored. The first release film of the composite sheet for protective film formation was removed, and the exposed surface of the film for protective film formation thus produced was attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness 300 μm).
Then, the second release film was removed from the protective film-forming film to expose the protective film-forming film. Moreover, the peeling film was removed from the adhesive layer of the support sheet obtained above, and the adhesive layer was exposed. Then, the exposed surface of the pressure-sensitive adhesive layer is attached to the exposed surface of the protective film-forming film and attached to the ring frame, whereby the substrate, the adhesive layer, the protective film-forming film, and the silicon wafer are in this order. The laminated body laminated | stacked in these thickness direction was fixed to the ring frame, and was left still for 30 minutes.

Then, using a UV irradiation apparatus ("RAD 2000 m / 8" manufactured by LINTEC Corporation), under the conditions of an illuminance of 195 mW / cm ² and a light quantity of 170 mJ / cm ^2, a film for protective film formation is provided via the substrate and the pressure-sensitive adhesive layer. The film for protective film formation was hardened by irradiating an ultraviolet ray, it was made into a protective film, and the silicon wafer with a protective film was obtained.
Next, using a dicing blade, the silicon wafer is diced together with the protective film (dicing of the silicon wafer with protective film) into pieces, and a silicon chip with a protective film having a size of 3 mm × 3 mm (silicon with protective film) Several chips were obtained.

Next, using a universal bond tester ("DAGE 4000" manufactured by Nordson Advanced Technology), only the protective film of the protected silicon chip at a speed of 200 μm / s with a shear tool under conditions of 23 ° C. Force was applied to the surface of the protective film. Then, the maximum value of the force applied until the protective film was broken was confirmed, and this was taken as the shear strength (N / 3 mm □).

The shear strength was similarly measured for the protective film formed by the composite sheet for protective film formation stored in a dark room. Relative to the shear strength of the protective film formed by the composite sheet for protective film formation stored in a dark room, the reduction rate of the shear strength of the protective film formed by the composite sheet for protective film formation stored for 30 days under fluorescent light When it was less than 20%, it was judged that the reduction rate of shear strength was low. The results are shown in Table 1.

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

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

The present invention is applicable to the manufacture of semiconductor devices.

1A, 1A ', 1B, 1C, 1D, 1E ... composite sheet for protective film formation, 10 ... support sheet, 10a ... surface of support sheet (first surface), 11 ... base material, 11a: surface of substrate (first surface) 12: adhesive layer 12a: surface of adhesive layer (first surface) 13, 23: protective film-forming film 130 ... Film for protective film formation after cutting, 13a, 23a ... surface (first surface) of film for protective film formation, 13b ... surface (second surface) for film for protective film formation, 13 ′ ... Protective film, 130 '... Protective film after cutting, 15 ... Peeling film, 151 ... First peeling film, 152 ... Second peeling film, 16 ... Bonding for jig Agent layer, 16a: surface of adhesive layer for jig, 9: semiconductor wafer, 9b: semiconductor wafer Surface, 9 '... semiconductor chip

Claims

Contains UV curable components,
The light transmittance at a wavelength of 350 nm is 20% or less,
The light transmittance at a wavelength of 550 nm is 25% or less,
The film for protective film formation whose light transmittance of wavelength 1600nm is 25% or more.
A composite sheet for forming a protective film, comprising a support sheet, and the film for forming a protective film according to claim 1 on the support sheet.
A process for attaching the film for protective film formation according to claim 1 or the film for protective film formation in the composite sheet for protective film formation according to claim 2 to a semiconductor wafer, and after being attached to the semiconductor wafer A step of irradiating the film for protective film formation with ultraviolet light to form a protective film, and cutting the semiconductor wafer together with the protective film or the film for protective film formation divides the semiconductor wafer into a plurality of pieces. And d) obtaining a semiconductor chip.