TW201741348A - Protective film forming film and composite sheet for forming protective film - Google Patents

Abstract

A protective film forming film of the present application is an energy beam-curable film. When the protective film forming film is irradiated with an energy beam and thereby a protective film is formed, the tension elastic modulus of the protective film is 1*10<SP>8</SP>Pa or greater. A composite sheet for forming a protective film of the present application includes a supporting sheet and the protective film forming film on the supporting sheet. When the protective film forming film is irradiated with the energy beam and thereby the protective film is formed, the adhesive force between the protective film and the supporting sheet is 50 to 1500mN/25mm.

Description

Protective film forming film and protective film forming composite sheet

The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film.

The priority of the Japanese Patent Application No. 2016-092015, filed on Jan. 28,,,,,,,,,,,,,,

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

A resin film containing an organic material is sometimes formed as a protective film on the back surface of the bare semiconductor wafer, and incorporated into the semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent cracking of the semiconductor wafer after the cutting step or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film is used, and the composite sheet for forming a protective film is provided with a film for forming a protective film for forming a protective film. In the composite sheet for forming a protective film, the film for forming a protective film can be formed into a protective film by curing, and the support sheet can be used as a dicing sheet, whereby the protective film can be formed into a protective film integrally formed with the dicing sheet. A composite sheet for forming.

In the composite sheet for forming a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film having thermosetting properties is mainly used, and the film for forming a thermosetting protective film is formed by curing by heating. Protective film. In this case, for example, on the back surface of the semiconductor wafer (the surface opposite to the surface on which the electrode is formed), the film for forming a protective film by thermosetting is attached, and then the composite sheet for forming a protective film is attached, and then heated. The film for forming a protective film is cured to form a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor wafer. Then, the semiconductor wafer is pulled away from the support sheet while being attached to the protective film, and picked up. Further, there is a case where the curing and cutting of the film for forming a protective film are performed in the reverse order.

However, since the heat curing of the film for forming a thermosetting protective film usually takes about several hours, it is desirable to shorten the curing time. In view of the above, the industry is investigating a film for forming a protective film which can be cured by irradiation with an energy ray such as ultraviolet rays for forming a protective film. For example, an energy ray-curable protective film formed on a release film is disclosed (refer to Patent Document 1); An energy ray-curable wafer protective film which forms a protective film having high hardness and excellent adhesion to a semiconductor wafer (see Patent Document 2).

On the other hand, in the semiconductor wafer, the back surface to be attached to the film for forming a protective film is usually ground and adjusted so that the thickness becomes a target value. As a result, the semiconductor wafer has the trace of the grinding (grinding trace) on the back surface. On the other hand, in the case of the protective film, it is also required to improve the appearance of the semiconductor wafer so that the grinding marks on the back surface of the semiconductor wafer are not recognized.

Further, in the protective film, generally, a surface on the opposite side to the surface to which the semiconductor wafer or the semiconductor wafer is bonded (in other words, a surface facing the support sheet) is irradiated with laser light. Printing (in this manual, sometimes referred to as "laser printing"). Further, the protective film is also required to have excellent print visibility. When the film for forming a protective film is in an energy ray-curable property, laser printing may be performed at the stage of the film for forming a protective film, not at the stage of the protective film.

As described above, the protective film and the film for forming a protective film generally contain a coloring agent to improve the appearance of the semiconductor wafer and to improve the visibility of the printing applied to itself.

However, when a protective film is formed by irradiating an energy ray to a film for forming a protective film containing a coloring agent, the effect is closer to the area of the surface on which the protective film forming film is attached to the semiconductor wafer or the semiconductor wafer due to the influence of the coloring agent. The more difficult it is to reach the energy line. As a result, typically, in the formed protective film, On the side of the illumination source, that is, in the region close to the surface opposite to the support sheet, the degree of hardening becomes higher, on the opposite side of the illumination source side of the energy line, that is, close to the attachment of the semiconductor wafer or the semiconductor wafer. In the area of the face, the degree of hardening becomes lower. When the difference in the degree of hardening occurs in the thickness direction of the protective film, the semiconductor wafer with the protective film is removed from the support sheet by the pin by the pin, and the film is picked up in the protective film. The supporting piece remains opposite to the surface to be pinned out by the pin. If such an erection trace remains, the visibility of the laser print applied to the same surface may be lowered.

On the other hand, the energy ray-curable protective film disclosed in Patent Document 1 and the energy ray-curable wafer protective film disclosed in Patent Document 2 are not intended to suppress such a pin-out caused by a pin.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 5144433.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-031183.

An object of the present invention is to provide an energy ray-curable protective film forming film and a protective film forming composite sheet comprising the same, wherein the energy ray-curable protective film forming film can be on the back side of a semiconductor wafer or a semiconductor wafer. Forming a protective film, even if it contains a coloring agent, When the semiconductor wafer with the protective film is picked up by the ejector method, it is also possible to suppress the surface of the protective film from remaining on the surface of the protective film.

The present invention provides a film for forming a protective film which is energy ray-curable, and when the film for forming a protective film is irradiated with an energy ray to form a protective film, the tensile modulus of the protective film is 1 × 10 ⁸ Pa or more.

In the film for forming a protective film of the present invention, the protective film may have a Shore D hardness of 55 or more.

Moreover, the present invention provides a composite sheet for forming a protective film, comprising: a support sheet, wherein the protective film forming film is provided on the support sheet, and the protective film forming film is irradiated with an energy ray to form a protective film, and the protective film and the The adhesion between the support sheets is 50mN/25mm to 1500mN/25mm.

By using the film for forming a protective film and the film for forming a protective film of the present invention, a protective film can be formed on the back surface of the semiconductor wafer or the semiconductor wafer, and the film with the protective film can be picked up even if the film for forming a protective film contains a coloring agent. In the case of a wafer, it is also possible to suppress the surface of the protective film from remaining on the surface of the protective film.

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

10‧‧‧Support tablets

10a‧‧‧Surface of the support sheet

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer

13, 23‧‧‧film for protective film formation

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

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

15‧‧‧Release film

151‧‧‧1st release film

152‧‧‧Second release film

16‧‧‧Layer layer for fixtures

16a‧‧‧ Surface of the adhesive layer for the fixture

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

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

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

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

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

Fig. 6 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

◇Protective film forming film

The film for forming a protective film of the present invention is energy ray-curable, and when the film for forming a protective film is irradiated with an energy ray to form a protective film, the tensile modulus of the protective film is 1 × 10 ⁸ Pa or more.

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

The film for forming a protective film is cured by irradiation with an energy ray to form a protective film. The protective film protects the back surface of the semiconductor wafer or the semiconductor wafer (the surface opposite to the electrode forming surface). The film for forming a protective film is soft and can be easily attached to an attached object.

The film for forming a protective film is energy ray curable, and the protective film can be formed by curing in a short time compared to the film for forming a protective film having thermosetting properties.

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

The film for forming a protective film is, for example, a film containing an energy ray-curable component (a) to be described later, and preferably a film containing a coloring agent (g).

The energy ray-curable component (a) is preferably uncured, preferably adhesive, more preferably uncured and adhesive.

In the present invention, the "energy line" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples of the energy line include ultraviolet rays, radiation, electron beams, and the like.

The ultraviolet light can be irradiated as an ultraviolet source by using, for example, a high pressure mercury lamp, a Fusion H-type lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode) lamp. The electron beam can illuminate an electron beam generated by an electron beam accelerator or the like.

In the present invention, the term "energy ray hardenability" means a property of being hardened by irradiation with an energy ray, and "non-energy ray curability" means a property that does not harden even when irradiated with an energy ray.

The tensile modulus (Young's modulus) of the protective film obtained by irradiating the energy-shielding film of the film for forming a protective film of the present invention is 1 × 10 ⁸ Pa or more, preferably 1.3 × 10 ⁸ Pa or more, more preferably 1.6 × 10 ⁸ Pa or more, particularly preferably 1.9 × 10 ⁸ Pa or more. When the tensile modulus of the protective film is at least the above lower limit value, the effect of suppressing the occurrence of the ejector marks by the pin remaining in the protective film is suppressed.

On the other hand, the upper limit of the tensile modulus of the protective film is not particularly limited. For example, the tensile modulus of the protective film may be 6 × 10 ⁹ Pa or less, 5.7 × 10 ⁹ Pa or less, and 5.4 × 10 ⁹ Pa or less. These upper limit values are preferred examples.

The tensile modulus of the protective film can be measured in accordance with JIS K7161:1994.

The tensile modulus of the protective film can be appropriately adjusted by, for example, adjusting the type and amount of the component contained in the film for forming a protective film.

For example, the type and amount of the component contained in the film for forming a protective film can be adjusted by the type and amount of the component contained in the protective film forming composition to be described later. Further, by adjusting the type and content of the energy ray-curable component (a2) in the component of the composition for forming a protective film, the tensile modulus of the protective film can be more easily adjusted.

The Shore D hardness of the protective film obtained by irradiating the energy-shielding film of the film for forming a protective film of the present invention is preferably 55 or more, more preferably 58 or more. Jia is 62 or more. When the Shore D hardness of the protective film is at least the above lower limit value, the protective film is less likely to be plastically deformed, and when the semiconductor wafer with the protective film is picked up by the pin by the pin, the surface of the protective film is prevented from remaining. The effect of the pin on the mark is made higher.

The upper limit of the Shore D hardness of the protective film is not particularly limited. However, the Shore D hardness of the protective film is preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less in terms of suppressing the effect of the protective film becoming brittle and further improving the reliability of the protective film. .

Even if the ejection force is large due to the pin, the effect of suppressing the residual pin caused by the pin is higher, and the protective film preferably has a Shore D hardness of 58 or more and tensile elasticity. The rate is 1 × 10 ⁸ Pa or more, more preferably the Shore D hardness is 62 or more, and the tensile modulus is 5 × 10 ⁹ Pa or more.

Further, in view of the above-described effect of suppressing the embrittlement of the protective film to be higher, and further improving the reliability of the protective film, the protective film preferably has a Shore D hardness of 90 or less and a tensile modulus of 9 × 10 ^{10 .} Below Pa, it is more preferable that the Shore D hardness is 80 or less and the tensile modulus is 5 × 10 ¹⁰ Pa or less.

The Shore D hardness of the protective film is a measured value obtained by laminating a plurality of films for forming a protective film in the thickness direction to form a film for forming a protective film having a total thickness of 6 mm. The laminate was cured to form a laminate of a protective film, and the laminate D of the protective film was measured at 23 ° C for the Shore D hardness.

The film for forming a protective film may be only one layer (single layer), or may be two or more layers. When the film is a plurality of layers, the layers may be the same or different, and the combination of the layers is not particularly limited. .

In the present specification, the present invention is not limited to the case of a film for forming a protective film. The term "multilayers may be the same or different" means that "all layers may be the same, or all layers may be different, and only a part of the layers may be the same. In addition, the phrase "different layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

The thickness of the film for forming a protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, still more preferably from 5 μm to 50 μm. When the thickness of the film for forming a protective film is at least the above lower limit value, a protective film having a higher protective ability can be formed. In addition, when the thickness of the film for forming a protective film is equal to or less than the above upper limit value, the thickness can be suppressed from being too thick.

Here, the "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means the entire layer of the film for forming a protective film. Total thickness.

The curing condition when the film for forming a protective film is cured to form a protective film is not particularly limited as long as the protective film can sufficiently exhibit the function of the protective film, and the type of film for forming a protective film can be used. Suitable choice.

For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably from 4 mW/cm ² to 280 mW/cm ² . Further, in the hardening, the amount of light of the energy ray is preferably from 3 mJ/cm ² to 1000 mJ/cm ² .

Fig. 1 is a cross-sectional view showing an embodiment of a film for forming a protective film of the present invention in a schematic manner. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, it is convenient to show a part that is a main part, and the size ratio of each component is not limited to the actual one. .

The film 13 for forming a protective film shown in the present invention includes a first release film 151 on one surface 13a of the film 13 for forming a protective film, and a second release film on the other surface 13b opposite to the surface 13a. 152.

Such a film 13 for forming a protective film is suitably stored, for example, in a roll shape.

The film 13 for forming a protective film can be formed using a composition for forming a protective film to be described later.

The tensile modulus of the film 13 for protective film formation (that is, the protective film) after hardening is 1 × 10 ⁸ Pa or more.

Each of the first release film 151 and the second release film 152 may be a known release film.

The first release film 151 and the second release film 152 may be the same or the same The peeling forces required for peeling off from the film 13 for forming a protective film are different from each other, for example.

The film 13 for forming a protective film shown in FIG. 1 is attached to a back surface of a semiconductor wafer (not shown) on which an exposed surface formed by removing either of the first release film 151 and the second release film 152 is attached. Further, the exposed surface formed by removing the other of the remaining ones of the first release film 151 and the second release film 152 serves as a bonding surface of the support sheet.

<<Constituent for forming a protective film>>

The film for forming a protective film can be formed using a composition for forming a protective film containing a constituent material of the film for forming a protective film. For example, a protective film forming composition is applied to the surface to be formed of the film for forming a protective film, and if necessary, it is dried, whereby a film for forming a protective film can be formed at a target portion. The content ratio of the components which are not vaporized at normal temperature in the composition for forming a protective film is usually the same as the content ratio of the components in the film for forming a protective film. In the present specification, the term "normal temperature" means a temperature which is not particularly cold or particularly hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

The protective film-forming composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll. Coating machine, roll coater, curtain coater, die coater, knife coater, screen coating Machine, meyer bar coater, contact coater, and the like.

The drying condition of the protective film-forming composition is not particularly limited, and when the protective film-forming composition contains a solvent to be described later, it is preferably heated and dried. The protective film-forming composition containing a solvent is preferably dried at, for example, 70 ° C to 130 ° C for 10 seconds to 5 minutes.

<Construction film forming composition (IV-1)>

The protective film-forming composition (IV-1) or the like containing the energy ray-curable component (a) is exemplified as the protective film-forming composition.

[Energy line hardening component (a)]

The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and this component is used to impart film-forming property or flexibility to the film for forming a protective film.

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray-curable group and having a molecular weight of 100 to 80,000. (a2). The polymer (a1) may be crosslinked or crosslinked by at least a part of the crosslinking agent (f) described later.

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

(Polymer (a1) having an energy ray-hardening group and having a weight average molecular weight of 80,000 to 2,000,000)

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). And an energy ray-curable compound (a12) having a functional group reactive with a group of another compound, wherein the energy ray-curable compound (a12) has a functional group An energy ray-curable group such as a reaction group and an energy ray-hardening double bond.

Examples of the functional group which can react with a group of another compound include a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (one or two hydrogen atoms of the amine group are substituted by a group other than a hydrogen atom) Base), epoxy group, and the like. However, in terms of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the functional group is preferably a group other than a carboxyl group.

Among these, the above functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional group (a11)

The acrylic polymer (a11) having a functional group may, for example, be a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group, or may be a polymer. In addition to these monomers, a polymer obtained by copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) is further used.

Further, the acrylic polymer (a11) may be a random copolymer. It can also be a block copolymer.

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

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

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

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

The number of the acrylic monomers having the functional group in the acrylic polymer (a11) may be one or two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

Examples of the acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (methyl) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate , isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate (lauryl (meth) acrylate), ( Tridecyl methyl methacrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecane (meth) acrylate Alkyl ester (alkyl palmitate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) Based on a carbon number of 1 to 18 The structure (meth) acrylate and the like.

Further, examples of the acrylic monomer having no functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxylated (meth)acrylate. (A) alkoxyalkyl-containing (meth) acrylate such as ester, ethoxyethyl (meth) acrylate; containing (meth) propylene (meth)acrylate having an aromatic group such as aryl (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivative; (meth)acrylic acid N, A non-crosslinkable (meth) acrylate having a tertiary amino group such as N-dimethylaminoethyl ester or N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomer having no functional group in the acrylic polymer (a11) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected. .

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

The non-acrylic monomers constituting the acrylic polymer (a11) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the functional group to the total mass of the structural unit constituting the acrylic polymer (a11) is preferred. It is from 0.1% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass, even more preferably from 3% by mass to 30% by mass. By setting the above ratio to such a range, the energy ray curability of the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be obtained. The content of the base is easily adjusted to a range in which the degree of hardening of the protective film is better.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

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

‧Energy line hardening compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group, and is compatible with the acrylic polymer (a11). The group of the functional group reaction is more preferably an isocyanate group as the above group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the above-mentioned group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

The energy ray-curable compound (a12) preferably has one to five of the energy ray-curable groups in one molecule, and more preferably has one to three energy ray-curable groups.

Examples of the energy ray-curable compound (a12) include 2-methylpropenyloxyethyl isocyanate and m-isopropenyl-α,α-dimethyl group. Benzyl isocyanate, methacryl oxime isocyanate, allyl isocyanate, 1,1-(bispropenyloxymethyl)ethyl isocyanate; by diisocyanate compound or polyisocyanate compound and (methyl) a propylene fluorenyl monoisocyanate compound obtained by the reaction of hydroxyethyl acrylate; a propylene fluorenyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound and hydroxyethyl (meth) acrylate Wait.

Among these, the energy ray-curable compound (a12) is preferably 2-methylpropenyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the aforementioned functional group derived from the acrylic polymer (a11) It is preferably from 20 mol% to 120 mol%, more preferably from 35 mol% to 100 mol%, still more preferably from 50 mol% to 100 mol%. By the above content ratio being such a range, the adhesion force of the protective film formed by hardening becomes larger. In the case where the energy ray-curable compound (a12) is a monofunctional compound (having one of the above-mentioned groups in one molecule), the upper limit of the ratio of the content is 100 mol%, but the energy is When the linear curable compound (a12) is a compound having two or more compounds (having two or more of the above groups in one molecule), The upper limit of the ratio of the aforementioned content sometimes exceeds 100 mol%.

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

When at least a part of the polymer (a1) is crosslinked by a crosslinking agent (f), the polymer (a1) may be any one of the acrylic polymers (a11) which does not conform to the above description. The monomer having a monomer reactive with the crosslinking agent (f) is polymerized, crosslinked in a group reactive with the crosslinking agent (f), or may be derived from the aforementioned energy ray-curable compound (a12) Crosslinking is carried out in the group reactive with the aforementioned functional groups.

The polymer (a1) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these may be used. Combinations and ratios can be arbitrarily chosen.

(Compound (a2) having an energy ray-hardening group and having a molecular weight of 100 to 80,000)

Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of from 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples of the group include (A) Base) acrylonitrile, vinyl, and the like.

When the compound (a2) satisfies the above conditions, it is not particularly limited. Examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and a phenol resin having an energy ray-curable group.

In the compound (a2), the low molecular weight compound having an energy ray-curable group may, for example, be a polyfunctional monomer or oligomer, and is preferably an acrylate-based compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) Acrylate, 2,2-bis[4-((meth)propenyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl)propenyloxy) Ethoxy)phenyl]anthracene, 2,2-bis[4-((meth)propenyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (three Cyclodecane dimethylol di(meth) acrylate), 1,10-nonanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9- Decanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(methyl) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) ) Eneoxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(methyl) Bifunctional (meth) acrylate such as acryloxypropane; isocyanurate Tris(2-(methyl)propenyloxyethyl) acid, ε-caprolactone modified tris-(2-(methyl)propenyloxyethyl) isocyanurate, ethoxylate Triglyceride (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, ethoxylate a polyfunctional (meth) acrylate such as pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate; A polyfunctional (meth) acrylate oligomer such as an acrylamide urethane oligomer.

In the above-mentioned compound (a2), as the epoxy resin having an energy ray-curable group or a phenol resin having an energy ray-curable group, for example, paragraph 0043 in "Japanese Patent Laid-Open Publication No. 2013-194102" can be used. Resin. Such a resin also conforms to the resin constituting the thermosetting component (h) to be described later, but in the present invention, the compound (a2) is regarded.

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

The protective compound-forming composition (IV-1) and the protective film-forming film may be used alone or in combination of two or more kinds. And the ratio can be arbitrarily chosen.

[Polymer without energy line hardening group (b)]

The protective film forming composition (IV-1) and the protective film forming film are contained. When the compound (a2) is used as the energy ray-curable component (a), it is preferred to further contain a polymer (b) having no energy ray-curable group.

The polymer (b) may be crosslinked at least in part by the crosslinking agent (f) or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an urethane urethane resin. , polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, and the like.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes referred to simply as "acrylic polymer (b-1)").

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include an alkyl (meth)acrylate, a (meth)acrylate having a cyclic skeleton, and a glycidyl group (A). Acrylate, hydroxyl group-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. Here, the "substituted amine group" is as described above.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, cetyl (meth) acrylate An alkyl group of an alkyl ester such as an ester (palmityl (meth)acrylate), a heptadecyl (meth)acrylate, or an octadecyl (meth)acrylate (stearyl (meth)acrylate) a chain structure with a carbon number of 1 to 18 Alkyl (meth)acrylate or the like.

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

Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth)acrylate and the like.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). 3 - hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Examples of the (meth) acrylate containing a substituted amino group include N-methylaminoethyl (meth) acrylate and the like.

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

As the polymer (b) which is crosslinked by at least a part of the crosslinking agent (f) and does not have the aforementioned energy ray-curable group, for example, a reactive functional group and a crosslinking agent in the above polymer (b) (f) a polymer of the reaction.

The reactive functional group is appropriately selected depending on the type of the crosslinking agent (f), and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amine group, etc., among which, it is preferred to have high reactivity with an isocyanate group. Hydroxyl. In the case where the crosslinking agent (f) is an epoxy compound, the reactive functional group may, for example, be a carboxyl group, an amine group or a guanamine group, and among these, it is preferably an epoxy group. A highly reactive carboxyl group. However, just prevent it In terms of circuit corrosion of the semiconductor wafer or the semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

The polymer (b) having the reactive functional group and having no energy ray-curable group may, for example, be a polymer obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), either or both of the acrylic monomer and the non-acrylic monomer exemplified as the monomer constituting the acrylic polymer (b-1) A monomer having the aforementioned reactive functional group may be used. The polymer (b) having a hydroxyl group as a reactive functional group may, for example, be a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and may be exemplified above. A polymer obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the acrylic monomer or non-acrylic monomer are substituted with the reactive functional group.

In the aforementioned polymer (b) having a reactive functional group, the ratio of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural unit constituting the polymer (b) is higher It is preferably from 1% by mass to 25% by mass, more preferably from 2% by mass to 20% by mass. By setting the above ratio to such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.

The weight average of the polymer (b) having no energy ray-curable group is obtained from the viewpoint that the film forming property of the protective film-forming composition (IV-1) is further improved. The molecular weight (Mw) is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000.

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

The composition (IV-1) for forming a protective film includes a composition containing either or both of the polymer (a1) and the compound (a2). In the case where the protective film-forming composition (IV-1) contains the compound (a2), it is preferred to further contain the polymer (b) having no energy ray-curable group, and in this case, Further, it further contains the aforementioned (a1). In addition, the protective film-forming composition (IV-1) may not contain the compound (a2) and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group.

When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the protective film-forming composition ( In the above IV-1), the content of the compound (a2) is preferably from 10 parts by mass to 400% by mass based on 100 parts by mass of the total of the polymer (a1) and the polymer (b) having no energy ray-curable group. More preferably, it is 30 mass parts to 350 mass parts.

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

When the protective film-forming composition (IV-1) contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) In the film for forming a protective film, the content of the polymer (b) is preferably from 3 parts by mass to 500 parts by mass, more preferably from 6 parts by mass to 6 parts by mass per 100 parts by mass of the energy ray-curable component (a). 450 parts by mass. When the content of the polymer (b) is in such a range, the energy ray hardenability of the film for forming a protective film becomes better.

In addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) may be selected from photopolymerization initiators depending on the purpose. 1 in the group consisting of (c), filler (d), coupler (e), crosslinker (f), colorant (g), thermosetting component (h), and general additive (z) Kind or more than two.

For example, by using the aforementioned energy ray hardening component (a) and heat The protective film-forming composition (IV-1) of the curable component (h), the film for forming a protective film formed by heating is improved in adhesion to the adherend by heating, and the film for protection film formation is protected. The strength of the film is also increased.

Further, by using the protective film forming composition (IV-1) containing the coloring agent (g), the protective film finally formed can improve the appearance of the semiconductor wafer, and the polishing marks on the back surface of the semiconductor wafer can be prevented from being recognized. Further, in the protective film, the laser printing performed on the surface facing the support sheet is excellent in visibility.

[Photopolymerization initiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compound; fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide a sulfonate compound such as benzyl phenyl sulfide or tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; Isoferrocene compound; thioxanthone compound such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butane Ketones, ethyl ketones, diphenyls such as 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) Ketone compound; peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; 2,4-diethyl thioxanthone; ,2- Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroindole and the like.

Further, as the photopolymerization initiator (c), for example, a ruthenium compound such as 1-chloroindole or a photosensitizer such as an amine can be used.

The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be Free to choose.

In the case of using the photopolymerization initiator (c), the content of the photopolymerization initiator (c) in the composition for forming a protective film (IV-1) relative to the content of the energy ray-curable compound (a) is 100. The mass part is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass to 16 parts by mass, still more preferably from 0.05 part by mass to 14 parts by mass.

[filler (d)]

When the film for forming a protective film contains the filler (d), it is easy to adjust the thermal expansion coefficient of the protective film obtained by curing the film for forming a protective film. In addition, the thermal expansion coefficient is most suitable for the object to be formed of the protective film, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved. Further, since the film for forming a protective film contains the filler (d), the moisture absorption rate of the protective film can be lowered or the heat dissipation property can be improved.

As the filler (d), for example, a material composed of a thermally conductive material can be cited.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, and boron nitride; and the inorganic fillers are spheroidized. Beads; surface modifiers of such inorganic fillers; single crystal fibers of such inorganic fillers; glass fibers, and the like.

Among these, the inorganic filler is preferably cerium oxide or aluminum oxide.

The average particle diameter of the filler (d) is not particularly limited, but is preferably from 0.01 μm to 20 μm, more preferably from 0.1 μm to 15 μm, still more preferably from 0.3 μm to 10 μm. When the average particle diameter of the filler (d) is in such a range, the adhesion to the object to be formed of the protective film can be maintained, and the decrease in the transmittance of light of the protective film can be suppressed.

In the present specification, the "average particle diameter" means the value of the particle diameter (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified. .

The filler (d) which is contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more kinds. When two or more types are used, the combinations thereof may be used. And the ratio can be arbitrarily chosen.

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

[coupler (e)]

By using a coupling agent having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesion of the film for forming a protective film to the adherend and the adhesion can be improved. In addition, by using the coupling agent (e), the protective film obtained by curing the film for protective film formation is not resistant to heat resistance and water resistance is improved.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group having an energy ray-curable component (a) and a polymer (b) having no energy ray-curable group, and more preferably a decane. Coupling agent.

Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Triethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxyanthracene Alkyl, 3-(2-aminoethylamino)propylmethyldiethoxydecane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide And methyltrimethoxydecane, methyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, imidazolium, and the like.

The coupler (e) contained in the film for forming a protective film (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, the combination thereof may be used. And the ratio can be arbitrarily chosen.

In the case of using the coupling agent (e), the protective film-forming composition (IV-1) and the film for forming a protective film have a content of the coupling agent (e) with respect to the energy ray-curable component (a) and The total content of the energy ray-curable group-containing polymer (b) is preferably from 0.03 parts by mass to 20 parts by mass, more preferably from 0.05 parts by mass to 10 parts by mass, even more preferably from 0.1 part by mass to 5 parts by mass. When the content of the coupling agent (e) is at least the above lower limit value, more remarkable effects by using the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, or The adhesion between the film for forming a protective film and the adherend is improved. Further, when the content of the coupling agent (e) is at most the above upper limit value, generation of outgas can be further suppressed.

[crosslinking agent (f)]

By using the crosslinking agent (f), the above energy ray hardening component (a) The polymer (b) having no energy ray-curable group is crosslinked, and the initial adhesion force and cohesive force of the film for forming a protective film can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. A reagent (a cross-linking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"). a terpolymer, an isocyanurate body, and an adduct of the above aromatic polyvalent isocyanate compound; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound; Wait. The term "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and is contained in ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. A reactant of a compound of low molecular weight active hydrogen. Examples of the adducts include a benzodimethyl diisocyanate adduct of trimethylolpropane described later. Further, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

As the above-mentioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-benzenedimethyl diisocyanate; 1,4-dimethylbenzene Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate to all or a part of hydroxyl groups of polyhydric alcohols such as trimethylolpropane A compound obtained by using one or more of hexamethylene diisocyanate and benzodimethyl diisocyanate; an isocyanuric acid diisocyanate or the like.

The organic polyimine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) or trimethylolpropane-tri-beta-nitrogen. Propidyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarbamamine) Based on melamine and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferred to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. . When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray are used. The reaction of the curable component (a) or the polymer (b) having no energy ray-curable group can easily introduce the crosslinked structure into the protective film. In the film.

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

In the case of using the crosslinking agent (f), in the protective film-forming composition (IV-1), the content of the crosslinking agent (f) is relative to the energy ray-curable component (a) and has no energy ray hardenability. The total content of the polymer (b) based on 100 parts by mass is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass, still more preferably from 0.5 part by mass to 5 parts by mass. When the content of the crosslinking agent (f) is at least the above lower limit value, a more remarkable effect by the use of the crosslinking agent (f) can be obtained. In addition, when the content of the crosslinking agent (f) is at most the above upper limit value, excessive use of the crosslinking agent (f) can be suppressed.

[coloring agent (g)]

Examples of the colorant (g) include known coloring agents such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigment and the organic dye include an ammonium dye, a cyanine dye, a merocyanine dye, a croconium dye, a squalilium dye, and an anthraquinone. Pigment, polymethine dye, naphthoquinone dye, pyranthene dye, phthalocyanine dye, naphthalocyanine dye, naphthalene phthalamide dye, azo dye, condensed azo Pigment, indigo pigment, perinone dye, anthraquinone dye, dioxane dye, quinacridone dye, isoindolinone dye, quinophthalone pigment, pyrrole a coloring matter, a thioindigo blue coloring matter, a metal complex coloring matter (metal stray salt dye), a dithiol metal complex dye, a nonylphenol dye, a triallyl methane dye, or an anthraquinone dye A naphthol-based dye, a methine-azo dye, a benzimidazolone dye, a dermoside-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, an anthraquinone dye, a platinum dye, and ITO. (Indium Tin Oxide; indium tin oxide) dye, ATO (Antimony Tin Oxide) pigment, and the like.

The coloring agent (g) contained in the film for forming a protective film (IV-1) and the film for forming a protective film may be used alone or in combination of two or more. When two or more kinds are used, the combination thereof may be used. And the ratio can be arbitrarily chosen.

In the case of using the coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted depending on the purpose. For example, printing may be performed on the protective film by laser irradiation, and the transmittance of the protective film may be adjusted by adjusting the content of the coloring agent (g) in the film for forming a protective film, thereby improving the print visibility. In this case, the ratio of the content of the colorant (g) to the total content of all the components other than the solvent in the protective film-forming composition (IV-1) (that is, the content of the coloring agent (g) in the film for forming a protective film) is preferably from 0.1% by mass to 10% by mass, more preferably from 0.4% by mass to 7.5% by mass, even more preferably from 0.8% by mass to 5% by mass. %. When the content of the coloring agent (g) is at least the above lower limit value, a more remarkable effect by the use of the coloring agent (g) can be obtained. In addition, when the content of the coloring agent (g) is at most the above upper limit value, excessive use of the coloring agent (g) can be suppressed.

[thermosetting component (h)]

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

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

(epoxy thermosetting resin)

The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).

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

‧Epoxy resin (h1)

Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolac epoxy. Two or more epoxy resins such as resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenyl skeleton type epoxy resin Compound.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy group of the polyfunctional epoxy resin is replaced with a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include a hypoethyl group (vinyl group), a 2-propenyl group (allyl group), and a (meth) acryl fluorenyl group. The (meth) acrylamide group or the like is preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, and is preferably from 300 to 30,000, more preferably from 400 to 3, in terms of the curability of the film for forming a protective film and the strength and heat resistance of the protective film. 10,000, especially 500 to 3000.

The epoxy equivalent of the epoxy resin (h1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 800 g/eq.

The epoxy resin (h1) may be used singly or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

‧Heat hardener (h2)

The heat hardener (h2) functions as a hardener for the epoxy resin (h1).

The thermosetting agent (h2) is, for example, a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group, or the acid group is anhydride-treated. More preferably, it is a phenolic hydroxyl group or an amine group.

In the thermosetting agent (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkylphenol. Resin, etc.

In the heat hardener (h2), as an amine-based hardener having an amine group, for example The dicyandiamide (hereinafter, abbreviated as "DICY") may be mentioned.

The heat hardener (h2) may also have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group in which an aromatic ring of the phenol resin is directly bonded to have an unsaturated hydrocarbon group. Compounds and the like.

The aforementioned unsaturated hydrocarbon group in the heat hardener (h2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) is preferably a phenol having a softening point or a high glass transition temperature in terms of improving the peeling property of the protective film from the support sheet. A hardener.

In the thermosetting agent (h2), for example, the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin preferably has a number average molecular weight of 300 to 30,000, more preferably Good for 400 to 10,000, especially for 500 to 3000.

In the heat curing agent (h2), for example, the molecular weight of the non-resin component such as biphenol or dicyandiamide is not particularly limited, and is, for example, preferably 60 to 500.

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

In the case of using the thermosetting component (h), the content of the thermosetting agent (h2) relative to the content of the epoxy resin (h1) in the protective film-forming composition (IV-1) and the film for forming a protective film. 100 parts by mass is preferably from 0.01 part by mass to 20 parts by mass.

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

[General Additives (z)]

The general-purpose additive (z) can be a known general-purpose additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives include plasticizers, antistatic agents, antioxidants, getters, and the like. .

The general-purpose additive (z) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one or more than two or more. When two or more types are used, the combinations thereof may be used. And the ratio can be arbitrarily chosen.

In the case of using the general-purpose additive (z), the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the film for forming a protective film is not particularly limited, and may be appropriately selected according to the purpose.

[solvent]

The protective film-forming composition (IV-1) preferably further contains a solvent. The handling property (IV-1) for forming a protective film containing a solvent is excellent in handleability.

The solvent is not particularly limited, and examples of preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1 - an alcohol such as butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; a decylamine such as dimethylformamide or N-methylpyrrolidone (a compound having a guanamine bond) )Wait.

The solvent contained in the protective film-forming composition (IV-1) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone, in that the component contained in the protective film-forming composition (IV-1) is more uniformly mixed. , toluene or ethyl acetate.

<<Method for Producing Composition for Protective Film Formation>>

The protective film forming composition such as the protective film-forming composition (IV-1) is obtained by blending the components constituting the protective film-forming composition.

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

When a solvent is used, it can be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using the following method, that is, not Put the solvent in Any of the other ingredients are pre-diluted to mix the solvent with the ingredients.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves. The method of mixing, etc.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and may be appropriately adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

In the same manner as the composite sheet for forming a protective film of the present invention to be described later, it is attached to the back surface of the semiconductor wafer or the semiconductor wafer opposite to the circuit surface, and is used as a composite sheet having a layer exhibiting adhesion on the support sheet. It is known that a crystal-cut wafer is present.

However, the adhesive layer provided in the diced wafer has a function of being mounted on a substrate, a lead frame, or another semiconductor wafer after being picked up from the support sheet together with the semiconductor wafer. The function of the agent. On the other hand, the film for forming a protective film in the composite sheet for forming a protective film of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally protected by curing. The film has the function of protecting the back side of the attached semiconductor wafer. As described above, the use of the film for forming a protective film in the present invention is different from that of the adhesive layer in the diced bonded wafer, and of course the required performance is also different. And, reflecting the difference in the use, usually, if it is connected to a crystal-cut wafer When the coating layer is compared, the film for forming a protective film tends to be hard. It is generally difficult to directly convert the adhesive layer in the die-cut wafer to the film for forming a protective film in the composite sheet for forming a protective film.

Method for producing ruthenium film for protective film formation

The film for forming a protective film of the present invention can be produced by applying a composition for forming a protective film to a release film (preferably, a release-treated surface of the release film), and drying it as necessary.

In the film for forming a protective film, for example, as shown in FIG. 1, the film for protective film formation is usually stored in a state in which a peeling film is bonded to both surfaces of the film. Therefore, the exposed surface of the film for forming a protective film formed on the release film as described above (the surface opposite to the side on which the release film is provided) is bonded to the release film (preferably, the release treatment of the release film) Face).

Method for using ◇ protective film forming film

As described above, by providing the film for forming a protective film of the present invention on the support sheet, a composite sheet for forming a protective film can be formed. The composite sheet for forming a protective film is used by attaching a film for forming a protective film to the composite sheet for forming a protective film to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface). In the same manner as in the case of the composite sheet for forming a protective film to be described later, the dicing, the pick-up of the semiconductor wafer with the protective film, and the like can be performed, and the target semiconductor device can be manufactured.

On the other hand, the film for forming a protective film of the present invention may be first set in half. The back side of the conductor wafer is not placed on the support sheet. That is, the film for forming a protective film is attached to the back surface of the semiconductor wafer. Then, the film for forming a protective film is irradiated with an energy ray, and the film for forming a protective film is cured to form a protective film. Then, the support sheet is bonded to the exposed surface of the protective film (the surface opposite to the side attached to the semiconductor wafer), thereby forming a composite film for forming a protective film. sheet. In the same manner as described above, the target semiconductor device can be manufactured by performing dicing, picking up of a semiconductor wafer with a protective film, and the like.

In the case where the film for forming a protective film is cured to form a protective film, the protective film is bonded to the support sheet. However, when the film for forming a protective film of the present invention is used, the film is used. The order of the steps can be reversed. In other words, after the film for forming a protective film is attached to the back surface of the semiconductor wafer, the support sheet is bonded to the exposed surface of the film for forming a protective film (the surface opposite to the side attached to the semiconductor wafer). Thus, the film for forming a protective film is a composite sheet for forming a protective film in an unhardened state. Then, the film for forming a protective film is irradiated with an energy ray, and the film for forming a protective film is cured to form a protective film. In the same manner as described above, the target semiconductor device can be manufactured by performing dicing, picking up of a semiconductor wafer with a protective film, and the like.

复合Protective film forming composite sheet

The composite sheet for forming a protective film of the present invention includes a support sheet, and the protective film forming film is provided on the support sheet, and when the protective film forming film is irradiated with an energy ray to form a protective film, the protective film and the support sheet are provided. The adhesion between the two is 50mN/25mm to 1500mN/25mm.

The composite sheet for forming a protective film of the present invention is previously provided with a function as a dicing sheet.

In the composite sheet for forming a protective film, when the tensile modulus of the protective film is within the above range and the adhesive force between the protective film and the support sheet is within the above range, even if the film for forming a protective film contains a coloring agent, The effect of suppressing the ejector marks caused by the pin remaining in the surface of the protective film opposite to the support sheet is suppressed.

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

In the composite sheet for forming a protective film of the present invention, the adhesive force between the protective film and the support sheet is from 50 mN/25 mm to 1500 mN/25 mm, preferably from 50 mN/25 mm to 1450 mN/25 mm, more preferably from 50 mN/25 mm to 1400 mN/ 25 mm, for example, may be any of 50 mN/25 mm to 1350 mN/25 mm, 50 mN/25 mm to 1300 mN/25 mm, and 50 mN/25 mm to 1250 mN/25 mm. By the adhesive force between the protective film and the support sheet being at least the above lower limit value, the protective film can be stably held in a sheet shape after the protective film is formed and the semiconductor wafer with the protective film is picked up. In addition, by making the adhesion between the protective film and the support sheet the aforementioned When the semiconductor wafer with the protective film is picked up by the pin by the pin, the film can be easily picked up even if it is gently ejected. Therefore, it is possible to suppress the remaining marks in the protective film from being caused by the pin. The effect becomes higher.

The adhesion between the protective film and the support sheet can be measured by the following method.

In other words, the composite sheet for forming a protective film having a width of 25 mm and having a predetermined length is attached to the adherend by the film for forming a protective film of the composite sheet for forming a protective film.

Then, the film for forming a protective film was cured by irradiation with an energy ray, and after the protective film was formed, the support sheet was peeled off at a peeling speed of 300 mm/min from the protective film attached to the adherend. In this case, the peeling system is a so-called 180° peeling in which the surface of the protective film and the support sheet are in contact with each other at an angle of 180°, and the support sheet is along the longitudinal direction of the support sheet (the composite sheet for forming a protective film) Stripped in the length direction. Then, the load (peeling force) at the time of 180° peeling was measured, and the measured value of the load (peeling force) was defined as the above-described adhesive force (mN/25 mm).

The length of the composite sheet for forming a protective film to be measured is not particularly limited as long as it is a range in which the adhesive force can be stably detected, and is preferably 100 mm to 300 mm. In addition, it is preferable to stabilize the attached state of the composite sheet for forming a protective film by attaching the composite sheet for forming a protective film to the adherend.

In the present invention, the adhesive force between the film for forming a protective film and the support sheet is not particularly limited, and may be, for example, 80 mN/25 mm or more, preferably 100 mN/25 mm or more, more preferably 150 mN/25 mm or more, and particularly preferably 200mN / 25mm or more. When the adhesive force is 100 mN/25 mm or more, peeling of the film for forming a protective film and the support sheet during dicing is suppressed. For example, the scattering of the semiconductor wafer having the film for forming a protective film on the back surface from the support sheet is suppressed.

On the other hand, the upper limit of the adhesive force between the film for forming a protective film and the support sheet is not particularly limited. For example, the adhesion may be any of 4000 mN/25 mm or less, 3500 mN/25 mm or less, and 3000 mN/25 mm or less. However, these upper limit values are only a preferred example.

The adhesion between the film for forming a protective film and the support sheet can be utilized between the protective film and the support sheet described above, except that the film for protective film formation for measurement is not cured by irradiation of the energy ray. The same method of adhesion is used for the measurement.

The adhesion between the protective film and the support sheet and the adhesive force between the film for forming a protective film and the support sheet can be adjusted, for example, by the type and amount of the component contained in the film for forming a protective film, and in the support sheet. The constituent material of the layer of the film for forming a protective film, the surface state of the layer, and the like are appropriately adjusted.

For example, the kind and amount of the component contained in the film for forming a protective film can be The type and amount of the component contained in the composition for forming a protective film are adjusted. Further, by adjusting the content of the component of the protective film-forming composition, for example, the type and content of the polymer (b) having no energy ray-curable group, the content of the filler (d), or the crosslinking agent (f) The content of the protective film or the film for forming a protective film and the support sheet can be more easily adjusted.

In the case where the layer of the film for forming a protective film in the support sheet is an adhesive layer to be described later, the constituent material of the adhesive layer can be appropriately adjusted by adjusting the kind and amount of the component contained in the adhesive layer. . Further, the type and amount of the component contained in the adhesive layer can be adjusted by the type and amount of the component contained in the adhesive composition described later.

On the other hand, when the layer of the film for forming a protective film in the support sheet is a substrate to be described later, the adhesion between the film for forming the protective film or the protective film and the support sheet is divided by the constituent material of the substrate. In addition, it can also be adjusted by the surface state of the substrate. Further, the surface state of the substrate can be adjusted, for example, by a surface treatment described later as a treatment for improving the adhesion between the substrate and the other layer, that is, by roughening treatment such as sand blasting or solvent treatment; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like, and any treatment such as primer treatment.

The thickness of the semiconductor wafer or the semiconductor wafer to be used as the composite sheet for forming a protective film of the present invention is not particularly limited, and it is preferably 30 μm to 1000 μm, more preferably 30 μm to 1000 μm, in order to obtain a more remarkable effect of the present invention. It is from 100 μm to 300 μm.

Hereinafter, the configuration of the composite sheet for forming a protective film will be described in detail.

◎Support film

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

Preferred examples of the support sheet include a support sheet in which an adhesive layer is laminated on a substrate in a direct contact manner, and a support sheet formed by laminating an adhesive layer on the substrate. Support sheets for materials.

Hereinafter, an example of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings in accordance with each of the above-mentioned support sheets.

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

In the drawings, the same components as those in the above-described drawings are denoted by the same reference numerals, and the detailed description of the component symbols is omitted.

The composite sheet 1A for forming a protective film shown here has an adhesive layer 12 on a substrate 11, and a film for forming a protective film on the adhesive layer 12. 13. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, in other words, the composite sheet 1A for forming a protective film has a structure in which a film 13 for forming a protective film is laminated on one surface 10a of the support sheet 10. In addition, the protective film forming composite sheet 1A and the protective film forming film 13 are provided with a release film 15 .

In the composite sheet 1A for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the protective film forming film 13 is formed over the entire surface of one surface 12a of the adhesive layer 12 for forming a protective film. A part of one surface 13a of the film 13, that is, a region in the vicinity of the peripheral portion, is laminated with the adhesive layer 16 for the jig, and the region and treatment of the adhesive layer 16 for the jig are not laminated on the surface 13a of the film 13 for forming a protective film. The surface 16a (upper surface and side surface) of the adhesive layer 16 is laminated with a release film 15.

In the composite sheet 1A for forming a protective film, the adhesion between the cured protective film forming film 13 (i.e., the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 50 mN/ 25mm to 1500mN/25mm.

The adhesive adhesive layer 16 may be, for example, a single layer structure containing an adhesive component, or may have a multilayer structure in which a double-layer layer of a core material has a layer containing an adhesive component.

The composite sheet 1A for forming a protective film shown in Fig. 2 is used in the following manner. In the state where the release film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to the surface 13a of the film 13 for forming a protective film, and the surface of the adhesive layer 16 for the jig is further used. The upper surface of 16a is attached to a jig such as a ring frame.

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

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except that the adhesive layer 16 for a jig is not provided. In the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the protective film forming film 13 is formed on the entire surface of the surface 12a of the adhesive layer 12 in the protective film. The entire surface layer of the surface 13a of the film 13 for formation has a release film 15.

The composite sheet 1B for forming a protective film shown in Fig. 3 is used in such a manner that a part of the central portion of the surface 13a of the film 13 for forming a protective film is attached in a state where the release film 15 is removed. On the back surface of the semiconductor wafer (not shown), a region in the vicinity of the peripheral portion is attached to a jig such as a ring frame.

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1C for forming a protective film shown here is formed in combination with the protective film shown in Fig. 2 except that the adhesive layer 12 is not provided. The splicing 1A is the same. In other words, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed only of the substrate 11. In addition, a film for forming a protective film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a layer is formed in a region near the peripheral portion of the surface 13a of the film 13 for forming a protective film. The adhesive layer 16 is provided with a release film on the surface 13a of the film 13 for protective film formation in the region where the adhesive layer 16 for the fixture is not laminated and the surface 16a (upper surface and side surface) of the adhesive layer 16 for the fixture. 15.

In the composite sheet 1C for forming a protective film, the adhesion between the cured protective film forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the substrate 11 is 50 mN/25 mm. Up to 1500mN/25mm.

The composite film 1C for forming a protective film shown in Fig. 4 is used in the same manner as in the case of the composite film 1A for protective film formation shown in Fig. 2, in the state where the release film 15 is removed, in the protective film. The back surface of the semiconductor wafer (not shown) is attached to the surface 13a of the film 13 for forming, and the upper surface of the surface 16a of the adhesive agent layer 16 is attached to a jig such as a ring frame.

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

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for protective film formation shown in FIG. 4 except that the adhesive layer 16 for a jig is not provided. That is, in the composite sheet 1D for forming a protective film, The protective film formation film 13 is laminated on one surface 11a of the substrate 11, and the release film 15 is formed over the entire surface 13a of the protective film formation film 13.

The composite film 1D for forming a protective film shown in Fig. 5 is used in the same manner as in the case of the composite film 1B for protective film formation shown in Fig. 3, in the state where the release film 15 is removed, in the protective film. A back surface of a semiconductor wafer (not shown) is attached to a partial region on the center side of the surface 13a of the film 13 for forming, and a region near the peripheral portion is attached to a jig such as a ring frame.

Fig. 6 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 3 except that the shape of the film for forming a protective film is different. In other words, the composite sheet 1E for forming a protective film has the adhesive layer 12 on the substrate 11, and the film 23 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, in other words, the composite sheet 1E for forming a protective film has a structure in which a film 23 for forming a protective film is laminated on one surface 10a of the support sheet 10. In addition, the protective film forming composite sheet 1E and the protective film forming film 23 are provided with a release film 15 .

In the composite sheet 1E for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a film 23 for forming a protective film is laminated on a central portion of a part of the surface 12a of the adhesive layer 12. And, in In the surface 12a of the adhesive layer 12, a release film 15 is laminated on the surface 23a (upper surface and side surface) of the protective film formation film 23 and the surface 23a (upper surface and side surface) of the protective film formation film 23.

When the protective film forming composite sheet 1E is viewed from above, the surface area of the protective film forming film 23 is smaller than the adhesive layer 12 and has a shape such as a circular shape.

In the composite sheet 1E for forming a protective film, the adhesion between the cured protective film forming film 23 (i.e., the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 50 mN/ 25mm to 1500mN/25mm.

The composite sheet 1E for forming a protective film shown in FIG. 6 is used in such a manner that a semiconductor wafer is attached to the surface 23a of the film 23 for forming a protective film in a state where the release film 15 is removed (illustration omitted) In the back surface of the adhesive layer 12, the region of the surface 12a of the adhesive layer 12 in which the protective film formation film 23 is not laminated is attached to a jig such as a ring frame.

Further, in the composite sheet 1E for forming a protective film shown in Fig. 6, the region where the protective film forming film 23 is not laminated on the surface 12a of the adhesive layer 12 may be laminated in the same manner as shown in Figs. 2 and 4 . An adhesive layer is used (not shown). The composite sheet 1E for forming a protective film having such an adhesive layer for a jig is used in the following manner, that is, the protection shown in FIGS. 2 and 4 In the same manner as the composite sheet for film formation, the surface of the adhesive layer for a jig is attached to a jig such as a ring frame.

In the composite sheet for forming a protective film of the present invention, the adhesive sheet for a jig can be provided regardless of the form of the support sheet and the film for forming a protective film. However, as shown in FIG. 2 and FIG. 4, the composite sheet for forming a protective film of the present invention having the adhesive layer for a jig is preferably provided with an adhesive layer for a protective film on the film for forming a protective film.

The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 2 to 6, and may be modified or deleted as shown in FIGS. 2 to 6 without departing from the effects of the present invention. The composite film for forming a protective film is partially formed, or another structure is added to the composite sheet for forming a protective film described above.

For example, in the composite sheet for forming a protective film shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the substrate 11 and the film 13 for forming a protective film. Any intermediate layer can be selected as the intermediate layer depending on the purpose.

Further, in the composite sheet for forming a protective film shown in FIG. 2, FIG. 3 and FIG. 6, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. In other words, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by sequentially laminating a substrate, an intermediate layer, and an adhesive layer. The intermediate layer referred to herein is the same as the intermediate layer which can be provided in the composite sheet for forming a protective film shown in Figs. 4 and 5 .

Further, in the composite sheet for forming a protective film shown in FIGS. 2 to 6, the layer other than the intermediate layer may be provided at an arbitrary position.

Further, in the composite sheet for forming a protective film of the present invention, a part of the gap may be formed between the release film and the layer directly in contact with the release film.

Further, in the composite sheet for forming a protective film of the present invention, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as described later, the layer directly contacting the film for forming a protective film in the support sheet such as the adhesive layer is preferably non-energy line curable. In such a composite sheet for forming a protective film, a semiconductor wafer with a protective film can be more easily picked up.

The support sheet can be transparent or opaque, and can be colored according to the purpose.

Among the inventions in which the film for forming a protective film has energy ray curability, the support sheet preferably transmits energy rays.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range and the energy ray (ultraviolet rays) is applied to the film for forming a protective film via the support sheet, the degree of hardening of the film for forming a protective film is further improved.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the aforementioned light transmittance can be 95% the following.

Further, in the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the light transmittance may be 95% or less.

Further, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the light transmittance may be 95% or less.

Next, each layer constituting the support sheet will be described in more detail.

○Substrate

The base material is in the form of a sheet or a film, and examples of the constituent material of the substrate include various resins.

Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-( A vinyl copolymer such as a methyl acrylate copolymer or an ethylene-bornene copolymer (a copolymer obtained by using ethylene as a monomer); a vinyl chloride resin such as a polyvinyl chloride or a vinyl chloride copolymer (using vinyl chloride as a vinyl chloride resin) Resin obtained by monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Poly(ethylene) 2,6-naphthalenedicarboxylate, a polyester such as a wholly aromatic polyester having an aromatic ring group; a copolymer of two or more of the foregoing polyesters; poly(meth)acrylic acid Ester; polyurethane; polyacrylamide Formate; polyimine; polyamine; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polyfluorene;

In addition, as the resin, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester may be used. The polymer alloy of the polyester and the resin other than the polyester is preferably a relatively small amount of the resin other than the polyester.

In addition, as the resin, for example, one or two or more kinds of the above-exemplified resins may be used as a cross-linking resin, and one or two or more kinds of ionic polymerizations of the above-exemplified resins may be used. Remodeling resin such as matter.

Further, in the present specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic acid.

The number of the resins constituting the substrate may be one or two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

The base material may be composed of one layer (single layer) or two or more layers. When the layer is composed of a plurality of layers, the layers may be the same or different, and the combination of the layers is not particularly limited.

The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. When the thickness of the substrate is in such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved.

Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

The substrate preferably has a high thickness precision, that is, it is preferable that the thickness unevenness is suppressed regardless of the portion. Among the above-mentioned constituent materials, examples of the material which can be used to constitute such a substrate having high thickness precision include polyolefins other than polyethylene and polyethylene, polyethylene terephthalate, and ethylene-acetic acid B. Ester copolymers and the like.

The base material may contain various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the above resin.

The optical characteristics of the substrate may satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited.

Further, in the invention in which the film for forming a protective film has energy ray curability, the substrate preferably transmits energy rays.

The surface of the substrate may be subjected to the following treatment to improve adhesion to other layers such as an adhesive layer provided on the substrate: by embossing treatment such as blasting or solvent treatment; or corona discharge treatment or electron beam treatment Oxidation treatment such as irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like.

In addition, the surface of the substrate may also be subjected to a primer treatment.

Further, the substrate may have an antistatic coating layer or a layer for the following use. When the composite sheet for forming a protective film is stacked and stored, the substrate is prevented from adhering to the other sheet or substrate to the adsorption stage.

Among these, the substrate is preferably subjected to electron beam irradiation treatment in terms of suppressing the occurrence of fragmentation of the substrate due to blade rubbing during cutting.

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

○Adhesive layer

The adhesive layer is in the form of a sheet or a film and contains an adhesive.

Examples of the pressure-sensitive adhesive include adhesion of an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin. The resin is preferably an acrylic resin.

Further, in the present invention, the term "adhesive resin" includes both an adhesive resin and a resin having adhesive properties, for example, not only a resin having adhesiveness but also being used in combination with other components such as additives. The resin exhibiting adhesiveness or a resin exhibiting adhesion by the presence of a trigger such as heat or water.

The adhesive layer may be composed of one layer (single layer) or two or more layers. When the layer is composed of a plurality of layers, the layers may be the same or different, and the combination of the layers is not particularly limited.

The thickness of the adhesive layer is preferably from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, still more preferably from 1 μm to 30 μm.

Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

The optical properties of the adhesive layer can satisfy the optical characteristics of the support sheet described above. That is, the adhesive layer may be transparent or opaque, and may be colored according to the purpose.

Further, in the invention in which the film for forming a protective film has energy ray curability, the pressure-sensitive adhesive layer preferably transmits energy rays.

The adhesive layer can be formed using an energy ray-curable adhesive, or can be formed using a non-energetic curable adhesive. The adhesive layer formed by the energy ray-curable adhesive can easily adjust the physical properties before and after hardening.

<<Adhesive composition>>

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive composition is applied to the surface to be formed of the adhesive layer, and if necessary, dried, whereby an adhesive layer can be formed at the target portion. A more specific method of forming the adhesive layer will be described in detail later together with the formation method of the other layers. The content ratio of the components which are not vaporized at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. Here, the "normal temperature" is as described above.

The adhesive composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll coater. Cloth machine, roll coater, curtain coater, die coater, knife coater, screen coater, wire bar coater, contact coater, etc.

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

In the case where the adhesive layer is an energy ray-curable property, the adhesive composition containing the energy ray-curable adhesive, that is, the energy ray-curable adhesive composition, for example, the following adhesive composition: adhesion The agent composition (I-1) contains a non-energy-curable adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)") and an energy ray-curable compound; The adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) (hereinafter sometimes referred to simply as "adhesive resin (I-2a)"), and the adhesive resin (I-) 2a) an unsaturated group is introduced into a side chain of the non-energy ray-curable adhesive resin (I-1a); the adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a), and an energy ray A hardening compound.

<Adhesive Composition (I-1)>

As described above, the aforementioned adhesive composition (I-1) contains non-energy hardening Adhesive resin (I-1a) and energy ray-curable compound.

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The number of the structural units of the acrylic resin may be one or two or more. When two or more types are used, the combinations and ratios may be arbitrarily selected.

The alkyl (meth)acrylate may, for example, be an alkyl (meth)acrylate having a carbon number of from 1 to 20 which constitutes an alkyl group of an alkyl ester, and the alkyl group is preferably a linear chain or a branch. Chained.

Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, (meth) propylene Cetyl acid ester (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), (A) Base) hexadecyl acrylate, eicosyl (meth) acrylate, and the like.

The acrylic polymer is preferably a structural unit having an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group, in terms of improving the adhesion of the adhesive layer. Further, the alkyl group preferably has a carbon number of 4 to 12, more preferably 4 to 8, in terms of further improving the adhesion of the adhesive layer. Further, the alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group is preferably an alkyl acrylate.

In the acrylic polymer, a structural unit derived from a functional group-containing monomer is preferably contained in addition to the structural unit derived from the alkyl (meth)acrylate.

Examples of the functional group-containing monomer include a monomer which can be reacted with a crosslinking agent to be described later to form a starting point for crosslinking, or can be contained by the functional group and the latter. The unsaturated group in the unsaturated group is reacted, and an unsaturated group is introduced into the side chain of the acrylic polymer.

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

That is, as the monomer having a functional group, for example, a hydroxyl group is mentioned Monomer, carboxyl group-containing monomer, amine group-containing monomer, epoxy group-containing monomer, and the like.

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

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

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

The number of the functional group-containing monomers constituting the acrylic polymer may be one or two or more. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

The acrylic polymer may have a structural unit derived from another monomer in addition to a structural unit derived from an alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer.

The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth)acrylate or the like.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

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

The acrylic polymer can be used as the above non-energy-curable adhesive resin (I-1a).

On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the above-mentioned energy ray hardening. Adhesive resin (I-2a).

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass.

[Energy curing compound]

The energy ray-curable compound contained in the adhesive composition (I-1) includes a monomer or oligomer which has an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray.

In the energy ray-curable compound, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI (A). Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; amine (meth)acrylate Ester; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.

In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the above-exemplified monomers.

The energy ray-curable compound is preferably (meth)acrylic acid in that the molecular weight is relatively large and the storage elastic modulus of the adhesive layer is not easily lowered. A urethane, (meth) acrylate urethane oligomer.

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

In the above-mentioned adhesive composition (I-1), the content of the energy ray-curable compound is preferably from 1% by mass to 95% by mass, more preferably from 5% by mass to 90% by mass, even more preferably from 10% by mass to 85% by mass. quality%.

[crosslinking agent]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, The adhesive composition (I-1) preferably further contains a crosslinking agent.

The crosslinking agent reacts with the aforementioned functional group to crosslink the adhesive resin (I-1a) with each other.

Examples of the crosslinking agent include isocyanate crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, benzodimethyl diisocyanate, and adducts of such diisocyanates (crosslinking agents having isocyanate groups). Epoxy crosslinking agent such as ethylene glycol glycidyl ether (crosslinking agent having glycidyl group); aziridine system such as hexa[1-(2-methyl)-aziridine]triphosphine triazine Crosslinking agent (crosslinking agent with aziridine group); metal chelate compound such as aluminum chelate A crosslinking agent (a crosslinking agent having a metal chelate structure); an isocyanurate crosslinking agent (a crosslinking agent having an isocyanuric acid skeleton), and the like.

The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the adhesive layer, and facilitating the acquisition.

The amount of the crosslinking agent contained in the adhesive composition (I-1) may be one or two or more. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 100 parts by mass per 100 parts by mass of the adhesive resin (I-1a). 20 parts by mass, particularly preferably from 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Acetophenone compound such as 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2 a fluorenylphosphine compound such as 4,6-trimethylbenzhydryldiphenylphosphine oxide; a sulfide compound such as benzylphenyl sulfide or tetramethylthiuram monosulfide; 1-hydroxycyclohexylbenzene Α-keto alcohol compound such as ketone; azo compound such as azobisisobutyronitrile; titanocene compound such as titanocene; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound such as diethyl hydrazine Benzene oxime; diphenyl oxime; benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-( 1-methylvinyl)phenyl]acetone; 2-chloroindole and the like.

In addition, as the photopolymerization initiator, for example, a ruthenium compound such as 1-chloroindole or a photo sensitizer such as an amine can be used.

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

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass per 100 parts by mass of the energy ray-curable compound. The part by mass is particularly preferably from 0.05 part by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-1), other additives which do not belong to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler (filler), a rust preventive, a colorant (pigment, dye), a sensitizer, and an adhesion-imparting agent. A known additive such as a reaction retarder or a crosslinking accelerator (catalyst).

In addition, the reaction retardation agent suppresses the cross-linking reaction outside the target in the adhesive composition (I-1) during storage by the action of the catalyst mixed in the adhesive composition (I-1). The reaction retardation agent is, for example, a compound which forms a chelate complex by a chelate compound, and more specifically, has two or more carbonyl groups (-C (in one molecule). Compound of =O)-).

The other additives contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

[solvent]

The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) has an applicability to the coating target surface by containing a solvent.

The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; and an ester (carboxylate) such as ethyl acetate; An ether such as tetrahydrofuran or dioxane; an aliphatic hydrocarbon such as cyclohexane or n-hexane; an aromatic hydrocarbon such as toluene or xylene; or an alcohol such as 1-propanol or 2-propanol.

As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) may be removed from the adhesive resin (I-1a) and used as the adhesive composition (I-1). When the adhesive composition (I-1) is produced, a solvent of the same kind or a different type as the solvent used in the production of the adhesive resin (I-1a) is separately added.

The solvent contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

<Adhesive Composition (I-2)>

As described above, the adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) which is a non-energy-curable adhesive resin (I). The side chain of -1a) is introduced with an unsaturated group.

[Adhesive resin (I-2a)]

The above-mentioned adhesive resin (I-2a) is made, for example, by a functional group in the adhesive resin (I-1a) and an unsaturated group having an energy ray polymerizable unsaturated group. The compound is obtained by reaction.

The unsaturated group-containing compound has, in addition to the above-mentioned energy ray-polymerizable unsaturated group, a group which can react with an adhesive resin (I- by reacting with a functional group in the adhesive resin (I-1a). 1a) Bonding.

Examples of the energy ray polymerizable unsaturated group include (meth)acryl fluorenyl group, vinyl group (ethylene group), allyl group (2-propenyl group), and the like, and (meth) propylene oxime is preferred. base.

The group which can be bonded to the functional group in the adhesive resin (I-1a) may, for example, be an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and may be bonded to a carboxyl group or an epoxy group. Hydroxyl groups and amine groups.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 10% by mass to 90% by mass.

[crosslinking agent]

When the acrylic polymer having the structural unit derived from the functional group-containing monomer is used as the adhesive resin (I-2a), for example, in the same manner as in the adhesive resin (I-1a), the adhesive composition is used. (I-2) may further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) is the same as the crosslinking agent in the adhesive composition (I-1).

The amount of the crosslinking agent contained in the adhesive composition (I-2) may be one or two or more. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the above-mentioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass based on the content of the adhesive resin (I-2a). 20 parts by mass, particularly preferably from 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can sufficiently perform a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-2) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass, per 100 parts by mass of the content of the adhesive resin (I-2a). It is preferably from 0.05 part by mass to 5 parts by mass to 10 parts by mass.

[Other additives]

In the adhesive composition (I-2), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

The other additives mentioned above in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

[solvent]

The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent mentioned in the adhesive composition (I-2) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-2) may be one or two or more. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive Composition (I-3)>

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

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass

[Energy curing compound]

The energy ray-curable compound to be contained in the adhesive composition (I-3) includes a monomer and an oligomer which have an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray, and examples thereof include The same compound as the energy ray-curable compound contained in the adhesive composition (I-1).

The energy ray-curable compound to be contained in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

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

[Photopolymerization initiator]

The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently perform a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

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

[Other additives]

In the adhesive composition (I-3), the range of the efficacy of the present invention is not impaired Other additives which do not belong to any of the above components may also be contained.

Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-3) may be used alone or in combination of two or more. When two or more kinds are used, the combinations and ratios may be arbitrarily selected.

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

[solvent]

The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-3) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)>

The foregoing mainly relates to the adhesive composition (I-1) and the adhesive composition (I-2). And the adhesive composition (I-3), but all the adhesive compositions other than the three adhesive compositions (in the present specification, referred to as "adhesive composition (I-1) to adhesion) As the adhesive composition other than the agent composition (I-3), the components described as the components contained in the above may be used in the same manner.

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray-curable adhesive composition, a non-energy-curable adhesive composition may be cited. Things.

Examples of the non-energy-curable adhesive composition include an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, and a polycarbonate. The adhesive composition (I-4) of the non-energy-curable adhesive resin (I-1a) such as an ester or an ester resin is preferably an adhesive composition containing an acrylic resin.

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

<Adhesive Composition (I-4)>

The preferred adhesive composition (I-4) is, for example, an adhesive composition containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)]

As the adhesive resin (I-1a) in the adhesive composition (I-4), it can be listed. The same adhesive resin as the adhesive resin (I-1a) in the adhesive composition (I-1) was used.

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass.

[crosslinking agent]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, The adhesive composition (I-4) preferably further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) is the same as the crosslinking agent in the adhesive composition (I-1).

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

In the above-mentioned adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 parts by mass to 50 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-1a). The parts by mass are more preferably from 0.1 part by mass to 20 parts by mass, particularly preferably from 0.3 part by mass to 15 parts by mass.

[Other additives]

In the adhesive composition (I-4), other additives not belonging to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

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

[solvent]

The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-4) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent composition (I-4) may be used alone or in combination of two or more. When two or more solvents are used, the combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-4), the content of the solvent is not particularly limited, and is suitable. It should be adjusted.

In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy line curable. The reason is that when the adhesive layer is energy ray-curable, the adhesive layer may be simultaneously hardened when the film for forming a protective film is cured by irradiation of the energy ray. When the adhesive layer and the film for forming a protective film are simultaneously cured, the film for forming a protective film and the adhesive layer after curing may adhere to the interface to such an extent that they cannot be peeled off. In this case, it is difficult to form the film for forming a protective film after curing on the back surface, that is, the semiconductor wafer (the semiconductor wafer with the protective film) of the protective film is peeled off from the support sheet having the adhesive layer after curing, and it is not possible to normally A semiconductor wafer with a protective film is picked up. In the present invention, by making the adhesive layer in the support sheet non-energy line hardenability, such a problem can be surely avoided, and the semiconductor wafer with the protective film can be more easily picked up.

The effect of the case where the adhesive layer is non-energy hardening is described herein, but even if the layer in the supporting sheet which is in direct contact with the film for forming a protective film is a layer other than the adhesive layer, as long as the layer is a non-energy line Sclerosing also works the same.

<<Manufacturing method of adhesive composition>>

Adhesive composition (I-1) to adhesive composition (I-1), adhesive composition (I-3), or adhesive composition (I-4) to adhesive composition (I-3) Adhesive composition other than by adhering the aforementioned adhesive and optionally as needed A component other than the agent is prepared by blending the components of the adhesive composition.

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

When a solvent is used, it can be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using the following method, that is, not Any one of the formulation components other than the solvent is diluted in advance to mix the solvent with the formulation components.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves. The method of mixing, etc.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and may be appropriately adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

Method for producing ruthenium film for forming protective film

The composite sheet for forming a protective film of the present invention can be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

For example, when a support sheet is produced, when the adhesive layer is laminated on the substrate, the above-mentioned adhesive composition is applied to the substrate, and dried as necessary.

On the other hand, for example, when a film for forming a protective film is laminated on an adhesive layer which has been laminated on a substrate, a film for forming a protective film can be directly formed by applying a composition for forming a protective film on the adhesive layer. A layer other than the film for forming a protective film may be used to form a composition of the layer, and the layer may be laminated on the adhesive layer by the same method. Thus, in the case where a laminated structure of two consecutive layers is formed using any of the compositions, the composition can be further coated on the layer formed of the above composition to form a layer. However, it is preferable to form a continuous two-layer laminated structure by using the above-mentioned composition to form a layer of the two subsequent layers in the second release film, which is formed. The exposed surface on the opposite side to the side in contact with the release film in the layer is bonded to the exposed surface of the remaining layer formed. In this case, the composition is preferably applied to the release-treated surface of the release film. After forming the laminate structure, the release film may be removed as needed.

For example, a composite sheet for forming a protective film formed by laminating an adhesive layer on a substrate and laminating a film for forming a protective film on the adhesive layer (a protective film comprising a support sheet as a laminate of a substrate and an adhesive layer) In the case of forming a composite sheet), an adhesive composition is applied onto a substrate, and if necessary, dried, whereby an adhesive layer is laminated on the substrate, and a protective film-forming composition is separately applied to the release film. The film for forming a protective film is formed in advance on the release film by drying it as needed. Then, the exposed surface of the film for forming a protective film is bonded to the exposed surface of the adhesive layer deposited on the substrate, and a film for forming a protective film is laminated on the adhesive layer, thereby forming a protective film. Composite sheet.

Further, when the adhesive layer is laminated on the substrate, as described above, the adhesive composition may be applied to the release film instead of applying the adhesive composition on the substrate, and dried as needed. Thereby, an adhesive layer is formed in advance on the release film, and the exposed surface of the layer is bonded to one surface of the substrate, whereby an adhesive layer is laminated on the substrate.

In either method, the release film may be removed at any point after the formation of the target laminate structure.

In this manner, the layer other than the base material constituting the composite sheet for forming a protective film can be laminated by being formed in advance on the release film and then bonded to the surface of the target layer. Therefore, such a step is appropriately selected as needed. In the layer, a composite sheet for forming a protective film can be produced.

In addition, the composite sheet for forming a protective film is usually stored in the following state, that is, the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side of the support sheet in the composite sheet for forming a protective film. There is a state of peeling film. Therefore, a composite sheet for forming a protective film can be obtained by applying a protective film forming composition or the like to the release film (preferably, a release-treated surface of the release film). The composition constituting the layer constituting the outermost layer is formed, and if necessary, dried, whereby a layer constituting the outermost layer is formed in advance on the release film, and an exposed surface on the opposite side to the side in contact with the release film in the layer is formed. Use any of the above methods to laminate the remaining layers without removing The film was peeled off while remaining in a bonded state.

Method for using ruthenium film for forming protective film

The composite sheet for forming a protective film of the present invention can be used, for example, by the method shown below.

In other words, the composite film for forming a protective film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) by the protective film forming film of the protective film forming composite sheet. Then, the film for forming a protective film is irradiated with an energy ray, and the film for forming a protective film is cured to form a protective film. Then, by cutting, the semiconductor wafer is divided together with the protective film to form a semiconductor wafer. Then, the state in which the semiconductor wafer is attached to the protective film (that is, in the form of a semiconductor wafer with a protective film attached thereto) is pulled away from the support sheet to be picked up.

Hereinafter, the semiconductor wafer of the obtained semiconductor wafer with the protective film obtained is flip-chip bonded to the circuit surface of the substrate by the same method as the prior method, and then a semiconductor package is produced. Then, the target semiconductor device can be fabricated using the semiconductor package.

In the case where the film for forming a protective film is cured to form a protective film and then diced, the case of performing the steps may be performed in the case of using the composite sheet for forming a protective film of the present invention. in contrast. In other words, after the composite sheet for forming a protective film is attached to the back surface of the semiconductor wafer, the semiconductor wafer is divided together with the film for forming a protective film by dicing to form a semiconductor wafer. Then, irradiating the film for forming a divided protective film The energy ray hardens the film for forming a protective film to form a protective film. In the same manner as described above, the semiconductor wafer with the protective film is pulled away from the support sheet and picked up to produce a target semiconductor device.

[Examples]

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

The components for producing a composition for forming a protective film are shown below.

‧ energy line hardening ingredients

(a2)-1: tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304).

‧ polymer without energy line hardening

(b)-1: butyl acrylate (hereinafter abbreviated as "BA") (10 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (70 parts by mass), and glycidyl methacrylate ( Hereinafter, an acrylic polymer obtained by copolymerizing "GMA" (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) (weight average molecular weight: 300,000) , glass transfer temperature -1 ° C).

‧Photopolymerization initiator

(c)-1: 2-(Dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone ("Irgacure 369" manufactured by BASF Corporation).

(c)-2: Ethylketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole -3-yl]-, 1-(O-ethinylhydrazine) ("Irgacure OXE02" manufactured by BASF Corporation).

‧Filler

(d)-1: cerium oxide filler (melted quartz filler, average particle diameter 8 μm).

‧ coupling agent

(e)-1: 3-methacryloxypropyltrimethoxydecane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent).

‧Colorant

(g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and a lanthanide red pigment (Pigment Red) 177) A pigment obtained by pigmenting at a mass ratio of 50 mass parts of the above three types of dyes/the amount of styrene acrylic resin = 1/3 (mass ratio).

[Example 1]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

The energy ray curable component (a2)-1, the polymer (b)-1, the photopolymerization initiator (c)-1, the photopolymerization initiator (c)-2, the filler (d)-1, The coupling agent (e)-1 and the coloring agent (g)-1 are dissolved or dispersed in methyl ethyl ketone so that the content (solid content, mass part) is as shown in Table 1. The mixture was stirred at 23 ° C to prepare a protective film-forming composition (IV-1) having a solid content concentration of 50% by mass.

(Manufacture of adhesive composition (I-4))

A non-energy-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, wherein the adhesive composition (I-4) contains an acrylic polymer (100 parts by mass, a solid content) And a trifunctional phthalic diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, a solid component), and further contains methyl ethyl ketone as a solvent. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass). And the weight average molecular weight is 600,000.

(Support for the manufacture of tablets)

The release treatment surface of the release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a film made of polyethylene terephthalate, was coated with the above-mentioned obtained The adhesive composition (I-4) was dried by heating at 120 ° C for 2 minutes to form a non-energy-curable adhesive layer having a thickness of 10 μm.

Then, a polypropylene film (Young's modulus: 400 MPa, thickness: 80 μm) which adheres to the exposed surface of the adhesive layer is obtained, whereby a support sheet having the above-mentioned adhesive layer on one surface of the substrate is obtained ( 10)-1.

(Manufacture of composite sheet for forming a protective film)

Release film (released by Lintec) on a single side of polyethylene terephthalate film by polyfluorination treatment The peeling-treated surface of "SP-PET381031" (thickness: 38 μm) was applied to the protective film-forming composition (IV-1) obtained by the knife coater, and dried at 100 ° C for 2 minutes. A film (13)-1 for forming a protective film for energy ray curability having a thickness of 25 μm was produced.

Then, the adhesive film in the support sheet (10)-1 obtained above was removed from the release film, and the exposed surface of the protective film formation film (13)-1 was adhered to the exposed surface of the adhesive layer. A film for forming a protective film for forming a substrate, an adhesive layer, a film for forming a protective film (13)-1, and a release film in this thickness direction are formed. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of film for forming a protective film>

(Tensile modulus of protective film)

The film (13)-1 for protective film formation obtained above was cut off to prepare a test piece.

Then, the test piece was irradiated with ultraviolet rays under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) to thereby form a film for forming a protective film ( 13)-1 hardening to obtain a protective film test piece.

Then, the tensile modulus (Young's modulus) of the protective film test piece at 23 ° C was measured in accordance with JIS K7161:1994. At this time, the width of the protective film test piece was set to 15 mm, the distance between the jigs was set to 10 mm, and the tensile speed was set to 50 mm/min. The results are shown in Table 2.

(Shore D hardness of the protective film)

The film (13)-1 for protective film formation obtained above was laminated so that the total thickness became 6 mm, and the obtained laminate was irradiated under the same conditions as those of the above-mentioned protective film. Ultraviolet rays are used to cure all of the film (13)-1 for forming a protective film to form a protective film.

Then, a constant pressure loader ("CL-150" manufactured by Kobunshi Co., Ltd.) was used for the laminate of the obtained protective film, and the Shore D hardness was measured at 23 °C. The results are shown in Table 2.

<Evaluation of composite sheet for forming a protective film>

(adhesion between the protective film and the support sheet)

The composite sheet for forming a protective film obtained as described above was cut into a size of 25 mm × 140 mm, and the release film was removed from the composite sheet for forming a protective film to expose one surface of the film for protective film formation (13)-1 as a pre-hardening test. sheet. On the other hand, a test piece of a double-sided adhesive tape was attached to the surface of a SUS (stainless steel) support plate (70 mm × 150 mm). Then, using the laminating machine ("LAMIPACKER LPD3214" manufactured by Fuji Co., Ltd.), the exposed surface of the film (13)-1 for protective film formation of the pre-hardened test piece is attached to the double-sided adhesive tape on the support plate. The support plate is attached to the pre-hardened test piece via a double-sided adhesive tape.

Then, using a UV irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), the film for protective film formation was irradiated with ultraviolet rays to the test piece before curing at illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² . (13)-1 hardens and obtains a test piece after hardening.

Then, using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), the following tensile test was performed, that is, at a peeling angle of 180°, a measurement temperature of 23° C., and a tensile speed of 300 mm/min. The support sheet (10)-1 (the laminate of the adhesive layer before curing and the substrate) was peeled off from the protective film, and the load (peeling force) at this time was measured, and the protective film and the support sheet (10)-1 were set. The adhesion between them. Further, as the measured value of the load, the support sheet (10)-1 was peeled off over a length of 100 mm, and in the measurement value at this time, the portion of the first peeled length of 10 mm and the portion of the last peeled length of 10 mm were respectively The measured value is excluded from the effective value, and the obtained value is used. The results are shown in Table 2.

(Residual suppression by the pin caused by the pin in the protective film)

The composite film for forming a protective film obtained as described above was attached to a #2000 polished surface of a 6-inch wafer (thickness: 350 μm) by the protective film forming film (13)-1 of the protective film-forming composite sheet. Further, the sheet was fixed in a ring frame and allowed to stand for 30 minutes.

Then, using a UV irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), a composite sheet for forming a protective film from the side of the support sheet (10)-1 under conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² The film (13)-1 for forming a protective film is cured by irradiation with ultraviolet rays to form a protective film.

Then, the ruthenium wafer was cut together with the protective film by a dicing blade to be singulated, and a 5 mm × 5 mm ruthenium wafer was obtained.

Then, using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.), one chip with a protective film was ejected by one pin, thereby picking up 20 wafers with a protective film. . Then, for the ten wafers with the protective film attached thereto, it is visually confirmed whether or not there is any residue in the surface of the protective film opposite to the support sheet, which is caused by the pin, and the mark of the remaining ejector is confirmed. The case where the film is zero is judged as "A", the case where it is one to three is judged as "B", and the case where it is four to ten is judged as "C", and the protective film is suppressed. The residual effect of the product is evaluated by the effect of the pin. The results are shown in Table 2. The column "Residual suppression of ejector marks" in Table 2 is described as the corresponding result.

<Manufacture and Evaluation of Composite Film for Forming Protective Film and Protective Film Forming>

[Embodiment 2]

The surface of the same substrate (polypropylene film, Young's ratio: 400 MPa, thickness: 80 μm) as the substrate used in the production of the support sheet (10)-1 was subjected to corona discharge treatment. Further, as shown in Table 2, the support sheet (10)-2 composed only of the surface-treated substrate was used instead of the support sheet (10)-1, and the same method as in Example 1 was used except for the above. A film for forming a protective film and a composite sheet for forming a protective film are produced and evaluated. The results are shown in Table 2. Furthermore, in the present embodiment, the electricity is equivalent to the substrate of the support sheet (10)-2. A film (13)-1 for forming a protective film is provided on the halo discharge treatment surface.

[Example 3]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of adhesive composition (I-4))

A non-energy-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, wherein the adhesive composition (I-4) contains an acrylic polymer (100 parts by mass, a solid content) And a trifunctional phthalic diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (0.5 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The acrylic polymer was obtained by copolymerizing BA (95 parts by mass) and HEA (5 parts by mass), and the weight average molecular weight was 800,000.

(Support for the manufacture of tablets)

In the same manner as in Example 1, except that the adhesive composition (I-4) obtained above was used, a non-energy-curable adhesive layer having a thickness of 10 μm was formed on the substrate to prepare a support sheet. (10)-3.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that the support sheet (10)-3 obtained above was used instead of the support sheet (10)-1. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 4]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

As shown in Table 1, the content (mixing amount) of the polymer (b)-1 was set to 2 parts by mass instead of 22 parts by mass, and the content (mixing amount) of the filler (d)-1 was 76 parts by mass. A protective film-forming composition (IV-1) was prepared in the same manner as in Example 1 except for the above.

(Manufacture of composite sheet for forming a protective film)

In the same manner as in Example 1, except that the protective film-forming composition (IV-1) obtained above was used, a film (13)-2 for forming a protective film for energy ray curability having a thickness of 25 μm was produced. .

Then, the protective film forming film (13)-2 was used instead of the protective film forming film (13)-1, and a protective film forming composite sheet was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 5]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

A protective film-forming composition (IV-1) was produced in the same manner as in Example 1.

(Manufacture of film for forming a protective film)

The release-treated surface of the release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a polyethylene terephthalate film by a polyphthalic acid treatment, was coated by a knife The protective film forming composition (IV-1) obtained above was applied and dried at 100 ° C for 2 minutes to prepare an energy ray-curable protective film forming film (13)-1 having a thickness of 25 μm. .

(Support for the manufacture of tablets)

The support sheet (10)-1 was produced in the same manner as in Example 1.

(Manufacture of composite sheet for forming a protective film)

The surface of the film (13)-1 obtained as described above which is opposite to the side on which the release film is provided is attached to a 6-inch wafer (thickness) 350 μm) #2000 ground surface.

Then, the film for protective film formation (13)-1 was irradiated with ultraviolet rays under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² by using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.). The film (13)-1 for forming a protective film is cured to form a protective film.

Then, the release film was removed from the protective film, and the adhesive layer of the support sheet (10)-1 obtained above was bonded to the exposed surface to prepare a composite sheet for forming a protective film with a ruthenium wafer, which was attached with twin crystals. The composite sheet base material for forming a protective film for a circle, an adhesive layer, a protective film, and a tantalum wafer are sequentially laminated in the thickness direction. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Embodiment 6]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

As shown in Table 1, a protective film was prepared in the same manner as in Example 1 except that the content (mixing amount) of the energy ray-curable component (a2)-1 was 10 parts by mass instead of 20 parts by mass. The composition for formation (IV-1).

(Manufacture of composite sheet for forming a protective film)

In the same manner as in Example 1, except that the protective film-forming composition (IV-1) obtained above was used, an energy-line-curable protective film forming film (13)-3 having a thickness of 25 μm was produced. .

In addition, the protective film forming film (13)-3 was used instead of the protective film forming film (13)-1, and a protective film forming composite sheet was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Embodiment 7]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

As shown in Table 1, a protective film was prepared in the same manner as in Example 1 except that the content (mixing amount) of the energy ray-curable component (a2)-1 was changed to 5 parts by mass in place of 20 parts by mass. The composition for formation (IV-1).

(Manufacture of composite sheet for forming a protective film)

In the same manner as in Example 1, except that the protective film-forming composition (IV-1) obtained above was used, an energy-line-curable protective film forming film (13)-4 having a thickness of 25 μm was produced. .

In addition, the protective film forming film (13)-4 was used in place of the protective film forming film (13)-1, and a protective film forming composite sheet was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Reference Example 1]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of adhesive composition)

An energy ray-curable adhesive composition having a solid content concentration of 30% by mass, wherein the adhesive composition contains an acrylic polymer (100 parts by mass, a solid content) and a trifunctional phthalic diisocyanate A coupling agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (6,6 parts by mass, solid content), and a photopolymerization initiator (2-hydroxy-1-{4-[4-(2-hydroxy-) 2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, "Irgacure 127" manufactured by BASF Corporation (3.0 parts by mass, solid content), and further contains a solvent as a solvent Ketoethyl ketone. The aforementioned acrylic polymer system a prepolymer obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass), and 2-methylpropenyloxyethyl isocyanate (21.4 parts by mass, relative to the hydroxyl group in HEA 100) An energy ray-curable acrylic polymer having a weight average molecular weight of 1,100,000 obtained by reacting a molar % and an isocyanate group in an amount of 80 mol %.

(Support for the manufacture of tablets)

In the same manner as in Example 1, except that the energy ray-curable adhesive composition obtained above was used in place of the adhesive composition (I-4), an energy ray hardening having a thickness of 10 μm was formed on the substrate. Support sheet (90)-1 of the adhesive layer.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that the support sheet (90)-1 obtained above was used instead of the support sheet (10)-1. The composition of the obtained composite sheet for forming a protective film is shown in Table 3.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Reference Example 2]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of adhesive composition)

A non-energy-curable adhesive composition having a solid content concentration of 30% by mass, the adhesive composition containing an acrylic polymer (100 parts by mass, a solid content), and a trifunctional phthalic diisocyanate It is a crosslinking agent ("Takenate D110N" by Mitsui Takeda Chemical Co., Ltd.) (0.5 mass part, solid content component), and further contains methyl ethyl ketone as a solvent. The acrylic polymer was obtained by copolymerizing BA (79 parts by mass), MA (16 parts by mass), and HEA (5 parts by mass), and had a weight average molecular weight of 600,000.

(Support for the manufacture of tablets)

A support sheet (90)-2 having a non-energy-curable adhesive layer having a thickness of 10 μm on a substrate was produced in the same manner as in Example 1 except that the adhesive composition obtained above was used.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that the support sheet (90)-2 obtained above was used instead of the support sheet (10)-1. The composition of the obtained composite sheet for forming a protective film is shown in Table 3.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the protective film formed as described above are used. The composite sheet was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 1]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

As shown in Table 1, a protective film was prepared in the same manner as in Example 1 except that the content (mixing amount) of the energy ray-curable component (a2)-1 was 2 parts by mass instead of 20 parts by mass. The composition for formation (IV-1).

(Manufacture of composite sheet for forming a protective film)

In the same manner as in Example 1, except that the protective film-forming composition (IV-1) obtained above was used, an energy-curable protective film forming film (93)-1 having a thickness of 25 μm was produced. .

Then, the film for protective film formation (93)-1 was used instead of the film for forming a protective film (13)-1, and a composite sheet for forming a protective film was produced in the same manner as in Example 1 except for the above. The composition of the obtained composite sheet for forming a protective film is shown in Table 3.

<Evaluation of Film for Forming Protective Film and Composite Sheet for Forming Protective Film>

The film for forming a protective film and the composite sheet for forming a protective film obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 3.

From the above results, it is clear that in the case of using the composite sheet for forming a protective film of Examples 1 to 7, the tensile modulus of the protective film is 2 × 10 ⁸ Pa or more, and the adhesion between the protective film and the support sheet is obtained. The force is 55 mN/25 mm to 1400 mN/25 mm, whereby the effect of suppressing the ejector marks caused by the pin remaining in the protective film is high. Further, in Examples 1 to 7, the Shore D hardness of the protective film was 56 or more.

On the other hand, in the case of using the composite sheet for forming a protective film of Reference Example 1 to Reference Example 2, the adhesive force between the protective film and the support sheet is 3300 mN/25 mm to 4860 mN/25 mm, thereby suppressing the residual in the protective film. The effect of the pin on the mark is low.

Further, in the case of using the composite sheet for forming a protective film of Comparative Example 1, the tensile modulus of the protective film was 9 × 10 ⁷ Pa, and therefore the effect of suppressing the occurrence of the ejector marks by the pin remaining in the protective film was suppressed. The protective film in Comparative Example 1 had a lower Shore D hardness than the protective films in Reference Examples 1 to 2.

(industry availability)

The invention can be used to fabricate semiconductor devices.

1A‧‧‧Composite film for protective film formation

10‧‧‧Support tablets

10a‧‧‧Surface of the support sheet

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer

13‧‧‧film for protective film formation

13a‧‧‧ Surface (one surface) of film for protective film formation

15‧‧‧Release film

16‧‧‧Layer layer for fixtures

16a‧‧‧ Surface of the adhesive layer for the fixture

Claims (3)

A film for forming a protective film is energy ray-curable; and when the film for forming a protective film is irradiated with an energy ray to form a protective film, the tensile modulus of the protective film is 1 × 10 ⁸ Pa or more. The film for forming a protective film according to claim 1, wherein the protective film has a Shore D hardness of 55 or more. A composite sheet for forming a protective film, comprising a support sheet, comprising the film for forming a protective film according to claim 1 or 2, wherein the protective film forming film is irradiated with an energy ray to form a protective film, the protection The adhesion between the film and the aforementioned support sheet is from 50 mN/25 mm to 1500 mN/25 mm.