TW201936827A - Film for forming protective coating, composite sheet for forming protective coating, and method of manufacturing semiconductor chip - Google Patents

Abstract

The present invention relates to an energy ray-curable film 13 for forming protective coating, wherein the rate of decrease of the gross value represented by the formula (G1-G2)/G1 x 100% is 30% or less, wherein G1 is a gloss value measured after the film 13 for forming protective coating is adhered to a semiconductor wafer and irradiated with energy rays, and G2 is a gloss value measured after the film 13 for forming protective coating is adhered to a semiconductor wafer, irradiated with energy rays and further heated at 260 DEG C for 5 minutes.

Description

Film for forming protective film, composite sheet for forming protective film, and method for producing semiconductor wafer

The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, and a method for producing a semiconductor wafer.
The present application is based on Japanese Patent Application No. 2017-208437, filed on Jan. 27,,,,,,,

In recent years, the manufacture of a semiconductor device using a mounting method called a so-called face down method has been developed. In the face-down method, a semiconductor wafer having electrodes such as bumps on a surface of a circuit is used, and the aforementioned electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface is exposed.

A resin film containing an organic material is formed on the back surface of the exposed semiconductor wafer as a protective film, and is assembled in a semiconductor device as a semiconductor wafer with a protective film.
The protective film serves to prevent cracks from occurring in the semiconductor wafer after the dicing step or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film for forming a protective film on a support sheet can be used. The film for forming a protective film can be cured to form a protective film. When a semiconductor wafer including a film for forming a protective film or a protective film on the back surface is divided into semiconductor wafers, the support sheet can be used to fix the semiconductor wafer. Further, the support sheet may be used as a dicing sheet, and the composite sheet for forming a protective film may be used as a composite sheet in which a film for forming a protective film and a dicing sheet are integrated.

As such a composite sheet for forming a protective film, for example, a composite sheet having a film for forming a thermosetting protective film which is cured by heating to form a protective film is mainly used. However, the heat curing of the film for forming a thermosetting protective film usually takes about several hours to several hours, so it is desirable to shorten the curing time. In the case of the formation of the protective film, a film for forming a protective film which can be cured (energy ray curability) by irradiation with energy rays such as ultraviolet rays has been studied.

Patent Document 1 discloses an energy ray-curable wafer protective film attached to the back surface of a circuit forming surface of a wafer. This energy ray-curable wafer protective film has a release film and an energy ray-curable protective film forming layer formed on the release film. The energy ray-curable protective film forming layer contains a non-energy ray-curable component other than the energy ray-curable component as a binder polymer component.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-056328

[Problems to be solved by the invention]

The semiconductor wafer in which the protective film is formed by using the energy ray-curable wafer protective film described in Patent Document 1 is bonded to a desired device by heating. By such heating, relatively low molecular weight components (so-called bleed out components) among the non-energy ray-curable components contained in the protective film are segregated on the surface of the protective film, so that the surface gloss of the protective film is remarkably reduce. Therefore, there is a problem that the design performance of the protective film is lowered and the visibility is lowered when marking on the surface of the protective film.

Therefore, the object of the present invention is to suppress the surface of the protective film even when the semiconductor wafer having the protective film of the cured film for forming a protective film on the back surface is heated to achieve bonding or the like. A film for forming a protective film having a reduced gloss, a composite sheet for forming a protective film comprising the film for forming a protective film, and a method for producing a semiconductor wafer using the protective film forming film or the protective film forming composite sheet.
[Means for solving problems]

In order to solve the above problems, the present invention provides a film for forming a protective film which is an energy ray-curable film for forming a protective film, wherein the film for forming a protective film is attached to a semiconductor wafer and irradiated with energy rays. The measured gloss value was 30% after the film for protective film formation was attached to the semiconductor wafer and irradiated with energy rays and further heated at 260 ° C for 5 minutes. the following.

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

The present invention provides a method for producing a semiconductor wafer, comprising the steps of: attaching a film for forming a protective film or a film for forming a protective film in the composite sheet for forming a protective film to a semiconductor wafer, and attaching the film The protective film forming film after the semiconductor wafer is irradiated with ultraviolet rays to form a protective film, and the semiconductor wafer is simultaneously cut by the protective film or the protective film forming film to divide the semiconductor wafer. Thereby, a plurality of semiconductor wafers are obtained.
[Effect of the present invention]

In the film for forming a protective film of the present invention, the surface of the protective film can be suppressed even when the semiconductor wafer having the protective film of the cured film for forming a protective film on the back surface is heated to achieve bonding or the like. The gloss is reduced. Furthermore, according to the present invention, there is provided a composite sheet for forming a protective film comprising the film for forming a protective film, and a method for producing a semiconductor wafer using the protective film forming film or the protective film forming composite sheet.

A film for forming a protective film according to an embodiment of the present invention, which is an energy ray-curable film for forming a protective film, wherein the film for forming a protective film is attached to a semiconductor wafer. The rate of decrease in the gloss value measured after the film for protective film formation was attached to the semiconductor wafer and irradiated with energy rays and further heated at 260 ° C for 5 minutes by the gloss value measured after the energy ray irradiation 30% or less, preferably 25% or less, and preferably 20% or less.
When the rate of decrease in the gloss value is equal to or less than the above-described upper limit, the semiconductor wafer of the protective film which is a cured product of the film for forming a protective film on the back surface is heated to achieve bonding or the like. It is possible to suppress a decrease in the surface gloss of the protective film.
The rate of decrease of the gloss value is preferably 0%, but it may be a sufficiently low rate of reduction so that the semiconductor wafer of the protective film having the cured film for the protective film formation on the back surface is heated to achieve In the case of the purpose of bonding or the like, the surface gloss of the protective film can be sufficiently suppressed from being lowered. From this point of view, the rate of decrease in the gloss value may be 1% or more, or may be 2% or more.
The combination of the upper limit and the lower limit is 0% or more and 30% or less, 1% or more and 25% or less, or 2% or more and 20% or less.
The gloss value can be measured using a gloss meter (for example, "VG7000" manufactured by Nippon Denshoku Industries Co., Ltd.) at an incident angle of 60°.
In the present specification, the "declination rate of the gloss value" can be obtained by dividing the difference between the gloss value before heating and the gloss value after heating by the gloss value before heating.

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

The film for forming a protective film is cured to form a protective film by irradiation with energy rays. The protective film is for protecting the back surface of the semiconductor wafer or the semiconductor wafer (the surface opposite to the electrode forming surface). The film for forming a protective film is soft and can be easily attached to an object to be attached.
Since the film for forming a protective film has energy ray curability, it is possible to form a protective film by curing in a shorter time than the film for forming a thermosetting protective film.

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

The film for forming a protective film contains at least an energy ray-curable component. An energy ray-polymerizable acrylic polymer (hereinafter also referred to as an "adduct" type acrylic polymer) which incorporates an energy ray-curable group in an acrylic polymer as the energy ray-curable component. Preferably, it is obtained by reacting a compound containing an energy ray-polymerizable group with a non-energy ray-curable acrylic polymer.

The energy ray-curable component is preferably uncured, preferably has adhesiveness, and is preferably uncured and adhesive.

In the present invention, the "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation, electron beams, and the like.
For example, ultraviolet rays can be irradiated by using a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp or the like as a source of ultraviolet rays. The electron beam can be irradiated by an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curability" refers to a property of being cured by irradiation with an energy ray, and "non-energy ray curability" means a property that does not solidify even when an energy ray is irradiated.

The film for forming a protective film may have only one layer (single layer) or a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be identical to each other or may be different from each other, and combinations of these plural layers may be used. There is no particular limitation.
In the present specification, the present invention is not limited to the case of the film for forming a protective film, and the phrase "the plural layers may be identical to each other or may be different from each other" means that "all layers may be the same, or all layers may be different. Or, it may be that only a part of the layers are the same, and "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer are different from each other".

The thickness of the film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. By setting the thickness of the film for forming a protective film to be equal to or higher than the above lower limit value, a protective film having higher protection ability can be formed. By setting the thickness of the film for forming a protective film to be equal to or less than the above upper limit value, it is possible to suppress the protective film from becoming too thick.
Here, the "thickness of the film for forming a protective film" means the thickness of the film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means all the layers constituting the film for forming a protective film. Total thickness.

The curing condition of the film for forming a protective film to form a protective film is not particularly limited as long as it is a degree of curing in which the protective film can sufficiently exhibit its function, and can be appropriately selected depending on the type of film for forming a protective film.
For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably 4 to 280 mW/cm ² . Further, at the time of the aforementioned curing, the amount of the energy ray is preferably 3 to 1000 mJ/cm ² .

Fig. 1 is a schematic cross-sectional view showing a film for forming a protective film according to an embodiment of the present invention. The following drawings used in conjunction with the description are for the sake of easy understanding of the features of the present invention and for the sake of convenience, the main part will be enlarged, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as the actual ones.

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

The film 13 for forming a protective film can be formed using the composition for forming a protective film described later.
The film 13 for forming a protective film has energy ray curability.

Any of the first release film 151 and the second release film 152 may be known.
The first release film 151 and the second release film 152 may be the same as each other or may be different from each other, and for example, the peeling force required when peeling off from the film for protective film formation 13 is different.

In the film 13 for forming a protective film shown in FIG. 1, a semiconductor wafer is attached to a surface on which one of the first release film 151 and the second release film 152 is removed (not shown in the drawing) )The back. Thereafter, the surface on which the other of the first release film 151 and the second release film 152 is exposed is removed, and serves as a bonding surface of the support sheet.

<<Protective film forming composition>>
The film for forming a protective film can be formed by using a composition for forming a protective film containing a constituent material. For example, a composition for forming a protective film is applied onto a surface on which a film for forming a protective film is to be formed, and dried as needed to form a film for forming a protective film at a target position.
In the composition for forming a protective film, the ratio of the content of each component which does not evaporate at normal temperature is usually the same as the ratio of the content of each component of the film for forming a protective film. In the present specification, the term "normal temperature" means a temperature which is not particularly cold or hot, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The application of the protective film-forming composition can be carried out by a known method, and examples thereof include an air knife coater, a blade coater, and a bar coater (Bar). Coater), Gravure coater, Roll coater, Roll knife coater, Curtain coater, Die coater A method of various coaters such as a Knife coater, a Screen coater, a Meyer bar coater, and a Kiss coater.

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

<Protective film forming composition (IV-1)>
The protective film-forming composition (IV-1) containing at least the energy ray-curable component (a) is exemplified as the protective film-forming composition.

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, that is, a component for imparting film formability, flexibility, and the like to the film for forming a protective film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and an energy ray-curable group having a molecular weight of 100 or more. And less than 80,000 compounds (a2). At least a part of the aforementioned polymer (a1) may have been crosslinked by a crosslinking agent (f) described later, or may be uncrosslinked.
In the present specification, the weight average molecular weight means a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000)
The polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 is exemplified by the above-mentioned adduct type acrylic polymer (a1-1). An energy ray can be obtained by using an acrylic polymer (a11) having a functional group reactive with a group possessed by another compound, and a group having a group reactive with the aforementioned functional group and having an energy ray-curable double bond. The energy ray curable compound (a12) of the curable group is reacted to obtain an adduct type acrylic polymer (a1-1).

Examples of the functional group that can react with a group of another compound include a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (hereinafter, "substituted amino group" means one or two of an amine group. A group in which a hydrogen atom is substituted by a group other than a hydrogen atom, an epoxy group or the like. However, from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the above functional group is preferably a group other than a carboxyl group.
Among the above, the above functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional group (a11)
The acrylic polymer (a11) having a functional group may, for example, be a polymer obtained by copolymerizing an acrylic monomer having the functional group with an acrylic monomer having no such functional group, or may be a polymer. In addition to these monomers, it is also copolymerized with a monomer other than the acrylic monomer (non-acrylic monomer).
The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl (meth) acrylate hydroxyalkyl ester, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol A non-(meth)acrylic unsaturated alcohol such as propylene alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton) or the like.

In the present specification, the term "(meth)acrylic acid" means a concept including both "acrylic acid" and "methacrylic acid". This also applies to other terms similar to (meth)acrylic acid.

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; fumaric acid and itaconol. An ethylenically unsaturated dicarboxylic acid (dicarboxylic acid having an ethylenically unsaturated bond) such as an acid, maleic acid or citraconic acid; an acid anhydride of the above ethylenically unsaturated dicarboxylic acid; methacrylic acid a carboxyalkyl (meth)acrylate such as 2-carboxyethyl ester.

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

The acrylic monomer having the functional group described above may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected. .

Examples of the acrylic monomer having no such functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (methyl) ) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, ortho(meth)acrylate Ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylic acid Cetyl ester (also known as palmityl (meth)acrylate), (methyl) An alkyl group constituting an alkyl ester such as heptadecanic acid octadecyl ester or octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) and having a chain of 1 to 18 carbon atoms Structure of alkyl (meth) acrylate and the like.

Examples of the acrylic monomer having no such functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate. An alkoxyalkyl group-containing (meth) acrylate such as ethoxyethyl (meth)acrylate; or an aromatic aryl (meth)acrylate such as phenyl (meth)acrylate Group of (meth) acrylate; non-crosslinkable (meth) acrylamide and its derivatives; (meth) acrylate N, N-dimethylaminoethyl ester, (meth) acrylate N A (meth) acrylate having a non-crosslinkable tertiary amino group such as N-dimethylaminopropyl ester.

The acrylic monomer which does not have the above-mentioned functional group of the above-mentioned acrylic polymer (a11) may be used alone or in combination of two or more. When two or more types are used, the combination may be arbitrarily selected. proportion.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
The non-acrylic monomers constituting the acrylic polymer (a11) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the aforementioned functional group with respect to the total amount of the structural unit constituting the acrylic polymer (a11) It is preferably 0.1 to 50% by mass, preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. The above-mentioned adduct-type acrylic polymer (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), is contained in the above range. The content of the medium energy ray-curable group can be easily adjusted within a range in which the protective film has a preferable degree of curing.

The acrylic polymer (a11) constituting the above-mentioned adduct type acrylic polymer (a1-1) may be used alone or in combination of two or more. When two or more types are used, any of them may be used. Choose their combination and ratio.

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

‧Energy ray curable compound (a12)
The energy ray-curable compound (a12) has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group, and is capable of functioning with the acrylic polymer (a11). The group of the radical reaction is preferred, and it is preferred to have an isocyanate group as the aforementioned group. In the case where the energy ray-curable compound (a12) has an isocyanate group as the above-mentioned group, for example, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the above-mentioned functional group.

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

Examples of the energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacryl oxime isocyanate. Allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate;
a propylene fluorenyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
An acrylonitrile monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth)acrylate.
Among the above, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the above-described adduct-type acrylic polymer (a1-1) may be used alone or in combination of two or more. When two or more types are used, Choose their combination and ratio arbitrarily.

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

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

In the case where at least a part of the polymer (a1) has been crosslinked by the crosslinking agent (f), the polymer (a1) is not a constituent of the acrylic polymer (a11) described above. Any one of the above monomers, and may be a polymer obtained by crosslinking a monomer having a group reactive with the crosslinking agent (f) and reacting with a crosslinking group (f), or It may also be a polymer which is derived from the aforementioned energy ray-curable compound (a12) and which is crosslinked at a group reactive with the aforementioned functional group.

The polymer (a1) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, The combination and ratio can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and having a weight average molecular weight of 100 or more and less than 80,000)
The energy ray-curable group in the compound (a2) having an energy ray-curable group and having a weight average molecular weight of 100 or more and less than 80,000 includes a group containing an energy ray-curable double bond, and A (meth) acrylonitrile group, a vinyl group, etc. are mentioned as a preferable example.

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

Among the above-mentioned compound (a2), examples of the low molecular weight compound having an energy ray-curable group include a polyfunctional monomer or oligomer, and the like, and an acrylate having a (meth) acrylonitrile group. Class compounds are preferred.
Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated B. Oxidized bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di( Methyl) acrylate, 2,2-bis[4-((meth)propenyloxyethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl)propene oxime) Ethyloxy)phenyl]anthracene, 2,2-bis[4-((meth)propenyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate ( Tricyclodecane dimethylol di(meth) acrylate), 1,10-nonanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9 -decanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol ( Methyl) acrylate, ethylene glycol di(meth)acrylic acid , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, Difunctional of neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, etc. Acrylate
Para-(2-(methyl)acryloxyethyl)isocyanurate, ε-caprolactone modified gin-(2-(methyl)propenyloxyethyl)isocyanurate , ethoxylated glycerol tri(meth) acrylate, neopentyl alcohol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (methyl) Acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol a polyfunctional (meth) acrylate such as (meth) acrylate;
A polyfunctional (meth) acrylate oligomer such as an urethane (meth) acrylate oligomer.

In the above-mentioned compound (a2), as an epoxy resin having an energy ray-curable group and a phenol resin having an energy ray-curable group, for example, "Japanese Patent Laid-Open No. 2013-194102" can be used. The materials described in paragraph 0043, etc. This resin also corresponds to the resin constituting the thermosetting component (h) described later, but in the present invention, it is treated as the above compound (a2).

The molecular weight of the compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.
In the case where the above compound (a2) is a monomer, the molecular weight can be calculated from the molecular formula thereof. Further, when the compound (a2) is an oligomer, the molecular weight thereof means a weight average molecular weight.

The compound (a2) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, Choose their combination and ratio arbitrarily.

The film for forming a protective film (the composition for forming a protective film) contains the energy ray-curable component (a), and is irradiated with ultraviolet rays for curing the film for forming a protective film into a protective film, and is made of an energy ray-curable group. When the energy ray-curable component (a) is polymerized, the polymer having a low molecular weight is hardly contained in the protective film. As a result, even if the protective film is heated, almost no polymer having a low molecular weight is segregated on the surface of the protective film.

Since the film for protective film formation (the composition for forming a protective film) contains the energy ray-curable component (a), it is measured after attaching the film for forming a protective film to a semiconductor wafer and irradiating with energy rays. The gloss value is a lower value of the gloss value measured by attaching the film for forming a protective film to a semiconductor wafer and irradiating with energy rays and further heating at 260 ° C for 5 minutes to become a lower value of 30% or less.

[Polymer having no energy ray-curable group (b)]
The protective film-forming composition (IV-1) and the film for forming a protective film may contain a polymer (b) having no energy ray-curable group.
At least a portion of the aforementioned polymer (b) may have been crosslinked by a crosslinking agent (f) described later, or may be uncrosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an urethane urethane resin. Polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, and the like.
Among the above, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes simply referred to as "acrylic polymer (b-1)").

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

The acrylic monomer constituting the acrylic polymer (b-1) may, for example, be an alkyl (meth)acrylate, a (meth)acrylate having a cyclic skeleton, or a glycidyl group ( Methyl) acrylate, hydroxyl group-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. Here, the "substituted amine group" is as described above.

Examples of the alkyl (meth)acrylate include (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate), ( Tridecyl methyl methacrylate, tetradecyl (meth) acrylate (also known as (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate Alkyl ester (also known as palmityl (meth)acrylate), (meth)acrylic acid An alkyl group constituting an alkyl ester such as an alkyl ester or octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) and having a chain structure of 1 to 18 carbon atoms (A) Base) alkyl acrylate and the like.

Examples of the (meth) acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isodecyl (meth)acrylate and (meth) acrylate dicyclopentanyl group. ;
An aralkyl (meth)acrylate such as benzyl (meth)acrylate;
a (meth)acrylic acid cycloalkenyl ester such as dicyclopentenyl (meth)acrylate;
A (meth)acrylic cycloalkenyloxyalkyl ester such as dicyclopentenyloxyethyl (meth)acrylate.

Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth)acrylate and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
The (meth) acrylate containing a substituted amino group may, for example, be N-methylaminoethyl (meth) acrylate or the like.

The non-acrylic monomer constituting the acrylic polymer (b-1) may, for example, be an olefin such as ethylene or norbornene; vinyl acetate; styrene or the like.

The polymer (b) having no energy ray-curable group which is crosslinked by at least a part of the crosslinking agent (f), for example, a reactive functional group and crosslinking in the above polymer (b) The polymer after the reaction of the agent (f).
The reactive functional group can be appropriately selected depending on the type of the crosslinking agent (f), and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group may, for example, be a hydroxyl group, a carboxyl group or an amine group. Among them, a hydroxyl group having high reactivity with an isocyanate group is preferred. When the crosslinking agent (f) is an epoxy compound, the reactive functional group may, for example, be a carboxyl group, an amine group or a guanamine group. Among them, a carboxyl group having high reactivity with an epoxy group is preferred. . However, from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

The polymer (b) having the reactive functional group and having no energy ray-curable group may, for example, be a polymer obtained by polymerizing a monomer having at least the aforementioned reactive functional group. In the case of the acrylic polymer (b-1), any one of the above-mentioned acrylic monomer and non-acrylic monomer exemplifying the monomer constituting the acrylic polymer (b-1) or For both, a monomer having the aforementioned reactive functional group can be used. The polymer (b) having a hydroxyl group as a reactive functional group may, for example, be a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate. In addition, a monomer formed by substituting one or two or more hydrogen atoms of the above-exemplified acrylic monomer or non-acrylic monomer with the reactive functional group may be polymerized. The resulting polymer.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group with respect to the total amount of the structural unit constituting the polymer (b) It is preferably 1 to 25% by mass, and preferably 2 to 20% by mass. By this ratio being within such a range, the degree of crosslinking in the aforementioned polymer (b) can be changed to a better range.

When the content of the polymer (b) having no energy ray-curable group having a low molecular weight in the film for forming a protective film is large, the protective film having the cured product of the film for forming a protective film is provided. In the case where the semiconductor wafer is heated to achieve the purpose of bonding or the like, the surface gloss of the protective film is lowered.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 200,000 or more, more preferably 250,000 or more, and still more preferably 300,000 or more. When the weight average molecular weight of the polymer (b) having no energy ray-curable group is at least the above lower limit value, the semiconductor is provided as a protective film having a cured product which is a film for forming a protective film on the back surface. In the case where the wafer is heated for bonding, it is still not easy to lower the surface gloss of the protective film. The upper limit of the weight average molecular weight of the polymer (b) having no energy ray-curable group is not particularly limited, but it does not have an energy ray-curable group from the viewpoint of easily producing a composite sheet for forming a protective film. The weight average molecular weight of the polymer (b) is preferably 2,000,000 or less. When the weight average molecular weight of the polymer (b) having no energy ray-curable group is 2,000,000 or less, the dispersibility in the composition (IV-1) for forming a protective film becomes good.
The combination of the upper limit and the lower limit is 200,000 or more and 2,000,000 or less, 250,000 or more and 2,000,000 or less, or 300,000 or more and 2,000,000 or less.

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

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

When the polymer (b) having no energy ray-curable group is introduced as an adduct into an energy ray-curable group such as an energy ray-curable double bond, the film for curing the protective film is cured into a protective film. The ultraviolet ray irradiation is carried out by the energy ray-curable group, and since the protective film contains almost no low molecular weight polymer, even if the protective film is heated, it is difficult for the low molecular weight polymer to segregate on the surface of the protective film. .

When the polymer (b) having no energy ray-curable group is introduced as an adduct into an energy ray-curable group such as an energy ray-curable double bond, the film for forming a protective film is attached to the semiconductor. The gloss value measured after the irradiation of the energy ray by the wafer, and the gloss value measured after the film for protective film formation is attached to the semiconductor wafer and irradiated with energy rays and further heated at 260 ° C for 5 minutes The rate of decline becomes a lower value of 30% or less.

The polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, the combination and ratio can be arbitrarily selected.

The composition (IV-1) for forming a protective film preferably contains the above compound (a2) and the above polymer (a1). The protective film-forming composition (IV-1) is preferably a polymer (b) containing the polymer (a1) and the compound (a2) but not containing an energy ray-curable group. The protective film forming composition (IV-1) may contain the above polymer (a1) but does not contain the aforementioned compound (a2).
As the polymer (a1), an adduct type acrylic polymer (a1-1) is preferred.

In the case where the protective film-forming composition (IV-1) contains the polymer (a1) and the compound (a2), the protective film-forming composition (IV-1) is relative to the polymer (a1). The total content of the compound (a2) is preferably 10 to 400 parts by mass, and preferably 30 to 350 parts by mass.

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

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

The protective film-forming composition (IV-1) may contain, in addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, depending on the purpose, which is selected from photopolymerization. Starting agent (c), filler (d), coupling agent (e), crosslinking agent (f), coloring agent (g), thermosetting component (h), curing accelerator (i) and general additive ( z) One or more of the group consisting of.
For example, by using the protective film forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed film for forming a protective film can be lifted by heating The adhesive force of the adhesive can also increase the strength of the protective film formed by the film for forming a protective film.

[Photopolymerization initiator (c)]
As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal may be mentioned. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- An acetophenone compound such as a ketone; an anthracene such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide a phosphine oxide compound; a sulfide such as a benzyl phenyl sulfide or a tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; or an azobisisobutyronitrile; Azo compound; titanocene compound such as titanocene; thioxanthone compound such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl) -2-benzyl-1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O a benzophenone compound such as a acetyl group; a peroxide; a diketone compound such as a diethylhydrazine group; Dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] Acetone; 2-chloropurine and the like.
As the photopolymerization initiator (c), for example, an anthracene compound such as 1-chloroindole; a photosensitizer such as an amine or the like can be used.

The photopolymerization initiator (c) contained in the composition for forming a protective film (IV-1) may be used alone or in combination of two or more. When two or more types are used, the photopolymerization initiator (c) may be optionally selected. Combination and proportion.

In the case of using the photopolymerization initiator (c), in the protective film-forming composition (IV-1), the photopolymerization initiator (100 parts by mass) based on the content of the energy ray-curable compound (a) The content of c) 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 forming a protective film contains the filler (d), the protective film obtained by curing the film for forming a protective film is easily adjusted in thermal expansion coefficient. Further, by optimizing the coefficient of thermal expansion for the object on which the protective film is to be formed, the reliability of the package obtained by using the composite sheet for forming a protective film can be further improved. By containing the filler (d) in the film for forming a protective film, the moisture absorption rate of the protective film can be lowered, and heat dissipation and the like can be improved.
As the filler (d), for example, a filler composed of a heat conductive material can be cited.

The filler (d) may be any of an organic filler and an inorganic filler, and an inorganic filler is preferred.
Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide red, cerium carbide, and boron nitride; and beads obtained by spheroidizing the above inorganic filler A surface-modified product of the above inorganic filler; a single crystal fiber of the above inorganic filler; a glass fiber or the like.
Among the above, the inorganic filler is preferably cerium oxide or aluminum oxide.

The average particle diameter of the filler (d) is not particularly limited, and is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. When the average particle diameter of the filler (d) is within such a range, the adhesion of the protective film to an object on which the protective film is to be formed can be maintained, and at the same time, the decrease in the light transmittance of the protective film can be suppressed.
In the present specification, the "average particle diameter" means a particle diameter (D50) value having a cumulative value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method unless otherwise specified.

The filler (d) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, the filler (d) may be used arbitrarily. Choose their combination and ratio.

In the case of using the filler (d), in the protective film-forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the formation of the protective film) The content of the filler (d) in the film is preferably from 10 to 85% by mass, more preferably from 20 to 80% by mass, particularly preferably from 30 to 75% by mass, and for example, may be from 40 to 70% by mass. Any one of 45 to 65 mass%. By the content of the filler (d) being in such a range, the adjustment of the above thermal expansion coefficient becomes easier.

[coupler (e)]
By using a material having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesion and adhesion of the film for forming a protective film to the adherend can be improved. By using the coupling agent (e), the protective film obtained by curing the film for forming a protective film can improve water resistance without lowering heat resistance.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group contained in the energy ray-curable component (a), the polymer (b) having no energy ray-curable group, or the like, and A decane coupling agent is preferred.
Preferable examples of the aforementioned decane coupling agent include, for example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropane. Triethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyl Diethoxy decane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyl Trimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxycarbamidopropyl)tetrasulfane, methyltrimethoxydecane, methyltriethoxydecane , vinyl trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

The coupling agent (IV) which is contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, Choose their combination and ratio arbitrarily.

In the case of using the coupling agent (e), the protective film-forming composition (IV-1) and the film for forming a protective film have a coupling agent (100 parts by mass) based on the content of the energy ray-curable component (a). The content of e) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.
When the content of the coupling agent (e) is at least the above lower limit value, the dispersibility of the filler (d) in the resin can be improved, and the adhesion of the film for forming a protective film to the adherend can be improved. The effect of using the coupling agent (e) is obtained. In addition, since the content of the coupling agent (e) is at most the above upper limit value, the occurrence of outgas is further suppressed.

[crosslinking agent (f)]
By crosslinking the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group by using the crosslinking agent (f), the initial adhesion of the film for forming a protective film can be adjusted. Cohesion.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine type crosslinking. A crosslinking agent (a crosslinking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc." a terpolymer of an aromatic polyvalent isocyanate compound or the like; an isocyanurate and an adduct; a terminal isocyanate amine formate prepolymer obtained by reacting the above polyvalent isocyanate compound with a polyol compound; Wait. The term "adduct" as used herein means an aromatic polyvalent isocyanate compound, an alicyclic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or hydrazine. A reaction product of a low molecular weight active hydrogen compound such as sesame oil. Examples of the adduct described above include a xylylene diisocyanate adduct of trimethylolpropane described later and the like. The term "terminal isocyanate urethane prepolymer" means a prepolymer having an urethane bond and having an isocyanate group at the terminal of the molecule.

The organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-dimethylbenzene Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of the polyol of trimethylolpropane or the like Any one or two or more kinds of compounds of isocyanate, hexamethylene diisocyanate, and xylylene diisocyanate; and isocyanuric acid diisocyanate.

The organic polyvalent imine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) or trimethylolpropane-tri-beta. - aziridine propionate, tetramethylol methane-tri-beta-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) three Extend melamine and so on.

In the case where an organic polyvalent isocyanate compound is used as the crosslinking agent (f), the polymer (b) having a hydroxyl group-containing polymer as the energy ray-curable component (a) or having no energy ray-curable group is good. In the case where the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and energy are used. The reaction between the radiation curable component (a) or the polymer (b) having no energy ray-curable group can easily introduce the crosslinked structure into the film for forming a protective film.

The crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, The combination and ratio can be arbitrarily selected.

In the case of using the crosslinking agent (f), in the protective film-forming composition (IV-1), the energy ray-curable compound (a) and the polymer having no energy ray-curable group (b) The total content of the component is 100 parts by mass, and the content of the crosslinking agent (f) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. Since the content of the crosslinking agent (f) is at least the above lower limit value, the effect of using the crosslinking agent (f) can be more significantly obtained. When the content of the crosslinking agent (f) is at most the above upper limit value, excessive use of the crosslinking agent (f) can be suppressed.

[coloring agent (g)]
The coloring agent (g) is, for example, a known coloring agent such as an inorganic pigment, an organic pigment, or an organic dye.

Examples of the organic pigment and the organic dye include an ammonium (Aminium) dye, a Cyanine dye, a merocyanine dye, and a Croconium dye. Squarylium pigment, Azulenium pigment, Polymethine pigment, Naphthoquinone pigment, Pyrylium pigment, Phthalocyanine pigment, Naphthalocyanine pigment, Naphtholactam pigment, azo (Azo) pigment, condensed azo dye, Indigo pigment, Perinone pigment, hydrazine (Perylene) pigments, Dioxazine pigments, Quinacridone pigments, Isoindolinone pigments, Quinophthalone pigments, Pyrrole Pigment, Thioindigo pigment, metal complex pigment (metal stray salt dye), Dithiol metal complex dye, indophenol ( Indole phenol), Triallyl methane, Anthraquinone, Naphthol, Azomethine, Benzimidazolone Pigment-like, Pyranthrone-based pigments, and Threne-based pigments.

Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, anthraquinone pigments, and the like. Platinum pigment, ITO (indium tin oxide) pigment, ATO (antimony tin oxide) pigment, and the like.

The coloring agent (g) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, Choose their combination and ratio arbitrarily.

When the coloring agent (g) is used, the content of the coloring agent (g) in the protective film forming composition (IV-1) and the protective film forming film can be appropriately adjusted depending on the purpose. For example, when the printing visibility is adjusted by adjusting the content of the coloring agent (g) and adjusting the light transmittance of the protective film, all of the protective film forming composition (IV-1) is not the solvent. The ratio of the total content of the components to the content of the colorant (g) (that is, the content of the colorant (g) in the film for forming a protective film) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass. It is particularly preferable to be 0.8 to 5% by mass. When the content of the coloring agent (g) is at least the above lower limit value, the effect of using the coloring agent (g) can be more significantly obtained. When the content of the coloring agent (g) is at most the above upper limit value, excessive use of the coloring agent (g) can be suppressed.

[thermosetting component (h)]
The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, The combination and ratio can be arbitrarily selected.

Examples of the thermosetting component (h) include an epoxy thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, a silicone resin, and the like, and an epoxy thermosetting resin is preferred.

(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (h1) and a heat curing agent (h2).
The epoxy-based thermosetting resin contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, Choose their combination and ratio arbitrarily.

‧Epoxy resin (h1)
Examples of the epoxy resin (h1) include known epoxy resins such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolac epoxy resins. , dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Compound.

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

The epoxy resin having an unsaturated hydrocarbon group may, for example, be a compound obtained by converting a part of an epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained by, for example, an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group.
In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting an epoxy resin or the like.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include vinyl (ethenyl, also called vinyl), 2-propenyl (also known as allyl), (A). The acrylonitrile group, the (meth) acrylamide group, and the like are preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, and is preferably from 300 to 30,000, and from 400 to 10,000, from the viewpoints of curability of the film for forming a protective film, and strength and heat resistance of the protective film. Preferably, it is particularly preferably from 500 to 3,000.
In the present specification, the "number average molecular weight" means a number average molecular weight expressed by a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method unless otherwise specified. The epoxy equivalent of the epoxy resin (h1) is preferably from 100 to 1000 g/eq, and more preferably from 150 to 800 g/eq.
In the present specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

The epoxy resin (h1) may be used alone or in combination of two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

‧Hot curing agent (h2)
The heat curing agent (h2) provides a function as a curing agent for the epoxy resin (h1).
The thermosetting agent (h2) is, for example, a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a functional group in which an acid group is an acid anhydride. Among them, a functional group having a phenolic hydroxyl group, an amine group, and an acid group as an acid anhydride is preferred, and A phenolic hydroxyl group or an amine group is preferred.

In the thermosetting agent (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolac type phenol resin, a dicyclopentadiene type phenol resin, and an aralkyl group. Phenolic resin and the like.
In the thermosetting agent (h2), examples of the amine-based curing agent having an amine group include dicyandiamide and the like.

The heat curing agent (h2) may also have an unsaturated hydrocarbon group.
The thermosetting agent (h2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of a hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to a phenol resin. a compound on the aromatic ring, and the like.
The aforementioned unsaturated hydrocarbon group in the heat curing agent (h2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

In the case where a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) has a high softening point or a high glass transition temperature from the viewpoint of improving the peeling property of the protective film from the support sheet. good.
In the present specification, the "glass transition temperature" is measured by measuring the DSC curve of a sample by using a differential scanning calorimeter, and is expressed by the temperature of the inflection point of the obtained DSC curve.

In the thermosetting agent (h2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene type phenol resin, or an aralkyl phenol resin is 300 to 30,000. Preferably, 400 to 10000 is preferred, and 500 to 3000 is particularly preferred.
The molecular weight of the non-resin component such as bisphenol or dicyandiamide in the thermosetting agent (h2) is not particularly limited, and is preferably, for example, 60 to 500.

The heat curing agent (h2) may be used singly or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the case of using the thermosetting component (h), the protective film-forming composition (IV-1) and the film for forming a protective film have a heat curing agent (h2) in an amount of 100 parts by mass based on the content of the epoxy resin (h1). The content is preferably 0.01 to 20 parts by mass.

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

[Curing accelerator (i)]
The curing accelerator (i) is a component for adjusting the curing speed of the film for forming a protective film.
Preferred examples of the curing accelerator (i) include, for example, tertiary grades such as tri-diamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and dimethylglycolyl phenol. Amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl -imidazoles such as 5-hydroxymethylimidazole; organophosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylboronic acid a tetraphenylboron salt such as a salt.

The curing accelerator (i) may be used singly or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.
In the case of using the curing accelerator (i), the content of the curing accelerator (I) in the protective film forming composition (IV-1) and the protective film forming film is not particularly limited, and may be used in combination. The ingredients are appropriately selected.

[General Additives (z)]
The general-purpose additive (z) may be a known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, and the like as preferred examples. .

The general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more types are used, Choose their combination and ratio arbitrarily.
In the case of using the general-purpose additive (z), the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the film for forming a protective film is not particularly limited, and may be appropriately selected depending on the purpose.

[solvent]
The protective film-forming composition (IV-1) preferably contains a solvent. The composition (IV-1) for forming a protective film containing a solvent has good handleability.
The solvent is not particularly limited, and examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (also referred to as 2-methylpropan-1-ol), and 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and guanamines such as dimethylformamide and N-methylpyrrolidone (Compound having a guanamine bond) and the like are preferred examples.
The solvent contained in the protective film-forming composition (IV-1) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

The film for forming a protective film of the present invention is a film for forming a protective film containing the following components: an energy ray-curable group having a total mass of 25 to 35 mass% based on the total mass of the film for forming a protective film. The polymer-type acrylic polymer (a1-1) of the polymer (a1) and the compound (a2) having an energy ray-curable group in an amount of 5 to 15% by mass based on the total mass of the film for forming a protective film. The ε-caprolactone-modified gin-(2-propenyl methoxyethyl) isocyanurate and the photopolymerization initiator are 0.3 to 0.9% by mass based on the total mass of the film for forming a protective film. (c) 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, the total mass of the film for forming a protective film is 52 to 62 3% by mass of the cerium oxide filler as the filler (d) and 3-methylpropenyloxypropyltrimethoxy as the coupling agent (e) in an amount of 0.1 to 0.7% by mass based on the total mass of the film for forming a protective film. Base decane.
Further, the above-mentioned adduct type acrylic polymer (a1-1) is an acrylic polymer (a11) formed by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate, and is an energy curable property. A polymer obtained by reacting 2-methylpropenyloxyethyl isocyanate of the compound (a12) is preferred.
Further, the ratio of the content of the energy ray-curable group derived from the energy-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 5 to 50 mol%. Preferably, it is preferably 20-40 mol%. Further, the above ratio may be 2 to 15 mol%.
Further, the film for forming a protective film preferably contains no polymer (b) having no energy ray-curable group.
The film for forming a protective film according to another aspect of the present invention further contains 25 to 40 parts by mass of a phthalocyanine-based blue pigment, 10 to 25 parts by mass of an isoindolinone-based yellow pigment, and 40 to 60 masses. a mixture of the above-mentioned three types of pigments in a total amount of the above-mentioned three kinds of pigments/the amount of the styrene acrylic resin = 1/3 (mass ratio), which is a pigment of the coloring agent (g) and which is formed on the film for protective film formation. The total mass is preferably 1 to 5% by mass.

<<Method for Producing Protective Film Forming Composition>>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending the respective components constituting the composition for forming a protective film.
The order of addition when the components are blended is not particularly limited, and two or more components may be added at the same time.
In the case of using a solvent, it may be used by mixing a solvent with any one of the compounding ingredients other than the solvent and preliminarily diluting the formulated component, or by disposing of any one of the ingredients other than the solvent. The solvent is directly diluted and used, and the solvent is directly mixed and used.
The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by stirring a stirrer or a stirring blade, a method of mixing by a mixer, or a method of applying ultrasonic waves.
The temperature and time during the addition and mixing of the respective components are not particularly limited as long as the respective components are not deteriorated, and can be appropriately adjusted, and the temperature is preferably 15 to 30 ° C.

Method for Producing Film for Protective Film Formation The film for forming a protective film can be produced by applying a composition for forming a protective film on a release film (preferably, a surface to be peeled off) and drying it as needed. The manufacturing method at this time is as described above.
For example, as shown in FIG. 1, the film for forming a protective film is usually stored in a state in which the release film is attached to both side surfaces thereof. Therefore, the exposed surface (the surface opposite to the side provided with the release film) formed on the release film on the release film as described above can be further bonded to the release film (with the release treated surface thereof) Better).

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

On the other hand, the film for forming a protective film may be provided on the back surface of the semiconductor wafer without being provided on the support sheet. For example, first, a film for forming a protective film is attached to the back surface of the semiconductor wafer, and the support sheet is bonded to the exposed surface of the film for forming a protective film (the surface opposite to the side attached to the semiconductor wafer) After the film for protective film formation in the attached state is irradiated with energy rays and cured into a protective film, the support sheet is attached to the exposed surface of the protective film (with the side attached to the semiconductor wafer) The surface on the opposite side is further formed into a composite sheet for forming a protective film. Thereafter, from this state, the target semiconductor wafer and the semiconductor device can be manufactured by the manufacturing method described later.

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

In the present invention, the laminated structure of the cured product (in other words, the support sheet and the protective film) of the support sheet and the film for forming a protective film is maintained even after the film for forming a protective film is cured. A composite sheet for forming a protective film.

The thickness of the semiconductor wafer to be used as the composite sheet for forming a protective film of the present invention is not particularly limited, and it is preferably 30 to 1000 μm from the viewpoint of being more easily divided into semiconductor wafers to be described later. ～400 μm is preferred.
Hereinafter, the structure of the composite sheet for forming a protective film will be described in detail.

◎ Support sheet The support sheet may be composed of one layer (single layer) or two or more layers. In the case where the support sheet is composed of a plurality of layers, these plural layers may be identical to each other or may be different from each other, and the combination of these plural 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 support sheet obtained by laminating a base material and having an adhesive layer in direct contact with the base material (the base material and the adhesive are directly contacted in this order and laminated) are obtained. A support sheet obtained by directly contacting the base material, the intermediate layer, and the adhesive in the thickness direction of the film layers in this order; a support sheet composed of only the base material, and the like.
Hereinafter, an example of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings for the types of each of the support sheets described above.

Fig. 2 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to an embodiment of the present invention.
In the drawings subsequent to FIG. 2, the constituent elements shown in the drawings which are the same as those already described are used with the same reference numerals as those shown in the drawings, and the detailed description thereof is omitted.

The composite sheet 1A for forming a protective film shown here includes a substrate 11, an adhesive layer 12 is provided on the substrate 11, and a film 13 for forming a protective film is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words, the composite sheet 1A for forming a protective film has a surface (referred to as "first surface" in the present specification) 10a on one side of the support sheet 10. The structure of the film 13 for forming a protective film is laminated. The composite sheet 1A for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

In the composite sheet 1A for forming a protective film, the adhesive layer 12 is laminated on the surface of one side of the substrate 11 (in the present specification, sometimes referred to as "first surface") 11a, and the film for forming a protective film 13 is laminated. On the surface of one side of the adhesive layer 12 (in the present specification, sometimes referred to as "first surface") 12a, the adhesive layer 16 for a jig is laminated on the first film 13 for forming a protective film. A part of the surface 13a (that is, a region in the vicinity of the edge portion), and a portion in which the release film 15 is laminated on the first surface 13a of the film for forming a protective film 13 without the buildup of the adhesive layer 16 for the jig and the jig The surface 16a (upper surface and side surface) of the adhesive layer 16 is on the surface.

In the composite film 1A for protective film formation, the film for protective film formation 13 contains the energy ray-curable component (a), and the above-described adduct-type acrylic polymer (a1-1) is preferable as the above (a).

The adhesive layer 16 for a jig may be, for example, a single layer structure containing an adhesive component, or may be a film layer containing an adhesive component laminated on both surfaces of a sheet of a core material. .

In the composite sheet 1A for protective film formation shown in FIG. 2, the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film for protective film formation 13 in a state where the release film 15 is removed. The upper side of the surface 16a of the adhesive layer 16 is attached to a jig of a ring frame or the like for use.

Fig. 3 is a schematic cross-sectional view showing a composite sheet for forming a protective film 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 adhesive layer 16 for a jig is not provided. In the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the film for forming a protective film 13 is laminated on the entire surface of the first surface 12a of the adhesive layer 12. The release film 15 is laminated on the entire surface of the first surface 13a of the film 13 for forming a protective film.

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

In the composite sheet 1B for forming a protective film, the back surface of the semiconductor wafer (not shown) is attached to the center side of the first surface 13a of the protective film forming film 13 in a state where the release film 15 is removed. A part of the area, and an area near the edge portion is attached to a jig of a ring frame or the like for use.

Fig. 4 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in Fig. 2 except that the adhesive layer 12 is not provided. In other words, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed only of the substrate 11. In addition, the film for protective film formation 13 is laminated on the first surface 11a of the substrate 11 (the first surface 10a of the support sheet 10), and the adhesive layer 16 for the fixture is laminated on the first surface 13a of the film 13 for forming a protective film. A part of the adhesive film 15 is laminated on the first surface 13a of the protective film forming film 13 and the adhesive for the jig is laminated on the first surface 13a of the protective film forming film 13 (a region in the vicinity of the edge portion). The surface 16a (upper surface and side surface) of the layer 16 is on.

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

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

Fig. 5 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to another embodiment of the present invention.
The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in Fig. 4 except that the adhesive layer 16 for a jig is not provided. In the composite sheet 1D for forming a protective film, the film for forming a protective 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 film 13 for forming a protective film. On the surface.

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

The composite sheet 1D for forming a protective film shown in Fig. 5 is the same as the composite sheet 1B for forming a protective film shown in Fig. 3, and the back surface of a semiconductor wafer (not shown) is attached with the release film 15 removed. The region near the center side of the first surface 13a of the protective film forming film 13 and the region near the edge portion are attached to a jig such as a ring frame for use.

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

In the composite sheet 1E for forming a protective film, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and the protective film forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12 (that is, On the central side of the area). Further, the release film 15 is laminated on the surface of the first surface 12a of the adhesive layer 12 where the protective film formation film 23 is not formed and the surface 23a (upper surface and side surface) of the protective film formation film 23.

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

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

In the composite sheet 1E for forming a protective film, the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for forming a protective film, and the adhesive layer is removed. Among the first surface 12a of the 12, the region where the film 23 for forming the protective film is not attached is attached to a jig such as a ring frame for use.

In the composite sheet 1E for forming a protective film shown in FIG. 6, the region where the protective film forming film 23 is not formed in the first surface 12a of the adhesive layer 12 may be laminated in the same manner as shown in FIGS. 2 and 4. The fixture has an adhesive layer (not shown). The composite sheet 1E for protective film formation having the adhesive layer for a jig as described above is the same as the composite sheet for forming a protective film shown in Figs. 2 and 4, and the surface of the adhesive layer for the jig is attached to the ring Fixtures such as frames are available for use.

As described above, in the composite sheet for forming a protective film, the support sheet and the film for forming a protective film may have any form, and may also have an adhesive layer for a jig. However, as shown in FIG. 2 and FIG. 4, it is preferable that the composite sheet for forming a protective film having the adhesive layer for a jig is provided with a pressure-sensitive adhesive layer for a protective film.

The composite sheet for forming a protective film according to the embodiment of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 2 to 6 , and may be in a range not impairing the effects of the present invention. 2 to a part of the structure for forming a protective film shown in Fig. 6 is modified or deleted, or another structure may be added to the structure described so far.

For example, in the composite sheet for forming a protective film shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the substrate 11 and the film 13 for forming a protective film. As the intermediate layer, any one can be selected depending on the purpose.
In the composite sheet for forming a protective film shown in FIG. 2, FIG. 3 and FIG. 6, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. In the composite sheet for forming a protective film of the present invention, the support sheet may be a support sheet obtained by laminating a base material, an intermediate layer, and an adhesive layer in the thickness direction of the film layers in this order. Here, the intermediate layer is the same as the intermediate layer which can be provided in the composite sheet for forming a protective film shown in FIGS. 4 and 5 .
In the composite sheet for forming a protective film shown in FIGS. 2 to 6, a film layer other than the intermediate layer may be provided at an arbitrary position.
In the composite sheet for forming a protective film, a part of the gap may be formed between the release film and the film layer directly contacting the release film.
In the composite sheet for forming a protective film, the size, shape, and the like of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as described later, the film layer which is in direct contact with the film for forming a protective film of the support sheet, such as an adhesive layer, is preferably non-energy ray curability. Such a composite sheet for forming a protective film can more easily pick up a semiconductor wafer with a protective film attached thereto.

The support sheet may be transparent or opaque or may be colored according to the purpose.
Among them, in the invention in which the film for forming a protective film has energy ray curability, the support sheet preferably allows transmission of energy rays.

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

In the support sheet, the light transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
When the light transmittance of the light is within such a range, when the film for protective film formation or the protective film is irradiated with laser light through the support sheet to be imprinted on these films, it can be more clearly engraved.
On the other hand, in the support sheet, the upper limit of the light transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the light transmittance of the above light may be 95% or less.

In the support sheet, the light transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance of the light is within such a range, when the film for protective film formation or the protective film is irradiated with laser light through the support sheet to be imprinted on these films, it can be more clearly engraved.
On the other hand, in the support sheet, the upper limit of the light transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the light transmittance of the above light may be 95% or less.

In the support sheet, the light transmittance of light having a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance of the light is within such a range, when the semiconductor wafer is irradiated with laser light via the support sheet and the protective film forming film or the protective film, the modification can be more easily formed on the semiconductor wafer. Floor.
On the other hand, in the support sheet, the upper limit of the light transmittance of light having a wavelength of 1342 nm is not particularly limited. For example, the light transmittance of the above light may be 95% or less.
Next, each layer constituting the support sheet will be described in more detail.

○Base material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, and polybutadiene; Polyolefin other than polyethylene such as polymethylpentene or norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene- An ethylene-based copolymer such as a decene copolymer (a copolymer obtained by using ethylene as a monomer); a vinyl chloride-based resin such as a polyvinyl chloride or a vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); Polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, poly 2, 6-naphthalene dicarboxylate, all structural units are polyesters such as wholly aromatic polyester having an aromatic cyclic group; copolymers of two or more kinds of the above polyesters; poly(meth)acrylate Polyurethane; urethane acrylate; polyimine; polyamine Polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone.
As the resin, for example, a polymer alloy such as a mixture of the above polyester and another resin may be mentioned. The polymer blend of the above polyester and other resin mixture or the like is preferably a relatively small amount of the resin other than the polyester.
For example, the cross-linking resin obtained by crosslinking one or more of the above-mentioned resins may be used, and one or more of the above-mentioned resins may be used. A modified resin such as an ionomer.

The resin constituting the substrate may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

The thickness of the substrate is preferably from 50 to 300 μm, and more preferably from 60 to 100 μm. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer can be further improved.
Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.
In the present specification, the "thickness" is a value obtained by measuring at any five places of an object to be measured by a contact thickness meter and averaging the measured values.

It is preferable that the substrate has a high precision in thickness, that is, it is preferable to suppress variation in thickness of any portion. Among the above-mentioned constituent materials, examples of the material which can be used for forming such a substrate having a high-precision thickness include polyolefins other than polyethylene and polyethylene, and polyethylene terephthalate. Ethylene-vinyl acetate copolymer and the like.

In addition to the main constituent materials such as the above resin, the substrate may further contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer).

The optical characteristics of the substrate are preferably such as to satisfy the optical characteristics of the support sheet described above. For example, the substrate may be transparent or opaque, or it may be colored according to the purpose, or other layers may be deposited.
Further, in the invention in which the film for forming a protective film has energy ray curability, the substrate is preferably allowed to transmit energy rays.

In order to improve the adhesion between the substrate and other layers of the adhesive layer or the like provided on the substrate, roughening treatment by sand blast treatment, solvent treatment, or the like may be applied to the surface of the substrate. , corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone, ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like.
The substrate may also be a substrate to which a primer treatment is applied to the surface.
The substrate may also have an antistatic coating; when the composite sheet for forming a protective film is stacked for storage, it is used to prevent the substrate from sticking to other sheets or the substrate to adhere to the film layer of the adsorption stage, and the like.

The substrate can be produced by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the above resin.

○Adhesive layer The above-mentioned adhesive layer is in the form of a sheet or a film and contains an adhesive. Examples of the pressure-sensitive adhesive include adhesion of an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin. Resin, and acrylic resin is preferred.

In the present invention, the term "adhesive resin" includes both the adhesive resin and the adhesive resin, and includes, for example, not only a resin having adhesiveness but also other additives such as additives. A resin which exhibits adhesiveness by a component, a resin which exhibits adhesiveness by the presence of a trigger of heat or water, etc.

The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. In the case of a plurality of layers, the plurality of layers may be identical to each other or may be different from each other. The combination of layers is not particularly limited.

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

The optical properties of the adhesive layer are preferably such as to satisfy the optical characteristics of the support sheet described above. The adhesive layer may be transparent or opaque or may be colored according to the purpose.
Further, in the invention in which the film for forming a protective film has energy ray curability, the adhesive layer preferably allows transmission of energy rays.

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

<<Adhesive composition>>
The adhesive composition containing the adhesive can be used to form the adhesive layer. For example, an adhesive composition is applied on a surface on which an adhesive layer is to be formed, and dried as needed to form an adhesive layer at a target position. A more specific method of forming the adhesive layer will be described in detail later with the formation of other layers. In the adhesive composition, the ratio of the content of the component which does not evaporate at normal temperature is usually the same as the ratio of the content of the aforementioned component of the adhesive layer.

The application of the adhesive composition can be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, and a roll. A method of various coaters such as a knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Myrtle bar coater, and an applicator coater.

The drying conditions of the adhesive composition are not particularly limited, but in the case where the adhesive composition contains a solvent described later, it is preferred to heat and dry it. It is preferred to dry the solvent-containing adhesive composition at 70 to 130 ° C for 10 seconds to 5 minutes.

When the adhesive layer has energy ray curability, the adhesive composition containing an energy ray-curable adhesive, that is, an energy ray-curable adhesive composition, for example, includes non-energy rays. Adhesive adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)") and an energy ray-curable compound adhesive composition (I-1); contained in non-energy rays The energy ray-curable adhesive resin (I-2a) in which the side chain of the curable adhesive resin (I-1a) is introduced with an unsaturated group (hereinafter sometimes referred to simply as "adhesive resin (I-2a)") Adhesive composition (I-2); an adhesive composition (I-3) containing the above-mentioned adhesive resin (I-2a) and an energy ray-curable compound, and the like.

<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 above-mentioned adhesive resin (I-1a) is preferably an acrylic resin.
The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.
The structural unit of the acrylic resin may be used alone or in combination of two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

The alkyl (meth)acrylate may, for example, be an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group may be linear or Branches are preferred.
Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, (a) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate ), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (methyl) Cetyl acrylate (also known as palmityl (meth) acrylate), (meth) propylene , Octadecyl (meth) acrylate, stearyl methacrylate (also known as (meth) acrylate, stearyl acrylate), (meth) acrylate, nonadecyl (meth) acrylate, eicosyl.

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

The above acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate.
As the above-mentioned functional group-containing monomer, for example, a reaction of the aforementioned functional group with a crosslinking agent described later as a starting point of crosslinking, by the aforementioned functional group and a subsequently described unsaturated group-containing compound may be mentioned. An unsaturated group reaction or the like can further introduce a monomer having an unsaturated group in a side chain of the acrylic polymer.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3. -Hydroxypropyl (meth)acrylate, hydroxyalkyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; A non-(meth)acrylic unsaturated alcohol such as an alcohol or propylene alcohol (an unsaturated alcohol having no (meth) acryl fluorene skeleton) or the like.

Examples of the carboxyl group-containing monomer include an ethyleny unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; and fumaric acid; , an ethylenically unsaturated dicarboxylic acid such as itaconic acid, maleic acid, citraconic acid or the like (a dicarboxylic acid having an ethylenically unsaturated bond); an acid anhydride of the aforementioned ethylenically unsaturated dicarboxylic acid; A carboxyalkyl (meth)acrylate such as 2-carboxyethyl methacrylate or the like.

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

The functional group-containing monomer constituting the acrylic polymer may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

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

The other monomers constituting the acrylic polymer may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be used alone or in combination of two or more. When two or more types are used, the combination may be arbitrarily selected. proportion.

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably from 5 to 99% by mass, based on the total mass of the above-mentioned adhesive composition (I-1). ～95 mass% is preferable, and it is particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
The energy ray-curable compound contained in the adhesive composition (I-1) includes a monomer or oligomer having an energy ray polymerizable unsaturated group and curable by irradiation with energy rays. .
Among the energy ray-curable compounds, as a monomer, for example, trimethylolpropane tri(meth)acrylate, neopentyl alcohol (meth) acrylate, neopentyltetrakis (meth) acrylate, and Polyvalent (meth) acrylate such as pentaerythritol hexa(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol (meth) acrylate Ethyl urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.
In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the monomers listed above.
The energy ray-curable compound is ethyl urethane (meth) acrylate or ethyl urethane (meth) acrylate from the viewpoint that the molecular weight is relatively large and the storage modulus of the adhesive layer hardly decreases. The oligomer is preferred.

The energy ray-curable compound to be contained in the adhesive composition (I-1) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the energy ray-curable compound is preferably from 1 to 95% by mass, based on the total mass of the adhesive composition (I-1). 90% by mass is preferred, and particularly preferably 10 to 85% by mass.

[crosslinking agent]
In the case where the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a) in addition to the structural unit derived from the alkyl (meth)acrylate Next, the adhesive composition (I-1) preferably contains a crosslinking agent.

The aforementioned crosslinking agent is, for example, a crosslinking agent which can react with the aforementioned functional groups to crosslink the adhesive resin (I-1a) with each other.
Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and an adduct of the above diisocyanate. An epoxy-based crosslinking agent such as ethylene glycol glycidyl ether (a crosslinking agent having a glycidyl group); a hexa[1-(2-methyl)-azepine group]triphosphorazine or the like Aziridine-based crosslinking agent (a crosslinking agent having an aziridine group); metal chelate crosslinking agent such as an aluminum chelate compound (crosslinking agent having a metal chelate structure); isocyanurate A crosslinking agent (a crosslinking agent having an isocyanuric acid skeleton) or the like.
The crosslinking agent is preferably an isocyanate crosslinking agent from the viewpoint of improving the cohesive force of the adhesive to improve the adhesion of the adhesive layer and easy availability.

The crosslinking agent contained in the adhesive composition (I-1) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the above-mentioned crosslinking agent is preferably 0.01 to 50 parts by mass, and 0.1 to 20 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-1a). The portion is preferably in a range of from 0.3 to 15 parts by mass.

[Photopolymerization initiator]
The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator can sufficiently carry out a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetylation of acetophenone compounds; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide a phosphine compound; a sulfide of a benzyl phenyl sulfide, a tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo such as azobisisobutyronitrile; a compound; a titanocene compound such as titanocene; a thioxanthone compound such as thioxanthone; a peroxide; a diketone compound such as a diethylidene group; a benzyl group; a dibenzyl group; a benzophenone; 4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroindole Wait.
As the photopolymerization initiator, for example, an anthracene compound such as 1-chloroindole; a photosensitizer such as an amine or the like can be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be used alone or in combination of two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and 0.03 to 10 parts by mass, based on 100 parts by mass of the energy ray-curable compound. Preferably, it is particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The adhesive composition (I-1) may contain other additives which do not correspond to any one of the above components, within a range not impairing the effects of the present invention.
Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler, a rust preventive, a colorant (pigment, dye), a sensitizer, a tackifier, and the like. A known additive such as a reaction inhibitor or a crosslinking accelerator (catalyst).
As the reaction inhibitor, for example, it is possible to suppress the undesired crosslinking reaction of the adhesive composition (I-1) during storage due to the action of the catalyst mixed in the adhesive composition (I-1). The reaction inhibitor may, for example, be a reaction inhibitor of a chelate complex formed by chelation with a catalyst, and more specifically, may have two or more carbonyl groups in one molecule (—C ( Reaction inhibitor of =O)-).

The other additives contained in the adhesive composition (I-1) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

[solvent]
The adhesive composition (I-1) may also contain a solvent. Since the adhesive composition (I-1) contains a solvent, the coatability to the surface to be coated can be improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; tetrahydrofuran, dioxane and the like. Ethers; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; and alcohols such as 1-propanol and 2-propanol.

As the solvent, for example, the solvent used in the preparation of the adhesive resin (I-1a) may be removed from the adhesive resin (I-1a) and used directly in the adhesive composition (I-1). Alternatively, a solvent which is the same as or different from that used in the preparation of the adhesive resin (I-1a) may be additionally added in the preparation of the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-1) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

<Adhesive Composition (I-2)>
As described above, the pressure-sensitive adhesive composition (I-2) contains an energy ray-curable 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).

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

The unsaturated group-containing compound reacts with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group, and thus the unsaturated group-containing compound has adhesion and adhesion. A compound of a group bonded to the resin (I-1a).

Examples of the energy ray polymerizable unsaturated group include (meth)acryl fluorenyl group, vinyl group (ethenyl (also referred to as vinyl), and allyl group (allyl, also called 2-propenyl group (2-). Propenyl)), etc., preferably a (meth) acrylonitrile group.
As a group which can be bonded to a functional group in the adhesive resin (I-1a), for example, an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and a hydroxyl group or an epoxy group may be mentioned. Bonded hydroxyl groups, amine groups, and the like.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, and glycidyl (meth) acrylate.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be used alone or in combination of two or more. When two or more types are used, the combination may be arbitrarily selected. proportion.

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

[crosslinking agent]
In the case of using, for example, the aforementioned acrylic polymer having the structural unit derived from the functional group-containing monomer in the adhesive resin (I-1a) as the adhesive resin (I-2a), the adhesive composition (I-2) It is preferred to further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) is the same as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-2) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). It is preferably in the range of 0.3 to 15 parts by mass.

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

The photopolymerization initiator in the adhesive composition (I-2) is the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be used alone or in combination of two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and 0.03 to 10 parts by mass based on 100 parts by mass of the adhesive resin (I-2a). The portion is preferably used, and is particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The adhesive composition (I-2) may contain other additives which do not correspond to any one of the above components, within a range not impairing the effects of the present invention.
As the other additives in the adhesive composition (I-2), other additives similar to those in the adhesive composition (I-1) can be mentioned.
The other additives contained in the adhesive composition (I-2) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

[solvent]
The adhesive composition (I-2) may also contain a solvent for the same purpose as the adhesive composition (I-1).
The solvent in the adhesive composition (I-2) is the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-2) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.
In the adhesive composition (I-2), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive Composition (I-3)>
As described above, the adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a) and an energy ray-curable compound.

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably from 5 to 99% by mass, based on the total mass of the above-mentioned adhesive composition (I-3). ～95 mass% is preferable, and it is particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
The energy ray-curable compound contained in the adhesive composition (I-3) includes monomers and oligomers which have energy ray-polymerizable unsaturated groups and are curable by irradiation with energy rays, and can be used. The energy ray-curable compound contained in the same adhesive composition (I-1) is listed.
The energy ray-curable compound to be contained in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, and 0.03 to 100 parts by mass based on the content of the adhesive resin (I-2a). 200 parts by mass is preferred, and particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently carry out a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) is the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be used alone or in combination of two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 20 parts by mass based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. Preferably, it is preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The adhesive composition (I-3) may contain other additives which do not correspond to any one of the above components, within a range not impairing the effects of the present invention.
As the other additives, other additives similar to those in the adhesive composition (I-1) can be mentioned.
The other additives contained in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

[solvent]
The adhesive composition (I-3) may also contain a solvent for the same purpose as the adhesive composition (I-1).
The solvent in the adhesive composition (I-3) is the same as the solvent in the adhesive composition (I-1).
The solvent to be used in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.
In the adhesive composition (I-3), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive Compositions Other than Adhesive Compositions (I-1) to (I-3)>
Heretofore, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been mainly described, and the components of these adhesive compositions have been described, It is also possible to use a general adhesive composition other than the three adhesive compositions (an adhesive composition referred to as "adhesive compositions (I-1) to (I-3) in the present specification). ").

The adhesive composition other than the adhesive composition (I-1) to (I-3) may be a non-energy ray-curable adhesive composition in addition to the energy ray-curable adhesive composition. Things.
Examples of the non-energy-ray-curable adhesive composition include an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, and a polycarbonate. The adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an ester resin is preferably an acrylic resin.

The adhesive composition other than the adhesive composition (I-1) to (I-3) preferably contains one or more kinds of crosslinking agents, and the content of the crosslinking agent may be the same as the above-mentioned adhesion. The composition of the composition (I-1) or the like.

<Adhesive Composition (I-4)>
As a preferable example of the adhesive composition (I-4), for example, an adhesive composition containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent can be mentioned.

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) in the adhesive composition (I-4) is the same 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 used alone or in combination of two or more. When two or more types are used, the combination may be arbitrarily selected. proportion.

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably from 5 to 99% by mass, based on the total mass of the above-mentioned adhesive composition (I-4). ～95 mass% is preferable, and it is particularly preferably 15 to 90% by mass.

[crosslinking agent]
In the case where the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a) in addition to the structural unit derived from the alkyl (meth)acrylate Next, the adhesive composition (I-4) preferably contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) is the same as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-4) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and 0.1 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1a). It is preferably in the range of 0.3 to 15 parts by mass.

[Other additives]
The adhesive composition (I-4) may contain other additives which do not correspond to any one of the above components, within a range not impairing the effects of the present invention.
As the other additives, other additives similar to those in the adhesive composition (I-1) can be mentioned.
The other additives contained in the adhesive composition (I-4) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

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

[solvent]
The adhesive composition (I-4) may also contain a solvent for the same purpose as the adhesive composition (I-1).
The solvent in the adhesive composition (I-4) is the same as the solvent in the adhesive composition (I-1).
The solvent to be used in the adhesive composition (I-4) may be used alone or in combination of two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.
In the adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.

In the composite sheet for forming a protective film, the adhesive layer preferably has non-energy ray curability. This is because when the pressure-sensitive adhesive layer has energy ray curability, when the film for forming a protective film is cured by irradiation with energy rays, it is not possible to suppress simultaneous curing of the pressure-sensitive adhesive layer. When the adhesive layer and the film for forming a protective film are simultaneously cured, the film for forming a protective film and the adhesive layer after curing may adhere to each other at an interface that cannot be peeled off. In this case, a semiconductor wafer (a semiconductor wafer with a protective film) having a film for forming a protective film (that is, a protective film) after curing on the back surface is difficult to be provided with a cured adhesive layer. The support sheet is peeled off, and it becomes impossible to normally pick up the semiconductor wafer with the protective film attached. By setting the adhesive layer in the support sheet to non-energy ray curability, such a problem can be surely avoided, and the semiconductor wafer with the protective film can be more easily picked up.

Here, the effect in the case where the adhesive layer is non-energy ray curable has been described, and even if the film layer which is in direct contact with the film for forming a protective film of the support sheet is a film layer other than the adhesive layer, As long as the film layer is non-energy ray curable, the same effect can be exhibited.

<<Manufacturing method of adhesive composition>>
The adhesive composition (I-1) to (I-3) can be obtained by blending the above-mentioned adhesive, a component other than the above-mentioned adhesive added as needed, and the like for constituting each component of the adhesive composition. An adhesive composition other than the adhesive compositions (I-1) to (I-3) such as the adhesive composition (I-4).
The order of addition when the components are blended is not particularly limited, and two or more components may be added at the same time.
In the case of using a solvent, it may be used by mixing a solvent with any one of the compounding ingredients other than the solvent and preliminarily diluting the formulated component, or by disposing of any one of the ingredients other than the solvent. The solvent is directly diluted and used, and the solvent is directly mixed and used.
The method of mixing the components at the time of preparation is not particularly limited, and can be appropriately selected from known methods such as a method of mixing by stirring a stirrer or a stirring blade, a method of mixing using a mixer, or a method of mixing by ultrasonic waves.
The temperature and time during the addition and mixing of the respective components are not particularly limited as long as the respective components are not deteriorated, and can be appropriately adjusted, and the temperature is preferably 15 to 30 ° C.

In the method for producing a composite sheet for forming a protective film, the composite sheet for forming a protective film can be produced by laminating the respective layers described above in a corresponding positional relationship. The method of forming each layer is as described above.
For example, in the case of producing a support sheet, in the case where an adhesive layer is laminated on a substrate, the above-mentioned adhesive composition can be applied to a substrate and dried as needed.

On the other hand, in the case where a film for forming a protective film is further laminated on the adhesive layer which has been laminated on the substrate, the composition for forming a protective film can be applied onto the adhesive layer to directly form a protective film. A film for formation. In addition to the film layer other than the film for protective film formation, the film for forming the film layer may be laminated on the adhesive layer in the same manner. As described above, in the case where any one of the compositions is used to form a continuous two-layer laminated structure, the composition may be further coated on the film layer formed of the foregoing composition to form a new layer.
However, the film layer which is later laminated among the two layers is previously formed on the other release film using the above composition, and the exposed surface of the formed film layer opposite to the side contacting the release film is It is preferable that the exposed surfaces of the other film layer which have been formed in advance are bonded to each other to form a continuous two-layer laminated structure. At this time, the above composition is preferably applied to the release-treated surface of the release film. After the buildup structure is formed, the release film can be removed as needed.

For example, a composite sheet for forming a protective film (a laminate of a support sheet substrate and an adhesive layer) formed by laminating a film on a substrate and a film for forming a protective film on the pressure-sensitive adhesive layer is formed. In the case of a composite sheet for forming a protective film, by applying an adhesive composition to a substrate and drying it as required, the adhesive is first laminated on the substrate, and then a protective film is additionally formed on the release film. The composition is dried as needed, and a film for forming a protective film is first formed on the release film. Then, the exposed surface of the film for forming a protective film and the exposed surface of the adhesive layer which has been laminated on the substrate are bonded to each other to laminate the film for forming a protective film on the adhesive layer, thereby obtaining a composite sheet for forming a protective film. .

In the case where the adhesive layer is laminated on the substrate, instead of applying the adhesive composition to the substrate as described above, the adhesive composition may be applied to the release film and dried as needed. The adhesive layer is first formed on the release film, and then the exposed surface of the layer and the surface on the substrate side are bonded to each other to laminate the adhesive on the substrate.
In either method, the release film can be removed at any time after the formation of the target laminate structure.

As described above, it is possible to laminate any layer other than the substrate constituting the composite sheet for forming a protective film in advance on the release film and to adhere to the surface of the target layer. A composite sheet in which a protective film is formed can be produced by selecting a film layer which can be used in this manner.

In the state in which the release film is bonded to the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side to the support sheet of the composite sheet for forming a protective film, the composite sheet for forming a protective film is stored. Therefore, a composition for forming the outermost layer constituting the composition for forming a protective film or the like may be applied to the release film (preferably, the release-treated surface of the release film), and dried as needed. First, the film layer constituting the outermost layer is formed on the release film, and then the other layers are laminated on the exposed surface on the opposite side to the side of the release film contacting the layer, and the release film is not removed. In the state of being directly bonded, a composite sheet for forming a protective film is obtained.

The method for producing a semiconductor wafer, the film for forming a protective film and the composite sheet for forming a protective film, can be applied to the production of a semiconductor wafer.
As a method of producing a semiconductor wafer in this case, for example, a production method including a film for forming a protective film which does not constitute the composite sheet for forming a protective film, or a protective film for forming the protective film is exemplified. a step of attaching a film for film formation to a semiconductor wafer (hereinafter sometimes referred to simply as "attachment step"), and a step of irradiating the film for forming a protective film after being attached to the semiconductor wafer to form a protective film by ultraviolet rays (hereinafter sometimes referred to simply as "protective film forming step"), a step of simultaneously cutting the semiconductor wafer and the protective film or protective film forming film to divide the semiconductor wafer to obtain a plurality of semiconductor wafers (The following is sometimes referred to simply as "segmentation step").

Hereinafter, the above manufacturing method will be described with reference to the drawings. FIG. 7 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor wafer in a case where a film for forming a protective film which does not constitute a composite sheet for forming a protective film is used. FIG. 8 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor wafer in the case of using a composite sheet for forming a protective film in which a film for forming a protective film and a support sheet are integrated in advance.

<<Method of Manufacturing Semiconductor Wafer in the Case of Using a Film for Forming a Protective Film Forming a Composite Sheet Forming a Protective Film>>
First, an embodiment of a production 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 is described as an example of a film for forming a protective film as shown in FIG. 1 (this embodiment) Sometimes it can be called "manufacturing method (1)").

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

After the attaching step of the manufacturing method (1), in the protective film forming step, the protective film forming film 13 after being attached to the semiconductor wafer 9 is irradiated with ultraviolet rays, and a protective film is formed on the semiconductor wafer 9. 13', as shown in Figure 7(b). After the second release film 152 is removed from the film for protective film formation 13, ultraviolet rays may be irradiated.

After the protective film forming step of the manufacturing method (1), before the above-described dividing step, as shown in FIG. 7(c), the supporting sheet 10 is attached to the protective film 13' to which the semiconductor wafer 9 is attached. The surface on the side (in the present specification, sometimes referred to as "first surface") 13a' is a surface on the opposite side (may be referred to as "second surface" in the present specification) 13b'. The support sheet 10 is a support sheet as shown in Fig. 2 and the like, and is attached to the protective film 13' by the adhesive layer 12 of the support sheet.

Next, in the dividing step of the manufacturing method (1), the semiconductor wafer 9 is cut together with the protective film 13' by dicing or the like to divide the semiconductor wafer 9 as shown in FIG. 7(d), and further A plurality of semiconductor wafers 9' are obtained. At this time, the protective film 13' is cut (divided) at a position along the edge portion of the semiconductor wafer 9'. This cut protective film 13' is indicated by reference numeral 130'.

Fig. 7 is a view showing a state in which the support sheet 10 is attached to the protective film 13' after the protective film forming step. However, in the manufacturing method (1), the protective film forming step may be performed after the support sheet 10 is attached to the protective film forming film 13.

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

<<Method of Manufacturing Semiconductor Wafer in the Case of Using a Composite Sheet Forming a Protective Film Forming Integrated with a Protective Film Forming Film and a Support Sheet in Advance>>
Next, an embodiment of the manufacturing method in the case of using a composite sheet for forming a protective film in which a film for forming a protective film and a support sheet are integrated in advance is used as a composite sheet for forming a protective film as shown in FIG. The example will be described (this embodiment may be referred to as "manufacturing method (2)").

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

After the attaching step of the manufacturing method (2), in the protective film forming step, the protective film forming film 13 after being attached to the semiconductor wafer 9 is irradiated with ultraviolet rays, and a protective film is formed on the semiconductor wafer 9. 13', as shown in Figure 8(b). At this time, the film 13 for forming a protective film is irradiated with ultraviolet rays through the support sheet 10.
Here, the composite sheet for forming a protective film after the protective film forming film 13 is the protective film 13' is denoted by reference numeral 1A'. This also applies to the following schema.

After the attaching step of the manufacturing method (2), in the dividing step of the manufacturing method (2), the semiconductor wafer 9 is cut together with the protective film 13' by dicing or the like to divide the semiconductor wafer 9 into As shown in FIG. 8(c), a plurality of semiconductor wafers 9' are further obtained. At this time, the protective film 13' is cut (divided) at a position along the edge portion of the semiconductor wafer 9' to become the protective film 130'.
By the above manner, the target semiconductor wafer 9' can be obtained as a semiconductor wafer with a protective film.

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

The method for manufacturing a semiconductor wafer in the case where the protective film forming film 13 shown in FIG. 1 , the supporting sheet 10 shown in FIG. 2 , and the protective film forming composite sheet 1A shown in FIG. 2 are used has been used. Although the method of manufacturing the semiconductor wafer of the present invention is not limited thereto.
For example, when a composite sheet for forming a protective film is used, a composite sheet for forming a protective film 1B to 1E shown in FIGS. 3 to 6 and a composite sheet for forming a protective film of the intermediate layer may be used. In the composite sheet for forming a protective film other than the composite sheet 1A for protective film formation shown in FIG. 2, a semiconductor wafer is produced in the same manner.
It is also possible to use a support sheet other than the support sheet 10 shown in FIG. 2 in which a support sheet composed only of a base material, a support sheet composed of an intermediate layer, and the like described above is used, and is manufactured in the same manner. Semiconductor wafer.
As described above, when the composite sheet for forming a protective film or the support sheet of the other embodiment is used, it is possible to appropriately add, change, delete, etc. the steps in the above-described manufacturing method based on the structural difference of the sheets. To manufacture a semiconductor wafer.

In the method of manufacturing a germanium semiconductor device, after the semiconductor wafer is obtained by the above-described manufacturing method, the semiconductor wafer is directly supported from the support in a state in which the divided protective film is attached (that is, as a semiconductor wafer with a protective film). The pieces are peeled off and picked up (not shown).
The obtained semiconductor wafer with the protective film-attached semiconductor wafer is placed face down on the circuit surface of the substrate, and is heated at 100 to 280 ° C by the surface on which the protective film is formed in the semiconductor wafer. It is used as a semiconductor package after flip-chip bonding. Then, by using this semiconductor package, a target semiconductor device (not shown) can be manufactured.
[Examples]

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

<Preparation raw material for protective film forming composition>
The raw materials for preparing the composition for forming a protective film are as follows.
[Energy ray curable component (a1-1)]
(a1-1)-1: an adduct type acrylic polymer (weight average molecular weight: 350,000, glass transition temperature: 6 ° C) in which an ultraviolet curable group was introduced into a side chain, and was obtained as follows: 2-methylpropenyloxyethyl isocyanate ("Karenz MOI (registered trademark)") manufactured by Showa Denko Co., Ltd. in a molar amount of 10 moles for methyl acrylate (85 parts by mass) and 2-hydroxy acrylate The ethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) copolymerized acrylic polymer was reacted with 100 hydroxy groups derived from 2-hydroxyethyl acrylate.
(a1-1)-2: an adduct-type acrylic polymer (weight average molecular weight: 350,000, glass transition temperature: 6 ° C) in which an ultraviolet curable group was introduced into a side chain, and was obtained as follows: Acrylic acid obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) at a molar amount of 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd.) at 30 mol The polymer is reacted with 100 hydroxy groups derived from 2-hydroxyethyl acrylate.
[Energy ray curable component (a2)]
(a2)-1: ε-caprolactone-modified ginseng-(2-propenyloxyethyl)isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional Base ultraviolet curable compound).
[Polymer having no energy ray-curable group (b)]
(b)-1: an acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight: 350,000, glass transition temperature: 6 ° C).
[Photopolymerization initiator (c)]
(c)-1: 2-(Dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (Irgacure (registered trademark) 369, manufactured by BASF Corporation ").
[Filler (d)]
(d)-1: cerium oxide filler (fused silica filler, average particle diameter: 8 μm).
[coupler]
(e)-1: 3-methacryloxypropyltrimethoxydecane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent).
[coloring agent (g)]
(g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (blue pigment 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (yellow pigment 139), and 50 parts by mass of ruthenium A pigment obtained by mixing the red pigment (red pigment 177) into a total amount of the above three kinds of pigments/the amount of the styrene acrylic resin = 1/3 (mass ratio).

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

[Example 1]
<Manufacture of composite sheet for forming a protective film>
(Preparation of Protective Film Forming Composition (IV-1))
10 parts by mass of the energy ray-curable component (a2)-1, 28 parts by mass of the adduct-type acrylic polymer (a-1)-1, 0.6 parts by mass of light per 100 parts by mass of the solid portion Polymerization initiator (c)-1, 57 parts by mass of filler (d)-1, 0.4 parts by mass of coupling agent (e)-1, and 3 parts by mass of coloring agent (g)-1 dissolved or dispersed in A In the ethyl ketone, the composition for forming a protective film (IV-1) having a solid content concentration of 50% by mass was prepared by stirring at 23 °C.

(Preparation of Adhesive Composition (I-4))
A non-energy ray curable adhesive composition (I-4) having a solid content concentration of 30% by mass, containing an acrylic polymer (100 parts by mass, a solid component), and an isocyanate crosslinking agent (Japanese polyurethane) "Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd., toluene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), and also contains methyl ethyl Ketone as a solvent. The acrylic polymer obtained by copolymerizing 2-ethylhexyl methacrylate (80 parts by mass) and HEA (20 parts by mass) has a weight average molecular weight of 600,000.

(manufacture of the support sheet)
A peeling film obtained by peeling off one surface of a film made of polyethylene terephthalate by polyfluorination treatment ("SP-PET 381031" manufactured by Lintec Co., Ltd." The above-mentioned adhesive composition (I-4) was coated on the above-mentioned release-treated surface having a thickness of 38 μm, and dried by heating at 120 ° C for 2 minutes to form a non-energy having a thickness of 10 μm. A radiation curable adhesive layer.
Next, a polypropylene-based film (thickness: 80 μm) as a substrate was attached to the exposed surface of the adhesive layer to obtain a substrate, an adhesive layer, and a release film in this order in the thickness direction of the layers. A support piece made up of layers.

(Manufacture of composite sheet for forming a protective film)
A release film obtained by peeling off one surface of a film made of polyethylene terephthalate by polyfluorination treatment (second release film, manufactured by Lintec) The above-mentioned protective film-forming composition (IV-1) was applied onto the surface of the release-treated surface of SP-PET 382150 (thickness: 38 μm), and dried by heating at 100 ° C for 2 minutes. An energy ray-curable film for forming a protective film having a thickness of 25 μm was produced.
Then, the release-treated surface of the release film (the first release film, "SP-PET 381031" manufactured by Linde Co., Ltd., thickness: 38 μm) is bonded to the obtained film for forming a protective film. 2 The exposed surface on the side of the release film is obtained by providing a laminated film having a first release film on the surface on one side of the film for forming a protective film and a second release film on the other surface.

Next, the release film was removed from the adhesive layer of the support sheet obtained above. The first release film was removed from the laminated film obtained above. After that, the surface exposed by the removal of the above-mentioned release film in the adhesive layer and the surface exposed by the removal of the first release film in the film for protective film are bonded to each other to produce a substrate and adhesion. The protective layer-forming composite sheet obtained by laminating the film layer, the film for forming a protective film, and the second release film in the thickness direction of these film layers in this order.

<Evaluation of Protective Film>
(Measurement of gloss value (glossiness) of protective film)
The surface of the film for forming a protective film which was exposed by removing the first release film from the above-mentioned laminated film was attached to a #2000 polished surface of an 8-inch tantalum wafer (thickness: 300 μm).
Then, the second release film is removed from the film for forming a protective film to expose the film for forming a protective film. The release film was removed from the adhesive layer of the support sheet obtained above to expose the adhesive layer. Thereafter, the exposed surface of the adhesive layer and the exposed surface of the film for forming a protective film are bonded to each other and attached to the annular frame, so that the substrate, the adhesive layer, the film for forming a protective film, and the wafer are formed. The laminate obtained by laminating in the thickness direction of these film layers was fixed to the ring frame and allowed to stand for 30 minutes.

Then, by using an ultraviolet irradiation device ("RAD 2000m/8" manufactured by Linde Co., Ltd.), the substrate and the adhesive were interposed under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² . In the agent layer, the film for forming a protective film is irradiated with ultraviolet rays to cure the film for forming a protective film into a protective film.

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

Next, the germanium wafer on which the protective film was formed was heated at 260 ° C for 5 minutes using an oven. Thereafter, the gloss value (gloss value after heating) of the surface of the protective film was measured under the same conditions as those for measuring the gloss before heating. When the rate of decrease from the gloss value before heating to the gloss value after heating was 30% or less, it was judged to be good. The measured decrease in gloss value before heating, gloss value after heating, and gloss value after heating are shown in Table 1.

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

[Comparative Example 1]
The addition type acrylic polymer (a1-1)-1 used in the production of the protective film forming composition (IV-1) is changed to a polymer having no energy ray-curable group (b) In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were produced in the same manner as in Example 1, and the protective film was evaluated. The results are shown in Table 1.

[Table 1]

As is clear from the above results, in Example 1, the gloss value before the heating of the surface of the protective film and the gloss value after heating were as high as 80 and 65, respectively, so that the rate of decrease in the gloss value after heating was as low as 19%. In Example 2, the gloss value before the heating of the surface of the protective film and the gloss value after heating were as high as 80 and 72, respectively, so that the rate of decrease in the gloss value after heating was also as low as 10%. This is considered to be because the adduct-type acrylic polymer is polymerized by irradiation of ultraviolet rays, so that the protective film contains almost no polymer having a low molecular weight, and even if the protective film is heated, there is no polymer having a low molecular weight. Segregation on the surface of the protective film.

On the other hand, in Comparative Example 1, the gloss value of the surface of the protective film before heating was as high as 80, and the gloss value after heating was as low as 9. This is considered to be because, in Comparative Example 1, a large amount of a low molecular weight polymer (b) having no energy ray-curable group was contained in the protective film, and the protective film was obtained. The polymer which is heated to cause the aforementioned low molecular weight polymer to segregate on the surface of the protective film, and thus the gloss value is lowered.

From the results of the examples and the comparative examples, it was confirmed that the polymer (b) having no energy ray-curable group in the protective film can be replaced by the adduct-type acrylic polymer (a1-1). The decrease in the gloss value caused by the heating of the surface of the protective film is suppressed.
[Industry profitability]

The present invention can be applied to the manufacture of a semiconductor device.

1A, 1A', 1B, 1C, 1D, 1E‧‧‧ Composite film for protective film formation

9‧‧‧Semiconductor wafer

9b‧‧‧Back of semiconductor wafer

9’‧‧‧Semiconductor wafer

10‧‧‧Support film

10a‧‧‧Surface of the support piece (first surface)

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate (first surface)

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer (first surface)

13, 23‧‧‧film for protective film formation

13a, 23a‧‧‧ Surface of the film for protective film formation (first surface)

13b‧‧‧ Surface of film for protective film formation (second surface)

13'‧‧‧ Protective film

130'‧‧‧After cut protective film

15‧‧‧Release film

151‧‧‧1st release film

152‧‧‧Second release film

16‧‧‧Adhesive adhesive layer

16a‧‧‧The surface of the adhesive layer for the fixture

Fig. 1 is a schematic cross-sectional view showing a film for forming a protective film according to an embodiment of the present invention.

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

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

Fig. 4 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to an embodiment of the present invention.

Fig. 5 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to an embodiment of the present invention.

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

FIG. 7 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor wafer in a case where a film for forming a protective film is used.

[Fig. 8] Fig. 8 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor wafer in the case of using a composite sheet for forming a protective film.

Claims (3)

A film for forming a protective film, which is an energy ray-curable film for forming a protective film, wherein a gloss value measured after attaching the film for forming a protective film to a semiconductor wafer and irradiated with an energy ray is The film for protective film formation was attached to a semiconductor wafer and the rate of decrease in the gloss value measured after irradiation with energy rays and further heating at 260 ° C for 5 minutes was 30% or less. A composite sheet for forming a protective film, comprising a support sheet, and comprising the film for forming a protective film according to the first aspect of the invention. A method of fabricating a semiconductor wafer, comprising the steps of: The film for forming a protective film according to the first aspect of the invention, or the film for forming a protective film in the composite sheet for forming a protective film according to claim 2, attached to the semiconductor wafer; The film for forming a protective film after being attached to the semiconductor wafer is irradiated with ultraviolet rays to form a protective film; The semiconductor wafer is simultaneously cut by the protective film or the film for forming a protective film, and the semiconductor wafer is divided to obtain a plurality of semiconductor wafers.