KR20180077174A - Film for forming protective film and composite sheet for forming protective film - Google Patents

Abstract

A film for forming a protective film for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip which contains the energy ray curable compound (B) and has the following characteristics: the film for forming a protective film is cured by irradiation of an energy ray, , The Young's modulus of the cured product is 500 MPa or more, and the elongation at break is 8% or more.

Description

Film for forming protective film and composite sheet for forming protective film

The present invention relates to a protective film forming film for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip, and a protective film forming composite sheet provided with the protective film forming film.

The present application claims priority based on Japanese Patent Application No. 2015-212845 filed on October 29, 2015, the contents of which are incorporated herein by reference.

2. Description of the Related Art In recent years, a semiconductor device using a mounting method called a face-down method has been manufactured. In the face-down method, a semiconductor chip having an electrode such as a bump is used on a circuit surface, and the electrode is bonded to the substrate. Therefore, the back surface opposite to the circuit surface of the semiconductor chip may be exposed.

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

In order to form such a protective film, for example, a protective sheet-forming composite sheet comprising a protective film-forming film on a support sheet is used. In the composite sheet for forming a protective film, the protective film forming film has a protective film forming ability, and the supporting sheet can be used as a dicing sheet, and the protective film forming film and the dicing sheet can be integrated.

As such a composite sheet for forming a protective film, for example, those having a protective film-forming film for forming a protective film by curing by heating have been mainly used so far. The semiconductor wafer is, for example, a semiconductor chip formed by dicing after a protective film forming composite sheet is attached to the back surface (the surface opposite to the electrode forming surface) with a protective film forming film. Then, after the film for forming a protective film is cured by heating to form a protective film, this semiconductor chip is picked up with the protective film attached thereto, or after picking up the semiconductor chip in a state where the protective film forming film is pasted, To form a protective film.

However, since heating and curing of the film for forming a protective film usually requires a long time of about several hours, shortening of the curing time is required. On the contrary, a film for forming a protective film that can be cured by irradiation of an energy ray such as ultraviolet rays is being studied, and a protective film (a film for preventing the occurrence of chipping during dicing of a semiconductor wafer (Refer to Patent Document 2), which can form a protective film excellent in laser mark recognizability, hardness and mounting reliability (see Patent Document 2), a protective film capable of forming a protective film having high hardness and excellent adhesion to a semiconductor chip See Patent Document 3).

Japanese Laid-Open Patent Publication No. 2009-147277 Japanese Laid-Open Patent Publication No. 2009-138026 Japanese Laid-Open Patent Publication No. 2010-031183

However, for the protective film forming film, for example, defects are generated in the outer edge portion of the semiconductor chip, so-called chipping is suppressed, and the protective action is high with respect to the semiconductor wafer or the semiconductor chip so as to suppress cracks and defects , And it is required to be able to form a protective film having a high reliability that can maintain a high protective effect even when exposed to a large temperature change. Therefore, there is still room for improvement in the conventional film for forming a protective film which can be cured by irradiation of energy rays.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has an object of providing a protective film forming film capable of forming a protective film having a high protecting effect and high reliability against a back surface of a semiconductor wafer or a semiconductor chip, And a composite sheet for use in the present invention.

In order to solve the above problems, the present invention provides a protective film forming film for forming a protective film on a back surface of a semiconductor wafer or a semiconductor chip containing an energy ray curable compound (B) , A Young's modulus of the cured product obtained by the above process is 500 MPa or more, and a elongation at break of 8% or more.

In the protective film forming film of the present invention, the ratio of the total content of the energy ray curable compound (B1) having 2 to 4 energy linear polymerizable groups in one molecule to the total content of the energy ray curable compounds (B) is 90 By mass or more.

Further, the present invention provides a protective sheet-forming composite sheet comprising the protective film-forming film on one surface of a support sheet.

That is, the present invention includes the following aspects.

[1] A film for forming a protective film for forming a protective film on the back surface of a semiconductor wafer or semiconductor chip containing the energy ray curable compound (B) and having the following characteristics: the protective film forming film is cured by irradiation of energy rays When a cured product is used, the Young's modulus of the cured product is 500 MPa or more and the elongation at break is 8% or more.

[2] In the protective film-forming film, the content of the energy ray-curable compound (B1) having 2 to 4 energy linear polymerizable groups in one molecule is preferably 90 mass% % Or more.

[3] A composite sheet for forming a protective film, comprising the protective film-forming film according to [1] or [2] on one surface of a support sheet.

According to the present invention, there is provided a protective film forming film capable of forming a protective film having a high protective effect and high reliability against a back surface of a semiconductor wafer or a semiconductor chip, and a protective sheet forming complex sheet provided with the protective film forming film do.

1 is a cross-sectional view schematically showing an embodiment of a protective film-forming composite sheet according to the present invention.
2 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film according to the present invention.
3 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to the present invention.
4 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to the present invention.
5 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to the present invention.

&Quot; Film for forming a protective film &

The film for forming a protective film according to the present invention is a film for forming a protective film for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip containing the energy ray curable compound (B) The Young's modulus of the obtained cured product (i.e., protective film) is 500 MPa or more, and the elongation at break is 8% or more. That is, another aspect of the protective film-forming film according to the present invention includes the energy ray-curable compound (B) and also has the following characteristics:

And the Young's modulus of the cured product is 500 MPa or more and the elongation at break is 8% or more when the protective film forming film is cured to form a cured product (protective film) by irradiation of an energy ray.

The cured product, that is, the protective film has a sufficiently high protective effect on the semiconductor wafer or the semiconductor chip, because the Young's modulus and the elongation at break are the lower limit value or more. For example, in the case of dicing a semiconductor wafer having the protective film forming film or protective film on the back surface thereof, the semiconductor chip finally obtained has cracks or defects such as occurrence of defects on its outer edge, Is suppressed. Further, since the Young's modulus and the elongation at break of the protective film are equal to or more than the lower limit value, the protective film can maintain a high protective action as described above, even when exposed to a large temperature change, and has high reliability. For example, although the semiconductor chip with a protective film is exposed to a large temperature change during its mounting, the protective film can maintain a high protective function even under such a condition.

As described above, the protective film forming film according to the present invention can form a protective film having high protective effect and reliability even by irradiation of energy rays.

The film for forming a protective film contains an energy ray-curable compound (B), thereby curing it by irradiation of an energy ray to form a protective film.

As used herein, the term " energy ray " means having both energy in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, electron beams, and the like.

The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, an LED, or the like as an ultraviolet ray source. The electron beam can be irradiated by an electron beam accelerator or the like.

The irradiation dose of the energy ray differs depending on the kind of the energy ray. For example, in the case of ultraviolet rays, the irradiance is preferably 50 to 500 mW / cm 2, and the light quantity is preferably 200 to 800 mJ / cm 2.

The film for forming a protective film may be formed using a composition for forming a protective film containing a component for constituting the protective film, and may be formed, for example, by coating the surface of the substrate with the protective film forming composition and drying the film. The ratio of the content of the components that are not vaporized at room temperature in the composition for forming a protective film is generally the same as the content of the components in the film for forming a protective film. In the present specification, the term " normal temperature " means a temperature that is not particularly cooled or heated, that is, a normal temperature, for example, a temperature of 15 to 25 캜.

The support is not particularly limited as long as it can maintain the shape of the protective film forming film. For example, the support may be used only for forming the protective film forming film, and after the protective film forming film is formed, Or may be used in a separate intended use while being laminated with a film for forming a protective film. As the support used for forming the above-mentioned protective film forming film, for example, a peelable film having a peeled surface can be cited. After the formation of the film for forming a protective film, the support which is further used for another application includes, for example, a support sheet or substrate such as a dicing sheet described later.

The thickness of the film for forming a protective film is not particularly limited, but is preferably 1 to 100 占 퐉, more preferably 5 to 75 占 퐉, and particularly preferably 5 to 50 占 퐉. When the thickness of the protective film forming film is equal to or more than the above lower limit value, the adhesive force to the semiconductor wafer or the semiconductor chip as the adhesion becomes greater. Further, since the thickness of the protective film-forming film is equal to or less than the upper limit value, the protective film as the cured product can be more easily cut by using the shearing force at the time of picking up the semiconductor chip.

In the present specification, the term " thickness " means a value expressed by an average obtained by measuring the thickness of the contact type thickness meter at any five positions.

<Composition for forming protective film>

The composition for forming a protective film contains an energy ray-curable compound (B), and preferably contains, for example, a polymer component (A) and an energy ray-curable compound (B) (A), an energy ray-curable compound (B) and a photopolymerization initiator (C).

Next, the components contained in the composition for forming a protective film and the film for forming a protective film will be explained.

[Polymer component (A)]

The polymer component (A) is a component that can be regarded as being formed by the polymerization reaction of the polymerizable compound, and is a polymer compound for imparting film forming property, flexibility, etc. to the protective film forming film. In the present invention, the polymerization reaction also includes a polycondensation reaction.

When the component contained in the protective film forming composition corresponds to both of the polymer component (A) and the energy ray-curable compound (B), these components are treated as the energy ray-curable compound (B). Examples of such a component include an acrylic polymer having a hydroxyl group and having a polymerizable group on the side chain via a urethane bond.

One kind of polymer component (A) may be used alone, or two or more kinds may be used in combination.

Examples of the polymer component (A) include an acrylic resin, a polyester, a polyurethane, an acryl urethane resin, a silicone resin, a rubber-based polymer, a phenoxy resin and the like, and an acrylic resin is preferable.

As the acrylic resin, a known acrylic polymer can be used.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 200,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the lower limit value described above, the adhesive force between the support sheet and the protective film to be described later is suppressed, and the pickup property of the semiconductor chip with a protective film is further improved. When the weight average molecular weight of the acrylic resin is not more than the upper limit value, the film for forming the protective film tends to follow the uneven surface of the adherend (semiconductor wafer or semiconductor chip), and voids, etc. between the adherend and the protective film- Occurrence is further suppressed.

In the present specification, the "weight average molecular weight" means a polystyrene reduced value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 占 폚, and more preferably -30 to 50 占 폚. Since the Tg of the acrylic resin is equal to or more than the above lower limit value, the adhesive force between the support sheet and the protective film is suppressed, and the pickup property of the semiconductor chip with the protective film is further improved. Further, when the Tg of the acrylic resin is not more than the upper limit value, the adhesive force between the adherend and the protective film forming film becomes greater.

Examples of the monomers constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, n-octyl (meth) acrylate, n-nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (Also referred to as "myristyl (meth) acrylate"), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (Meth) acrylate having 1 to 18 carbon atoms and an alkyl group constituting an alkyl ester such as octadecyl (meth) acrylate, heptadecyl (meth) acrylate and octadecyl Alkyl esters;

(Meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meta) acrylic acid ester having a cyclic skeleton such as methacrylic acid imide;

(Meth) acrylic acid esters such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

(Meth) acrylate and glycidyl group-containing (meth) acrylate such as glycidyl (meth) acrylate.

Among these, as the monomer constituting the acrylic resin, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate are preferable.

On the other hand, in the present specification, the term "(meth) acrylic acid" includes both "acrylic acid" and "methacrylic acid". The term "(meth) acrylate" is a concept including both "acrylate" and "methacrylate", and the term "(meth) acryloyl group" Acryloyl group &quot; and &quot; methacryloyl group &quot;.

Examples of the monomer constituting the acrylic resin include monomers other than (meth) acrylic acid esters such as (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-methylol acrylamide.

The monomers constituting the acrylic resin may be one kind or two or more kinds.

The acrylic resin may have a functional group capable of binding with other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. The functional group may be bonded to another compound via a cross-linking agent (G) described below, or may be bonded directly to another compound without interposing the cross-linking agent (G). The acrylic resin tends to bond with another compound by the functional group, and thus the package reliability of the semiconductor device obtained using the protective film forming film tends to be improved.

When the composition for forming a protective film contains an acrylic resin as the polymer component (A), the content of the acrylic resin in the protective film forming composition is preferably 5 to 50 mass% with respect to the total mass of all components other than the solvent in the protective film forming composition , More preferably from 10 to 45 mass%. When the content of the acrylic resin is in this range, the adhesive force between the support sheet and the protective film is suppressed, and the pickup property of the semiconductor chip with a protective film is further improved.

When the protective film-forming film contains an acrylic resin as the polymer component (A), the content of the acrylic resin in the protective film-forming film is preferably from 5 to 50 mass%, more preferably from 10 to 50 mass% And more preferably 45% by mass.

In the present invention, by reducing the adhesive force (peeling force) between the support sheet and the protective film, the pickup property of the semiconductor chip with a protective film is further improved, or the film for forming the protective film is easily followed on the uneven surface of the adherend, (Hereinafter sometimes simply referred to as &quot; thermoplastic resin &quot;) may be used alone as the polymer component (A) in order to further suppress generation of voids and the like between the protective film forming film Or may be used in combination with an acrylic resin.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, more preferably 3000 to 80000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably -30 to 150 캜, more preferably -20 to 120 캜.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The thermoplastic resin may be used singly or in combination of two or more.

[Energy ray-curable compound (B)]

The energy ray curable compound (B) is a component which can be cured (polymerized) by irradiation of an energy ray. The energy ray curable compound (B) is a component for curing the protective film forming film and forming a hard protective film (that is, a cured product obtained by irradiating the energy ray to the protective film forming film), and either of the monomer and oligomer .

The energy ray curable compound (B) may be used singly or in combination of two or more kinds.

The content of the energy ray curable compound (B) in the protective film forming composition is preferably 3 to 30 mass%, more preferably 5 to 25 mass%, with respect to the total mass of all components other than the solvent in the protective film forming composition .

The content of the energy ray curable compound (B) in the film for forming a protective film is preferably 3 to 30 mass%, more preferably 5 to 25 mass%, based on the total mass of the protective film forming film.

Examples of the energy ray curable compound (B) include compounds having one or more energy linear polymerizable groups in one molecule.

The energy ray polymerizable group is not particularly limited as long as it is a group that undergoes a polymerization reaction by irradiation of an energy ray. When one molecule of the energy ray-curable compound (B) has two or more energy ray polymerizable groups, They may be the same or different. That is, the two or more energy ray polymerizable groups of one molecule of the energy ray-curable compound (B) may be all the same, all of the same or a part of them may be the same.

Examples of the energy ray polymerizable group include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

The energy ray curable compound (B) is preferably a polyfunctional compound having two or more energy ray polymerizable groups in one molecule. The content of the polyfunctional compound in the composition for forming a protective film and the film for forming a protective film is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or less based on the total mass of the energy ray curable compound (B) (B) contained in the composition for forming a protective film and the film for forming a protective film may be 100 mass% or less, more preferably 100 mass% or less, and even more preferably 98 mass% or more and 100 mass% May be all the above-mentioned polyfunctional compounds.

The molecular weight of the energy ray curable compound (B) is preferably 1000 or less, more preferably 100 to 1000, further preferably 150 to 800, particularly preferably 200 to 550. When the molecular weight of the energy ray curable compound (B) is in this range, the protective film formed has a higher protective effect and reliability.

The energy ray curable compound (B) is preferably a (meth) acrylate compound, more preferably a polyfunctional (meth) acrylate compound having two or more energy ray polymerizable groups in one molecule, (Meth) acrylate compound having two or more acryloyl groups is particularly preferable. On the other hand, the term "(meth) acrylate compound" means a (meth) acrylic acid ester or a derivative thereof. In the present specification, the term "derivative" means a compound in which at least one hydrogen atom in the original compound is substituted with a group (substituent) other than a hydrogen atom.

Examples of the polyfunctional (meth) acrylate compound having two or more of the above (meth) acryloyl groups include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di Acrylate, di (meth) acrylate (also referred to as tricyclodecane dimethylol diacrylate), caprolactone modified dicyclopentenyl (meth) acrylate, ethylene oxide modified di (meth) Bifunctional (meth) acrylate compounds such as maleic anhydride, maleic anhydride, maleic anhydride, and maleic anhydride;

(Meth) acrylate, propylene oxide-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri ) Acrylate, tris (acryloxyethyl) isocyanurate, bis (acryloxyethyl) hydroxyethyl isocyanurate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, - trifunctional (meth) acrylate compounds such as caprolactone modified tris (acryloxyethyl) isocyanurate;

Tetrafunctional (meth) acrylate compounds such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate;

(Meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate and propionic acid-modified dipentaerythritol penta (meth) acrylate;

(Meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate.

Of these, tricyclodecane dimethylol diacrylate and? -Caprolactone modified tris (acryloxyethyl) isocyanurate are preferred.

The energy ray curable compound (B) preferably has 2 to 4 energy ray polymerizable groups in one molecule, more preferably 2 to 3 energy ray polymerizable groups. By using such an energy ray-curable compound (B), the protective film to be formed has higher protection effect and reliability. In the present specification, among the energy ray curable compounds (B), those having 2 to 4 energy linear polymerizable groups in one molecule are defined as &quot; energy ray curable compound (B1) &quot;, and those having at least 5 energy linear polymerizable groups May be collectively referred to as &quot; energy ray curable compound (B2) &quot;.

As the energy ray curable compound (B1), it is preferable that the number of energy ray polymerizable groups contained in one molecule is 2 to 3, and for example, tricyclodecane dimethylol diacrylate,? -Caprolactone modified tris (acryloxyethyl) iso And cyanurate.

The content of the energy ray-curable compound (B) (i.e., the energy ray-curable compound (B1)) having 2 to 4 energy linear polymerizable groups in one molecule in the protective film forming composition and the protective film- More preferably not less than 95% by mass and not more than 100% by mass, particularly preferably not less than 98% by mass and not more than 100% by mass, particularly preferably not less than 100% by mass, based on the total mass of the resin (B) , That is, the energy ray-curable compound (B) contained in the protective film forming composition and the protective film forming film may all be the energy ray curable compound (B1).

In the composition for forming a protective film and the film for forming a protective film, the content of the energy ray-curable compound having 2 to 3 energy linear polymerizable groups in one molecule is preferably 80 mass% or less, More preferably 90% by mass or more and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less, particularly preferably 100% by mass or less %, That is, the energy ray-curable compound (B) contained in the composition for forming a protective film and the film for forming a protective film may all be energy ray-curable compounds having 2 to 3 energy linear polymerizable groups in one molecule.

The content of the energy ray-curable compound (B) in the composition for forming a protective film and the film for forming a protective film is preferably 1 to 150 parts by mass, more preferably 5 to 130 parts by mass based on 100 parts by mass of the polymer component (A) And particularly preferably from 10 to 110 parts by mass. When the content of the energy ray-curable compound (B) is not less than the above lower limit value, the protective film to be formed maintains a high protective effect even when exposed to a large temperature change, and reliability is further enhanced. When the above content of the energy ray curable compound (B) is not more than the upper limit value, the adhesive force between the support sheet and the protective film is suppressed, and the pickup property of the semiconductor chip with the protective film is further improved.

[Photopolymerization initiator (C)]

The photopolymerization initiator (C) is a component for generating a radical by irradiation of an energy ray and initiating a curing reaction by radical polymerization of the energy ray curable compound (B).

The photopolymerization initiator (C) may be a known one, and specific examples thereof include 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, hydroxy-1- {4- [4- (2-hydroxy-2-methylpyridin-2- ylmethyl) -Propionyl) -benzyl] phenyl} -2-methyl-propan-1-one; Acetophenone, dimethylaminoacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, Acetophenone-based compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; Benzoin ether compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and anisoin methyl ether; Ketal compounds such as benzyl dimethyl ketal and acetophenone dimethyl ketal; Aromatic sulfonyl chloride-based compounds such as 2-naphthalenesulfonyl chloride; Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime); Benzophenone compounds such as benzophenone, p-phenylbenzophenone, benzoylbenzoic acid, dichlorobenzophenone, 4,4'-diethylaminobenzophenone and 3,3'-dimethyl-4-methoxybenzophenone; Anthraquinone compounds such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, and 2-amino anthraquinone; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4- Thioxanthone compounds such as 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; p-dimethylaminobenzoic acid ester; Camphorquinone; Halogenated ketones; Acylphosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; Acylphosphonate and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone].

Of these, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] - and 1- (O-acetyloxime) are preferred.

The content of the photopolymerization initiator (C) in the composition for forming a protective film is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, more preferably 0.2 to 5 parts by mass based on 100 parts by mass of the polymer component (A) Particularly desirable. When the content of the photopolymerization initiator (C) is not less than the lower limit value, the curing reaction of the energy ray curable compound (B) proceeds more efficiently. Further, when the above content of the photopolymerization initiator (C) is not more than the upper limit value, the protective film to be formed has higher protection effect and reliability.

The content of the photopolymerization initiator (C) in the protective film forming composition is preferably 0.1 to 3% by mass based on the total mass of the protective film forming composition or protective film forming film.

[Filler (D)]

The composition for forming a protective film and the film for forming a protective film may contain a filler (D). The protective film forming film contains the filler (D), so that the coefficient of thermal expansion can be easily adjusted. Therefore, the package reliability can be improved by optimizing the thermal expansion coefficient of the protective film after curing of the protective film forming film to the semiconductor chip.

In addition, by using a composition for forming a protective film containing the filler (D), the moisture absorption rate of the protective film after curing can be reduced or the thermal conductivity of the protective film after curing can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.

Preferred examples of the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, bengale, silicon carbide, boron nitride and the like; Beads sphericalized with silica or the like; Single crystal fibers such as silica; Glass fibers and the like.

Among these, the inorganic filler is preferably a silica filler or an alumina filler.

The filler (D) may be used singly or in combination of two or more kinds.

When the filler (D) is used, the content of the filler (D) relative to the total mass of components other than the solvent of the composition for forming a protective film (i.e., the content of the filler (D) relative to the total mass of the film for forming a protective film) By mass to 80% by mass, and more preferably 7% by mass to 65% by mass. Since the content of the filler (D) is equal to or more than the above lower limit value, the effect of using the filler (D) is more remarkably obtained. Further, when the content of the filler (D) is not more than the upper limit value, the protective film to be formed has higher protection effect and reliability.

[Colorant (E)]

The composition for forming a protective film and the film for forming a protective film may contain a colorant (E).

Examples of the colorant (E) include known pigments such as an inorganic pigment, an organic pigment, and an organic dye.

Examples of the organic pigments and organic dyes include organic pigments such as an aminium type dye, a cyanine type dye, a merocyanine type dye, a chromium type dye, a squarylium type dye, an azulene type dye, a polymethine type dye, Based dye, a perylene-based dye, a dioxazine-based dye, a quinacridone-based dye, a quinacridone-based dye, a quinacridone-based dye, (Metal complex dyes), dithiol metal complex system pigments, indole phenol based pigments, triarylmethane based pigments, anthraquinone based pigments, isoindolinone based pigments, quinophthalone based pigments, pyrrole based pigments, thioindigo based pigments, Based dye, a quinone-based dye, a dioxazine-based dye, a naphthol-based dye, an azomethine-based dye, a benzimidazolone-based dye, a pyranthrone-based dye and a threne-based dye.

Examples of the inorganic pigment include carbon black, a cobalt dye, an iron dye, a chromium dye, a titanium dye, a vanadium dye, a zirconium dye, a molybdenum dye, a ruthenium dye, a platinum dye, Tin oxide) -based dye, ATO (antimony tin oxide) -based dye, and the like.

Of these, phthalocyanine-based pigments, isoindolinone-based pigments, and anthraquinone-based pigments are preferred.

The colorant (E) may be used alone or in combination of two or more.

When the colorant (E) is used, the content of the colorant (E) in the protective film-forming film may be appropriately adjusted depending on the purpose. For example, the protective film may be printed by laser irradiation, and the visible visibility can be controlled by controlling the light transmittance of the protective film by controlling the content of the colorant (E) in the protective film forming film. In this case, the content of the colorant (E) relative to the total mass of the components other than the solvent of the composition for forming the protective film (that is, the content of the colorant (E) relative to the total mass of the protective film forming film) is 0.1 to 10 mass% More preferably from 0.4 to 7.5% by mass, and particularly preferably from 0.8 to 5% by mass. Since the content of the coloring agent (E) is the lower limit value or more, the effect of using the coloring agent (E) is more remarkably obtained. Further, since the content of the coloring agent (E) is not more than the upper limit value, excessive use of the coloring agent (E) is suppressed.

[Coupling agent (F)]

The composition for forming a protective film and the film for forming a protective film may contain a coupling agent (F). The film for forming a protective film contains a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (F), so that adhesion and adhesion to an adherend can be improved. Further, the protective film formed of a film for forming a protective film containing the coupling agent (F) does not inhibit heat resistance, and water resistance is improved.

The coupling agent (F) is preferably a compound having a functional group capable of reacting with a functional group contained in the polymer component (A), the energy ray-curable compound (B) and the like, more preferably a silane coupling agent.

Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-tributylaminopropyl) trimethoxysilane, Ethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolylsilane and the like.

Of these, 3-methacryloxypropyltrimethoxysilane and the like are preferable.

The coupling agent (F) may be used alone or in combination of two or more.

When the coupling agent (F) is used, the content of the coupling agent (F) in the composition for forming a protective film and the film for forming a protective film is preferably such that when the total content of the polymer component (A) and the energy ray- , Preferably 0.03 to 20 mass parts, more preferably 0.05 to 10 mass parts, particularly preferably 0.1 to 5 mass parts. Since the content of the coupling agent (F) is not less than the lower limit value, the effect of using the coupling agent (F) is more remarkably obtained. Further, since the above content of the coupling agent (F) is not more than the upper limit value, generation of outgas is further suppressed.

[Crosslinking agent (G)]

When the above-mentioned acrylic resin having a functional group such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group or isocyanate group capable of bonding with other compound as the polymer component (A) is used, For crosslinking, a crosslinking agent (G) can be used. By using the cross-linking agent (G) for crosslinking, the initial adhesive force and cohesive force of the protective film forming film can be controlled.

Examples of the crosslinking agent (G) include organic polyvalent isocyanate compounds and organic polyvalent organic compounds.

Examples of the organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, and trimer compounds, isocyanurate compounds and adducts thereof (such as ethylene glycol, propylene glycol, neo Such as trimethylolpropane, xylene diisocyanate adduct of trimethylolpropane, etc.), a terminal obtained by reacting an organic polyisocyanate compound with a polyol compound (for example, a reaction product with a low-molecular active hydrogen-containing compound such as trimethylolpropane, Isocyanate urethane prepolymer and the like.

More specific examples of the organic polyisocyanate compound include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; A compound in which either or both of tolylene diisocyanate and hexamethylene diisocyanate are added to all or part of the hydroxyl groups in polyols such as trimethylolpropane; And lysine diisocyanate.

Examples of the organic polyvalent amine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxamide), trimethylolpropane-tri- Tetramethylolmethane-tri-? -Aziridinylpropionate, and N, N'-toluene-2,4-bis (1-aziridine carboxamide) triethylene melamine.

As the crosslinking agent (G), 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate are particularly preferred.

When an isocyanate crosslinking agent is used as the crosslinking agent (G), a hydroxyl group-containing polymer is preferably used as the acrylic resin as the polymer component (A). When the crosslinking agent (G) has an isocyanate group and the acrylic resin has a hydroxyl group, the crosslinking structure can be easily introduced into the protective film forming film by the reaction of the crosslinking agent (G) and the acrylic resin.

When the crosslinking agent (G) is used, the content of the crosslinking agent (G) in the protective film forming composition or in the protective film forming film is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polymer component (A) More preferably from 0.1 to 10 parts by mass, and particularly preferably from 0.5 to 5 parts by mass.

[General purpose additive (H)]

The composition for forming a protective film and the film for forming a protective film may contain the general-purpose additive (H) in addition to the above-described components.

Examples of the general-purpose additive (H) include known plasticizers, antistatic agents, antioxidants, gettering agents, and sensitizers.

[menstruum]

It is preferable that the composition for forming a protective film further contains a solvent since the handling property is improved by dilution.

The solvent contained in the protective film forming composition is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond), and the like.

The protective film forming composition may contain only one kind of solvent or two or more kinds of solvents.

When the composition for forming a protective film contains a solvent, the content of the solvent is preferably such that the solid content of the composition is from 35 to 75 mass% with respect to the total mass of the composition.

The composition for forming a protective film is obtained by blending the respective components described above for constituting the protective film.

The order of addition in the mixing of each component is not particularly limited, and two or more components may be added at the same time.

In the case of using a solvent, the solvent may be used by previously mixing the solvent with any of the ingredients other than the solvent. Alternatively, the solvent may be used beforehand without diluting any of the ingredients other than the solvent. And may be used by mixing.

A method of mixing the respective components at the time of mixing is not particularly limited, and a method of mixing and stirring an agitator or an agitating blade; A method of mixing using a mixer; And a method in which ultrasonic waves are added and mixed.

As described above, the protective film forming film according to the present invention can be formed, for example, by coating a surface of a support with a protective film forming composition and drying the film.

The application of the composition for forming a protective film to the surface of the support may be carried out by a known method and may be carried out by a known method such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, And a method of using various coaters such as a coater, a screen coater, a Meyer bar coater, and a kiss coater.

When the protective film forming composition is dried, the drying temperature is preferably 80 to 130 ° C, and the drying time is preferably 10 seconds to 10 minutes.

The protective film formed by curing the protective film forming film according to the present invention by irradiation of energy rays has a Young's modulus of 500 MPa or more and a breaking elongation of 8% or more.

The Young's modulus of the protective film can be preferably 550 MPa or more, for example, by adjusting the content of the protective film forming film such as the energy ray curable compound (B), and may be 1000 MPa or more, 1400 MPa or more, 1800 MPa or more It is also possible to do.

On the other hand, the upper limit value of the Young's modulus of the protective film is not particularly limited, but is preferably 10000 MPa and more preferably 5000 MPa in terms of dicing property and package reliability.

That is, the Young's modulus of the protective film is preferably 500 MPa or more and 10000 MPa or less, more preferably 550 MPa or more and 5000 MPa or less, more preferably 1000 MPa or more and 5,000 MPa or less, still more preferably 1400 MPa or more and 5,000 MPa or less, and particularly preferably 1800 MPa or more and 5,000 MPa or less.

On the other hand, in the present invention, "Young's modulus" means that the Young's modulus is obtained from the slope of the stress deformation curve at the initial stage of the test when the test piece is subjected to a tensile test at a tensile speed of 200 mm / min. The Young's modulus can be measured simultaneously at the time of measurement of the &quot; elongation at break &quot;

The elongation at break of the protective film can be preferably 10% or more, for example, 15% or more, 20% or more, and 20% or more, for example, by adjusting the content of the protective film- 30% or more, 40% or 50% or more.

On the other hand, the upper limit value of the elongation at break of the protective film is not particularly limited, but it is preferably 100% from the viewpoint of easiness of obtaining a durability at the time of dicing.

That is, the elongation at break of the protective film is 8% to 100%, 10% to 100%, 15% to 100%, 20% to 100%, 30% to 100%, 40% to 100% , 50% or more and 100% or less, and particularly preferably 100%.

In the present invention, the tensile fracture strain in the case where the test piece according to JIS K7161: 1994 and JIS K7127: 1999 does not have a yield point, or the tensile fracture strain in the case where the test piece has a yield point is referred to as &quot; fracture elongation &quot;.

The elongation at break was measured using a specimen having a width of 15 mm and a length of 140 mm and measuring the elongation of the specimen when the specimen was stretched at a tensile speed of 200 mm / Measured values.

Another aspect of the film for forming a protective film according to the present invention is a protective film-forming film in which a protective film having a Young's modulus of 590 MPa or more and 1960 MPa or less and a breaking elongation of 10.7% or more and 56.0% or less is formed by irradiation of energy rays.

"Composite sheet for forming a protective film"

The composite sheet for forming a protective film according to the present invention is provided with a film for forming a protective film according to the present invention on one surface of a support sheet.

The composite sheet for forming a protective film according to the present invention is for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip.

The support sheet includes, for example, one made of only a base material and another layer formed by laminating another layer on a base material.

Hereinafter, the composite sheet for forming a protective film according to the present invention will be described in more detail.

1 is a cross-sectional view schematically showing an embodiment of a protective film-forming composite sheet according to the present invention. In order to facilitate understanding of the features of the present invention, the parts used in the following description may be enlarged for the sake of convenience, and the dimensional ratios and the like of the respective components are not limited to the actual dimensions.

The composite sheet 1A for forming a protective film shown here comprises a pressure-sensitive adhesive layer 12 on a base material 11 and a protective film forming film 13 on the pressure-sensitive adhesive layer 12. [ The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12. The composite sheet 1A for forming a protective film is formed on one surface 10a of the support sheet 10, Film 13 is laminated. In addition, the protective sheet film-forming composite sheet 1A further comprises a peeling film 15 on the protective film-forming film 13. The protective film forming film 13 is the protective film forming film according to the present invention described above.

The pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11 and the surface 12a of the pressure-sensitive adhesive layer 12 (that is, the pressure-sensitive adhesive layer 12) The surface 13a of the protective film forming film 13 (that is, the protective film forming film (that is, the surface of the protective film forming film 13) An adhesive agent layer 16 for a jig is laminated on a part of the surface 13a of the protective film forming film 13 opposite to the surface in contact with the pressure sensitive adhesive layer 12, And the surface 16a of the adhesive layer 16 for jig (that is, the upper surface: the surface opposite to the surface in contact with the protective film forming film 13 in the adhesive layer for jig 16) (Side surface in the adhesive layer 16 for the jig located on the center side of the composite sheet 1A for forming the protective film).

The adhesive layer 16 for a jig may be, for example, a single-layer structure containing an adhesive component or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet as a core.

In the composite sheet 1A for forming a protective film shown in Fig. 1, the back surface of a semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13 with the peeling film 15 removed, The upper surface of the surface 16a of the adhesive layer 16 for jig is affixed to a jig such as a ring frame.

2 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film according to the present invention. In Fig. 2, the same components as those shown in Fig. 1 are given the same reference numerals as those in Fig. 1, and a detailed description thereof will be omitted. This is also true in the diagrams after FIG.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in Fig. 1, except that the adhesive layer 16 for jig is not provided. That is, in the case of the protective sheet-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11 and the surface 12a of the pressure-sensitive adhesive layer 12 The surface 13a of the protective film forming film 13 (that is, the surface for forming a protective film 13) is laminated on the entire surface of the protective film forming film 13 And a release film 15 is laminated on the entire surface of the film 13 opposite to the surface in contact with the pressure-sensitive adhesive layer 12. The protective film forming film 13 is the protective film forming film according to the present invention described above.

The composite sheet 1B for forming a protective film shown in Fig. 2 is a semiconductor wafer (not shown) formed on a part of the surface 13a of the protective film forming film 13 at a central portion in a state that the peeling film 15 is removed. And the area near the outer edge portion of the protective film forming film 13 is used by being attached to a jig such as a ring frame.

3 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to 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. 1 except that the pressure-sensitive adhesive layer 12 is not provided. That is, in the case of the protective sheet-forming composite sheet 1C, the supporting sheet is composed of the substrate 11 alone. The protective film forming film 13 is laminated on one surface 11a of the substrate 11 and the surface 13a of the protective film forming film 13 (the substrate 13 in the protective film forming film 13 The adhesive layer 16 for the jig is laminated on a part of the surface 13a of the protective film forming film 13 and the adhesive layer 16 for the jig is laminated on the surface 13a of the protective film forming film 13 The surface of the adhesive layer 16 for the jig and the surface 16a of the adhesive layer 16 for the jig (that is, the upper surface: the surface opposite to the surface in contact with the protective film forming film 13 in the adhesive layer 16 for jig, And a release film 15 is laminated on the side of the adhesive layer 16 for jig located on the center side of the composite sheet 1C for forming a protective film. The protective film forming film 13 is the protective film forming film according to the present invention described above.

The composite sheet 1C for forming a protective film shown in Fig. 3 has a structure in which the surface 13a (13a) of the protective film forming film 13 is formed in a state in which the peeling film 15 is removed in the same manner as the composite sheet 1A for forming a protective film, And the upper surface of the surface 16a of the adhesive layer 16 for jig is attached to a jig such as a ring frame.

4 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to 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. 3 except that the adhesive layer 16 for jig is not provided. That is, in the composite sheet 1D for forming a protective film, the protective film forming film 13 is laminated on one surface 11a of the substrate 11, and the surface 13a of the protective film forming film 13 (The surface opposite to the surface in contact with the base material 11 in the forming film 13). The protective film forming film 13 is the protective film forming film according to the present invention described above.

The composite sheet 1D for forming a protective film shown in Fig. 4 has a structure in which the surface 13a (13a) of the protective film forming film 13 is removed in a state in which the peeling film 15 is removed in the same manner as the protective film- (Not shown) is attached to a part of the center side of the protective film forming film 13, and a region near the outer edge portion of the protective film forming film 13 is attached to a jig such as a ring frame.

5 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet according to the present invention.

The composite sheet 1E for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in Fig. 1 except that the shape of the protective film-forming film is different. That is, the composite sheet 1E for forming a protective film has a pressure-sensitive adhesive layer 12 provided on a substrate 11 and a protective film forming film 23 provided on the pressure-sensitive adhesive layer 12. [ The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12 and the composite sheet 1E for protecting film is formed on one surface 10a of the support sheet 10 (The surface on the side of the protective film forming layer 12). Further, the protective sheet film-forming composite sheet 1E further comprises a peeling film 15 on the protective film-forming film 23. The protective film forming film 23 is the protective film forming film according to the present invention described above, and is the same as the protective film forming film 13 except that the shape is different.

In the composite sheet 1E for protecting film formation, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11 and the surface 12a of the pressure-sensitive adhesive layer 12 And a protective film forming film 23 is laminated on a part of the surface (the surface opposite to the contacting surface). A surface 23a of the surface 22a of the pressure-sensitive adhesive layer 12 on which the protective film forming film 23 is not laminated and the surface 23a of the protective film forming film 23 The surface of the film 23 that is not in contact with the pressure-sensitive adhesive layer 12).

The protective film forming film 23 has a surface area smaller than that of the pressure sensitive adhesive layer 12 and has, for example, a circular shape, when viewed from the top and looking down on the protective sheet film forming composite sheet 1E.

5, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film forming film 23 in the state that the peeling film 15 is removed, A surface of the surface 12a of the pressure-sensitive adhesive layer 12 on which the protective film forming film 23 is not laminated is used by being attached to a jig such as a ring frame.

The composite sheet for forming a protective film according to the present invention is not limited to those shown in Figs. 1 to 5, and may be modified or deleted in some of the configurations shown in Figs. 1 to 5 within the range not hindering the effects of the present invention, Another configuration may be added to what has been described so far.

For example, in the composite sheet for forming a protective film shown in Figs. 3 and 4, an intermediate layer may be formed between the substrate 11 and the protective film forming film 13 or the protective film forming film 23.

As the intermediate layer, any one can be selected depending on the purpose.

In the composite sheet for forming a protective film shown in Figs. 1, 2 and 5, an intermediate layer may be formed between the substrate 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film according to the present invention, the support sheet may be a laminate of a substrate, an intermediate layer and a pressure-sensitive adhesive layer in this order. Here, the intermediate layer is the same as the intermediate layer in the protective sheet-forming composite sheet shown in Figs. 3 and 4.

In the composite sheet for forming a protective film shown in Figs. 1 to 5, the layers other than the intermediate layer may be formed at arbitrary points.

Next, the protective film forming film other than the protective film forming film constituting the protective film forming composite sheet will be described in more detail.

<Description>

The material of the substrate is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), high density polyethylene (abbreviated as HDPE Polypropylene, an ethylene / propylene copolymer, a polybutene, a polybutadiene, a polymethylpentene, a polyvinyl chloride film, a vinyl chloride copolymer, a polyethylene terephthalate, a polyethylene naphthalate, a polybutylene terephthalate, (Meth) acrylic acid copolymers, ethylene / (meth) acrylic acid ester copolymers, polystyrene, polycarbonate, fluorine resins, and the like. A modified product, a crosslinked product, or a copolymer.

The thickness of the base material can be appropriately selected according to the purpose, but is preferably 50 to 300 占 퐉, more preferably 60 to 100 占 퐉. When the thickness of the substrate is within this range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or semiconductor chip are further improved.

The base material may be composed of one layer (single layer), or may be composed of a plurality of layers (for example, two to four layers) of two or more layers. When the base material is composed of a plurality of layers, these layers may be the same or different from each other. That is, all layers may be the same, all layers may be different, or only some layers may be the same. When the plural layers are different from each other, the combination of the plural layers is not particularly limited. Here, the fact that the plural layers are different from each other means that at least one of the material and the thickness of each layer is different from each other.

On the other hand, when the base material is composed of a plurality of layers, the total thickness of the respective layers may be set to the thickness of the preferable base material.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer formed thereon, the substrate may be subjected to a surface treatment such as a sand blast treatment, a solvent treatment, a corona discharge treatment, an electron beam irradiation treatment, a plasma treatment, , A flame treatment, a chromic acid treatment, an oxidation treatment such as a hot air treatment, or the like. Further, the surface of the substrate may be subjected to a primer treatment.

<Pressure-sensitive adhesive layer>

The above-mentioned pressure-sensitive adhesive layer may be appropriately constructed and known.

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing various components for constituting the pressure-sensitive adhesive layer. The ratio of the content of components which are not vaporized at room temperature in the pressure-sensitive adhesive composition is generally the same as the content of the components in the pressure-sensitive adhesive layer.

In the case where the pressure-sensitive adhesive layer contains a component which is polymerized by irradiation of energy rays, the semiconductor chip can be easily picked up by irradiating the energy ray to decrease the adhesiveness. Such a pressure-sensitive adhesive layer can be formed by using various pressure-sensitive adhesive compositions containing a component which is polymerized by irradiation of energy rays such as, for example, an energy ray-polymerizable acrylic polymer.

Preferable examples of the pressure-sensitive adhesive composition include those containing an acrylic polymer and an energy ray-polymerizable compound (pressure-sensitive adhesive composition (i)) as long as they contain a component that is polymerized by irradiation of energy rays (energy ray- ), An acrylic polymer having a hydroxyl group and having a polymerizable group in its side chain (for example, having a hydroxyl group and having a polymerizable group on its side chain via a urethane bond) and an isocyanate crosslinking agent (Sometimes referred to as pressure-sensitive adhesive composition (ii)), and further preferably contains a solvent.

The pressure-sensitive adhesive composition may further contain any of various additives such as a photopolymerization initiator, a dye, a pigment, an anti-deterioration agent, an antistatic agent, a flame retardant, a silicone compound and a chain transfer agent in addition to the above-

Preferable examples of the pressure-sensitive adhesive composition include those containing an acrylic resin and a crosslinking agent (a pressure-sensitive adhesive composition (iii)), a pressure-sensitive adhesive composition ), And the like, and may contain an optional component such as a solvent and other components not corresponding to a solvent.

The thickness of the pressure-sensitive adhesive layer can be appropriately selected according to the purpose, but is preferably 1 to 100 占 퐉, more preferably 1 to 60 占 퐉, and particularly preferably 1 to 30 占 퐉.

The pressure-sensitive adhesive composition is obtained, for example, by blending each component for constituting a pressure-sensitive adhesive layer such as an acrylic polymer, and is obtained, for example, in the same manner as in the case of the composition for forming a protective film, .

The pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to a desired spot and drying it.

At this time, if necessary, the applied pressure-sensitive adhesive composition may be crosslinked by heating. The heating conditions can be, for example, 100 占 폚 to 130 占 폚 for 1 minute to 5 minutes, but the present invention is not limited thereto.

Here, in the case of irradiating the energy ray through the support sheet at the target point, it is preferable that each layer such as the substrate, the pressure-sensitive adhesive layer, etc. constituting the support sheet has a high transmittance of energy rays.

Hereinafter, a method for producing a composite sheet for forming a protective film will be described in detail.

&Lt; Method for producing a composite sheet for forming a protective film &

The composite sheet for forming a protective film according to the present invention can be produced by forming a film for forming a protective film according to the present invention on one surface of a support sheet.

For example, a composite sheet for forming a protective film having a support sheet made of only a substrate can be produced by coating a surface of a substrate with a composition for forming a protective film and drying the film to form a protective film forming film, (Film) on a film for forming a protective film. The formation conditions of the protective film forming film in this case are the same as those described above.

Such a production method is preferable, for example, as a production method of a composite sheet for forming a protective film shown in Figs.

For example, a protective sheet-forming composite sheet comprising a support sheet comprising a substrate and a pressure-sensitive adhesive layer laminated on the substrate is obtained by coating the surface of a substrate with a pressure-sensitive adhesive composition and drying the pressure-sensitive adhesive layer to form a pressure- For example, by forming a film for forming a protective film on the pressure-sensitive adhesive layer using a pressure-sensitive adhesive, and optionally forming another layer (film) such as an adhesive layer for jig or a release film on the protective film forming film.

In this case, for example, a film for forming a protective film can be formed by coating a composition for forming a protective film on the pressure-sensitive adhesive layer. However, in general, the laminated structure of the substrate, the pressure-sensitive adhesive layer and the film for forming a protective film can be obtained by, for example, applying a film for forming a protective film formed by coating a composition for forming a protective film on the surface of the release layer of the release film and drying, , And the protective film forming film is formed separately such as by removing the above-mentioned release film, if necessary, and the resultant is adhered to the surface of the pressure-sensitive adhesive layer.

The laminated structure of the base material, the pressure-sensitive adhesive layer and the film for forming a protective film may be formed by forming a pressure-sensitive adhesive layer on a release film by using, for example, a pressure-sensitive adhesive composition, Sensitive adhesive layer on the release film and the protective film forming film on the release film are superimposed on each other, the release film laminated on the pressure-sensitive adhesive layer is removed, and the surface of the exposed pressure-sensitive adhesive layer The surface on which the film is not formed).

In any of the above methods, after forming a laminated structure of a substrate, a pressure-sensitive adhesive layer and a film for forming a protective film, another layer (film) such as an adhesive layer for a jig or a peeling film is formed , A protective sheet-forming composite sheet comprising a support sheet in which a pressure-sensitive adhesive layer is laminated on a substrate can be produced. In any case, the forming conditions of the pressure-sensitive adhesive layer and the protective film-forming film are the same as those described above.

Such a production method is preferable, for example, as a production method of a composite sheet for forming a protective film shown in Figs. 1, 2 and 5.

For example, in the case of producing a composite sheet for forming a protective film having a surface area smaller than that of the pressure-sensitive adhesive layer in the protective film forming film when viewed from the top and looking down on the composite sheet for protecting film formation as shown in Fig. 5, In the method, a protective film-forming film cut out in advance into a predetermined size and shape may be formed on the pressure-sensitive adhesive layer.

<Method of using a protective film-forming film or a protective film-forming composite sheet>

As a method for using the protective film-forming film or the protective film-forming composite sheet according to the present invention, for example, use methods 1 to 4 described below can be mentioned.

[How to use 1]

In the use method 1, the protective film forming film of the composite sheet for forming a protective film is first attached to the back surface of the semiconductor wafer, and the protective sheet forming complex sheet is fixed to the dicing apparatus.

Subsequently, the film for forming a protective film is cured by irradiation of energy rays to form a protective film. When a conventional film for forming a protective film is used, it takes a long time of several hours, for example, to cure the film by heating. Compared with a film for forming a protective film according to the present invention, For example, even a short time of less than one minute such as several seconds can be hardened, and a semiconductor chip with a protective film can be obtained in a remarkably shorter time than in the prior art.

When the back grind tape is attached to the surface (electrode forming surface) of the semiconductor wafer, the back grind tape is usually removed from the semiconductor wafer, and then the protective film forming film is cured.

Subsequently, the semiconductor wafer is diced into a semiconductor chip.

Then, the semiconductor chip is peeled off from the support sheet together with the protective film adhered to the back surface thereof to pick up the semiconductor chip, thereby obtaining a semiconductor chip with a protective film. In the case where the support sheet is formed by laminating a pressure-sensitive adhesive layer on a substrate, the pressure-sensitive adhesive layer is one having a non-energy ray curable property which does not contain a component that is polymerized by irradiation of energy rays.

In the use method 1, the protective film forming film or the protective film is irradiated with a laser beam through the supporting sheet at any timing from when the protective film forming film is attached to the semiconductor wafer to dicing, Quot ;. &lt; / RTI &gt; In the case of printing on a film for forming a protective film, a protective film printed by curing the film is obtained.

In this case, when printing is performed, gas is generated, and this gas is the cause, and peeling may finally appear between the support sheet and the protective film. However, when the protective film forming film is printed, The frequency and degree of peeling can be reduced.

This is presumably because the adhesion between the protective film-forming film and the support sheet is higher than the adhesion between the protective film and the support sheet.

[How to use 2]

In use method 2, the film for forming a protective film is attached to the back surface of a semiconductor wafer.

Subsequently, the film for forming a protective film is cured by irradiation of energy rays to form a protective film. As a result, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a significantly shorter time than in the prior art. When the back grind tape is pasted on the surface (electrode forming surface) of the semiconductor wafer, the back grind tape is usually removed from the semiconductor wafer, and then the protective film forming film is cured.

Then, the support sheet is attached to the exposed surface of the protective film. In the case where the support sheet is formed by laminating a pressure-sensitive adhesive layer on a substrate, the pressure-sensitive adhesive layer can be any of those having energy ray curable properties containing a component polymerized by irradiation of energy rays and those having a specific energy ray curable property as described above .

Subsequently, the semiconductor wafer is diced into a semiconductor chip.

Then, the semiconductor chip is peeled off from the support sheet together with the protective film adhered to the back surface thereof to pick up the semiconductor chip, thereby obtaining a semiconductor chip with a protective film. In the case where the support sheet is formed by laminating a pressure-sensitive adhesive layer on a substrate, the semiconductor chip with a protective film can be more easily picked up by curing the pressure-sensitive adhesive layer.

In the use method 2, laser light is irradiated to the protective film directly on the protective film-forming film or to the protective film through the support sheet at any timing from when the protective film forming film is attached to the semiconductor wafer to dicing, The film or the protective film may be printed. In the case of printing on a film for forming a protective film, a protective film printed by curing the film is obtained.

[How to use 3]

In the use method 3, the protective film forming film is attached to the back surface of the semiconductor wafer.

Then, the support sheet is attached to the exposed surface of the protective film forming film. In the case where the support sheet is formed by laminating a pressure-sensitive adhesive layer on a substrate, the pressure-sensitive adhesive layer is one having a non-energy radiation curable property.

Subsequently, the film for forming a protective film is cured by irradiation of energy rays to form a protective film. As a result, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a significantly shorter time than in the prior art. When the back grind tape is pasted on the surface (electrode forming surface) of the semiconductor wafer, the back grind tape is usually removed from the semiconductor wafer, and then the protective film forming film is cured.

Subsequently, the semiconductor wafer is diced into a semiconductor chip.

Then, the semiconductor chip is peeled off from the support sheet together with the protective film adhered to the back surface thereof to pick up the semiconductor chip, thereby obtaining a semiconductor chip with a protective film.

In the use method 3, laser light is irradiated to the protective film forming film directly or through the support sheet at any timing from when the protective film forming film is attached to the semiconductor wafer to dicing, Alternatively, laser light may be irradiated to the protective film through the support sheet to perform printing on the protective film. In the case of printing on a film for forming a protective film, a protective film printed by curing the film is obtained.

Further, in the case of printing on the protective film forming film after the application of the supporting sheet, the frequency and degree of peeling between the supporting sheet and the protective film are reduced as in the case of the above-mentioned use method 1, .

[How to use 4]

In the use method 4, the protective film forming film is attached to the back surface of the semiconductor wafer.

Then, the support sheet is attached to the exposed surface of the protective film forming film. In the case where the support sheet is formed by laminating a pressure-sensitive adhesive layer on a substrate, the pressure-sensitive adhesive layer is one having a non-energy radiation curable property.

Subsequently, the semiconductor wafer is diced into a semiconductor chip.

Subsequently, the film for forming a protective film is cured by irradiation of energy rays to form a protective film. As a result, as in the case of the above-mentioned use method 1, a semiconductor chip with a protective film can be obtained in a significantly shorter time than in the prior art.

Then, the semiconductor chip is peeled off from the support sheet together with the protective film adhered to the back surface thereof to pick up the semiconductor chip, thereby obtaining a semiconductor chip with a protective film.

In the use method 4, laser light is irradiated to the protective film forming film directly or through the support sheet at any timing from when the protective film forming film is attached to the semiconductor wafer to dicing, . By curing the printed film for forming a protective film, a protective film to be printed is obtained.

In the use method 4, in the case of printing on the protective film forming film after the application of the supporting sheet, as in the case of the above-mentioned use method 1, The frequency and degree of peeling can be reduced.

By using the film for forming a protective film or the composite sheet for forming a protective film according to the present invention, the protective film has a sufficiently high protective function until a semiconductor chip with a protective film is obtained. For this reason, occurrence of cracks and defects such as suppression of chipping in the semiconductor chip is suppressed. In addition, the protective film can maintain such a high protective effect even when exposed to a large temperature change, and has high reliability.

One aspect of the protective film forming film, which is one embodiment of the present invention,

1. A protective film forming film for forming a protective film on a back surface of a semiconductor wafer or a semiconductor chip;

The protective film-

An energy ray curable compound (B)

At least one member selected from the group consisting of a polymer component (A), a photopolymerization initiator (C), a filler (D), a colorant (E), a coupling agent (F), a crosslinking agent (G) &Lt; / RTI &gt;

The component (B) is a (meth) acrylate compound, and further contains an energy ray curable compound (B1) having 2 to 4 energy linear polymerizable groups in one molecule,

The component (A) is an acrylic resin having a weight average molecular weight (Mw) of 10000 to 2000000 and a glass transition temperature of -60 to 70 ° C,

The component (C) is selected from the group consisting of ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- At least one;

The content of the component (B) is 3% by mass or more and 30% by mass or less based on the total mass of the protective film-forming film;

The content of the component (B1) in the component (B) is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less relative to the total mass of the component (B) Is not less than 98 mass% and not more than 100 mass%, particularly preferably not more than 100 mass%;

When the component (A) is contained, the content of the component (A) is 5 to 50% by mass, preferably 10 to 45% by mass, based on the total mass of the protective film-

When the component (C) is included, the content of the component (C) is 0.1 to 3 mass% with respect to the total mass of the protective film-forming film;

The total content of each component constituting the protective film forming film is not more than 100% by mass;

In addition, a film for forming a protective film having the following characteristics can be mentioned.

And the Young's modulus of the cured product is 500 MPa or more and 1000 MPa or less, preferably 550 MPa or more and 5,000 MPa or less, and the elongation at break is 8% or more and 100% or less, when the film for forming a protective film is cured to form a cured product (protective film) Or less, preferably 10% or more and 100% or less.

The Young's modulus of the cured product may be 590 MPa or more and 1960 MPa or less, and the elongation at break may be 10.7% or more and 56% or less.

Another aspect of the film for forming a protective film, which is one embodiment of the present invention,

1. A protective film forming film for forming a protective film on a back surface of a semiconductor wafer or a semiconductor chip;

The protective film-

At least one energy ray curable compound (B) selected from the group consisting of tricyclodecane dimethylol diacrylate and? -Caprolactone modified tris (acryloxyethyl) isocyanurate;

(A) polymerized with at least one monomer selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate;

Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) (C);

At least one component selected from the group consisting of a filler (D), a colorant (E), a coupling agent (F), a crosslinking agent (G) and a general purpose additive (H);

With respect to the total mass of the protective film forming film,

The content of the component (B) is 10% by mass or more and 20% by mass or less,

The content of the component (A) is 20 to 32 mass%

The content of the component (C) is 0.6 mass% or more;

When the protective film forming film is cured by irradiating with an energy ray to obtain a cured product (protective film)

The Young's modulus of the cured product is 590 MPa or more and 1960 MPa or less,

The breaking elongation is 10.7% or more and 56.0% or less

And a film for forming a protective film.

Example

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

The raw materials used in the preparation of the protective film forming composition are shown below.

The polymer component (A)

(A) -1: an acrylic resin (weight average molecular weight: 800,000) obtained by copolymerizing 10 parts by mass of butyl acrylate, 70 parts by mass of methyl acrylate, 15 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of glycidyl methacrylate, Glass transition temperature-1 [deg.] C).

Energy ray-curable compound (B)

(B1) -1: tricyclodecane dimethylol diacrylate (KAYARAD R-684, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Yaku Chemical Co., Ltd.)

(A-9300-1CL, Shin-Nakamura Chemical Co., Ltd., trifunctional ultraviolet ray curable compound, molecular weight 537) modified with? -Caprolactone modified tris (2-acryloxyethyl) isocyanurate

(B2) -1: A mixture of dipentaerythritol hexaacrylate (hexafunctional ultraviolet ray curable compound, molecular weight 578) and dipentaerythritol pentaacrylate (pentafunctional ultraviolet ray curable compound, molecular weight 525) (KAYARAD DPHA, )

Photopolymerization initiator (C)

(C) -1: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- GACURE (registered trademark) OXE02 &quot;

· Filler (D)

(D) -1: silica filler (fused quartz filler, average particle diameter 8 占 퐉)

· Colorant (E)

(E) -1: 32 parts by mass of a phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of an isoindolinone yellow pigment (Pigment Yellow 139) and 50 parts by mass of an anthraquinone red pigment (Pigment Red 177) , And the pigment is obtained so that the total amount of the three kinds of pigments and the styrene acrylic resin amount is 1/3 (mass ratio).

· Coupling agent (F)

(F) -1: 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd., silane coupling agent)

[Example 1]

&Lt; Preparation of protective film-forming film &

(Preparation of protective film forming composition)

(B) -1 (10 parts by mass), a photopolymerization initiator (C) -1 (0.3 parts by mass), a photopolymerization initiator (C) -2 (D) -1 (56 parts by mass), the colorant (E) -1 (2 parts by mass) and the coupling agent (F) -1 (0.4 part by mass) were mixed to obtain a composition for forming a protective film. Table 1 shows the kinds of the blending components and blending amounts thereof. Here, the compounding amounts shown in Table 1 are all solid contents. In Table 1, the polymer component (A) is simply referred to as &quot; (A) &quot;, and each component is represented only by its sign.

(Production of protective film forming film)

A knife coater was used for the exfoliated surface of a release film ("SP-PET381031" manufactured by Linftec Co., Ltd., thickness 38 μm) having one surface of the polyethylene terephthalate film peeled off by silicone treatment, The composition was coated and dried at 120 占 폚 to obtain a protective film forming film (thickness: 25 占 퐉). The above-mentioned peeling film was further adhered to the exposed surface of the resulting protective film-forming film so that the peeling-treated surface thereof was in contact with the protective film-forming film to obtain a laminate having the peeling film formed on both surfaces of the protective film-forming film. The obtained laminate was rolled up and stored.

&Lt; Evaluation of protective film forming film &gt;

(Evaluation of Young's modulus and elongation at break of protective film)

The laminate thus obtained was loosened and irradiated with ultraviolet rays under conditions of an illumination of 230 mW / cm 2 and a light quantity of 170 mJ / cm 2 to cure the protective film forming film to form a protective film.

Subsequently, the protective film with the peeling film was cut to a size of 15 mm in width and 140 mm in length, and the peeling film was removed from both surfaces to obtain a test piece. (Label) for testing was stuck from both ends of the test piece to a portion of 20 mm in the longitudinal direction according to JIS K7161: 1994 and JIS K7127: 1999, Quot; IS 500N &quot;), this portion was fixed with a gripping tool so that the distance between the earths was 100 mm, and a tensile test was conducted at a tensile speed of 200 mm / min.

Then, the stress strain curve at this time was prepared, the Young's modulus was calculated from the slope of the stress strain curve at the beginning of the test, and the elongation at break was calculated from the elongation of the test piece at the time of breaking. The results are shown in Table 1.

(Evaluation of reliability of protective film)

The laminate thus obtained was loosened and one of the peeling films was removed from one side of the protective film forming film. The peeling film was peeled off from the surface of the protective film by using a tape mounter (Lintel Co., Ltd.) on the polished surface of a silicon wafer (200 mm diameter, Manufactured by Adwill RAD-3600F / 12), the exposed surface of the protective film-forming film provided with the above-mentioned release film was attached to one side while heating to 70 ° C. Subsequently, ultraviolet rays were irradiated under conditions of an illumination of 230 mW / cm 2 and a light quantity of 170 mJ / cm 2 to cure the protective film forming film to form a protective film on the polished surface of the silicon wafer.

Subsequently, a dicing sheet ("Adwill G-562" manufactured by Lin Tec Co., Ltd.) was pasted from the protective film and another dicing sheet was removed and a dicing machine ("DFD651" The silicon wafer having the protective film formed thereon was diced into a size of 3 mm x 3 mm to obtain a semiconductor chip with a protective film.

Next, a semiconductor chip with a protective film obtained as described above was placed on the pre-conditioning shown below, which mimics the process when the semiconductor chip is mounted. That is, after the semiconductor chip with the protective film was baked at 125 占 폚 for 20 hours, moisture was absorbed for 168 hours under the condition of 85 占 폚 and relative humidity 85%, and then the semiconductor chip with the protective film immediately after being taken out from this moisture- Lt; RTI ID = 0.0 &gt; 260 C &lt; / RTI &gt; Then, 25 semiconductor chips with the protective film thus obtained were placed in a cold / heat shock apparatus ("TSE-11-A" manufactured by ESPEC), held at -65 ° C for 10 minutes, held at 150 ° C for 10 minutes The cooling / heating cycle was repeated 1000 times.

Subsequently, all the semiconductor chips with a protective film were taken out from the heat and shock apparatus, and the presence or absence of lifting and peeling at the junction between the semiconductor chip and the protective film and the presence or absence of cracks in the semiconductor chip were measured using a scanning ultrasonic imaging apparatus Quot; D9600 ^TM CSAM &quot;) was used and the cross-section of the semiconductor chip with a protective film was observed. The number of semiconductor chips with a protective film on which at least one of the above-mentioned lifting, peeling, and cracking has occurred is counted. When the number of semiconductor chips is two or less, the reliability is determined as A (B). &Lt; / RTI &gt; The results are shown in Table 1.

&Lt; Preparation and evaluation of protective film-forming film &gt;

[Examples 2 to 4, Comparative Examples 1 to 6]

A film for forming a protective film was prepared and evaluated in the same manner as in Example 1, except that the kind of the blending component and the blending amount thereof in the production of the protective film forming composition were changed as shown in Table 1.

The results are shown in Table 1.

As is apparent from the above results, the protective films formed from the protective film forming films of Examples 1 to 4 had a high Young's modulus and elongation at break, a sufficient protective effect, and high reliability.

In contrast, the protective films formed from the protective film forming films of Comparative Examples 1 to 2, 4, and 6 had low breaking elongation, insufficient protective effect, and low reliability. It is presumed that the energy ray-curable compound (B2) -1 is used in Comparative Examples 1 and 2, and the amount of the energy ray-curable compound (B1) -1 used in Comparative Example 4 is excessively large. In Comparative Example 6, both of these causes are applied.

In addition, the protective films formed from the protective film forming films of Comparative Examples 3 and 5 had a low Young's modulus and chipping occurred during dicing, so that a semiconductor chip with a protective film could not be obtained and the reliability of the protective film could not be evaluated. This is presumably because the amount of the energy ray curable compound (B1) -1 used in Comparative Example 3 was too small in Comparative Example 5, and the amount of the energy ray curable compound (B2) -1 used was too small.

INDUSTRIAL APPLICABILITY The present invention is industrially very useful because it can be used for manufacturing a semiconductor chip or the like whose back surface is protected by a protective film.

A composite sheet for forming a protective film, 10: supporting sheet, 10a: surface of a supporting sheet, 11: base material, 11a: surface of a base material, 12: The surface of the pressure-sensitive adhesive layer, 13, 23: The protective film-forming film, 13a, 23a: The surface of the protective film-forming film, 15: Adhesive agent layer 16a ... surface of the adhesive layer for jig

Claims (3)

A film for forming a protective film for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip containing an energy ray curable compound (B) and having the following characteristics:
When the protective film forming film is cured by irradiating with an energy ray to obtain a cured product, the Young's modulus of the cured product is 500 MPa or more and the elongation at break is 8% or more. The method according to claim 1,
In the film for forming a protective film, the content of the energy ray curable compound (B1) having 2 to 4 energy linear polymerizable groups in one molecule is preferably not less than 90% by mass with respect to the total mass of the energy ray curable compound (B) Forming film. A composite sheet for forming a protective film, comprising the protective film forming film according to claim 1 or 2 on one surface of a support sheet.

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