TWI721158B - 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 maximum height (Rt) of the cross-section of at least one surface (β’) of the protective film is less than 10 μm. 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. A surface (β) of the protective film forming film that forms the surface (β’) of the protective film when the protective film forming film is irradiated with the energy beam faces the supporting sheet.

Description

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

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

This application claims priority based on Japanese Patent Application No. 2016-092008 filed in Japan on April 28, 2016, and the content of the application is cited herein.

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

There may be cases where a resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and the protective film is incorporated into a semiconductor device in the form of a semiconductor chip with a protective film. The protective film is used to prevent the semiconductor chip from cracking after the dicing step or packaging.

In order to form such a protective film, for example, a protective film forming film that can form a protective film by curing is used. As the protective film formation film, for example, a film provided with a release film on both sides or a film provided on a support sheet and provided with a release film on the exposed surface is used. As a composite sheet for forming a protective film in which a film for forming a protective film is provided on a support sheet, in addition to forming a protective film, it can also be used as a dicing sheet.

As such a film for forming a protective film, the following film for forming a protective film has been mainly used heretofore. The film for forming a protective film can be cured by heating regardless of the presence or absence of a support sheet to form a protective film. In this case, for example, a thermosetting protective film forming film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface), or a thermosetting protective film forming film is formed into a protective film After the composite sheet is attached to the protective film forming film of the protective film forming composite sheet, the protective film forming film is cured by heating to become a protective film, and the semiconductor wafer and the protective film are divided by dicing And make a semiconductor wafer. Then, the semiconductor wafer is directly picked up while keeping the protective film attached. Furthermore, there are cases where the curing and cutting of the protective film forming film are performed in the reverse order of the above.

On the other hand, usually by irradiating laser light on the surface of the protective film that is on the opposite side of the attaching surface to the semiconductor wafer (in the protective film forming composite sheet, the surface of the protective film facing the support sheet) Implement printing (sometimes referred to as "laser printing" in this manual). And, for the protective film, printing is required Excellent visibility.

However, if the laser printing surface of the protective film becomes rough in the stage before the laser printing, the laser printing cannot be clearly performed, and the printing visibility deteriorates. In this way, it is estimated that the reason for the roughening of the laser printing surface of the protective film is that at the stage of the protective film formation film, the surface equivalent to the laser printing surface has become rough, or the thermosetting protective film formation film is in use It becomes soft and easily deformed during heating by hardening, or the ingredients such as fillers move to the surface direction. Therefore, it is desirable to use a protective film forming film that can be cured by at least irradiating energy rays such as ultraviolet rays without heating, and to harden the protective film forming film so that the laser printing surface does not become rough.

As a film for forming such an energy-ray curable protective film, for example, an energy-ray curable protective film formed on a release film (refer to Patent Document 1); a film capable of forming a high hardness and excellent adhesion to a semiconductor wafer is disclosed The protective film is an energy ray-curable chip protective film (refer to Patent Document 2).

However, neither the energy ray hardening type protective film disclosed in Patent Document 1 nor the energy ray hardening type wafer protection film disclosed in Patent Document 2 aims to clearly perform laser printing on the protective film.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5144433.

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

The object of the present invention is to provide a film for forming an energy ray curable protective film and a composite sheet for forming a protective film having the aforementioned energy ray curable film for forming a protective film. The film for forming a protective film can be used on a semiconductor wafer or A protective film is formed on the back side of the semiconductor wafer, so that the protective film can be clearly printed by laser.

In order to solve the above-mentioned problems, the present invention provides a protective film formation film, which is an energy-ray curable protective film formation film. When the protective film formation film is irradiated with energy rays to form a protective film, the surface of at least one of the protective films The maximum profile height (Rt) of (β') is less than 10μm.

In the film for forming a protective film of the present invention, it is preferable that the gloss value of the surface (β') is 45 or more.

In the protective film forming film of the present invention, it is preferable that the maximum cross-sectional height (Rt) of at least one surface (β) is less than 10 μm, and the surface (β) is protected by irradiating energy rays to the protective film forming film When filming, it becomes the surface (β') of the aforementioned protective film.

In addition, the present invention provides a composite sheet for forming a protective film, which is provided with a support sheet, the film for forming the protective film is provided on the support sheet, and the surface (β) of the film for forming the protective film faces the support sheet. before The surface (β) is a surface that becomes the surface (β') of the protective film when the film for forming a protective film is irradiated with energy rays to become a protective film.

By using the protective film forming film and the protective film forming composite sheet of the present invention, the protective film can be formed on the semiconductor wafer or the back surface of the semiconductor wafer, so that the protective film can be clearly laser printed.

1C, 1D‧‧‧Composite sheet for forming protective film

10‧‧‧Support film

10a‧‧‧(supporting film) surface

11‧‧‧Substrate

11a‧‧‧(of the substrate) surface

13‧‧‧Film for forming protective film

13a‧‧‧(The surface of the protective film forming film) (1st side)

13b‧‧‧(The surface of the protective film forming film)

15‧‧‧Peeling film

151‧‧‧The first peeling film

152‧‧‧Second peeling film

16‧‧‧Adhesive layer for fixture

16a‧‧‧(Adhesive layer for jig) surface

Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film forming film of the present invention.

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

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

◇Film for forming protective film

The protective film forming film of the present invention is an energy-ray curable protective film forming film, and the maximum cross-section of at least one surface (β') of the protective film when the protective film forming film is irradiated with energy rays to form a protective film The height (Rt) is less than 10μm.

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

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

The above-mentioned protective film formation film is energy ray curable, so that the protective film can be formed by curing in a short time compared to a thermosetting protective film formation film.

In addition, in this specification, the "protective film formation film" means the protective film formation film before curing, and the "protective film" means the protective film formation film after curing.

As the film for forming the protective film, for example, a film containing the energy ray curable component (a) described later can be cited.

The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably has adhesiveness and uncured.

In the present invention, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum; examples of the energy rays include ultraviolet rays, radiation rays, electron beams, and the like.

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

In the present invention, the "energy ray curability" refers to the property of curing by irradiation of energy rays, and the term "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

Either one or both surfaces of the protective film obtained by irradiating the film for protective film formation of the present invention with energy rays become a surface (β') with a maximum cross-sectional height (Rt) of less than 10 μm. The surface (β') is the surface on the opposite side of the protective film from the surface to which the semiconductor wafer or the semiconductor wafer is attached, and can be a surface for laser printing to be described later.

In the protective film, the maximum cross-sectional height (Rt) of the surface (β') does not reach the aforementioned upper limit, whereby the laser printing on the surface becomes clear and the printing visibility is excellent. The reason for this effect is that the film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film to form a protective film.

In addition, in this specification, the "maximum section height (Rt)" means the maximum roughness curve calculated in accordance with JIS B 0601:2013 (ISO 4287:1997, Amd.1:2009) unless otherwise specified. The section height (Rt) is sometimes simply referred to as "Rt".

The maximum cross-sectional height (Rt) of the surface (β') of the protective film is preferably 9 μm or less, more preferably 8 μm or less.

The lower limit of the maximum profile height (Rt) of the surface (β') is not particularly limited set. For example, the maximum cross-sectional height (Rt) of the surface (β') may be 0.5 μm or more.

The gloss value of the surface (β') of the protective film is preferably 45 or more, more preferably 50 or more, for example, 60 or more, 70 or more.

The upper limit of the gloss value of the surface (β') is not particularly limited. For example, the gloss value of the surface (β') may be 95 or less.

In addition, in this specification, the term "gloss value" refers to the 60° specular gloss obtained by measuring the 60° specular gloss on the surface of the object to be measured from above, as long as there is no special description. The value.

The surface (β) of the film for forming a protective film is a surface that becomes the surface (β') of the protective film when the film for forming a protective film is irradiated with energy rays to become a protective film. In addition, the surface (β) of the protective film formation film is the surface opposite to the surface to which the semiconductor wafer is attached (in the protective film formation composite sheet, the protective film formation film is the surface facing the support sheet) ), which can eventually become the laser printing surface of the protective film.

In any one surface or both surfaces (β) of the protective film forming film, the maximum cross-sectional height (Rt) is preferably less than 10 μm, more preferably 9 μm or less, still more preferably 8.5 μm or less, and particularly preferably 8 μm the following.

The lower limit of the maximum cross-sectional height (Rt) of the surface (β) is not particularly limited. For example, the maximum cross-sectional height (Rt) of the surface (β) may be 0.5 μm or more.

Since the maximum cross-sectional height (Rt) of the surface (β) of the protective film forming film does not reach the aforementioned upper limit, more significant effects of the present invention can be obtained. That is, when the surface (β) becomes the laser printing surface of the protective film, the laser printing on the surface (the surface derived from the surface (β)) becomes clear, and the printing visibility is excellent. The reason for this effect is that the film for forming the protective film is energy-ray curable, and the curing is completed in a short time without heating. Unlike the thermosetting film for forming a protective film, it does not require heating during curing, which can prevent the film for forming a protective film from becoming soft and easily deformed during curing, or containing ingredients such as fillers in the film for forming a protective film Move towards the surface. In addition, by completing the hardening in a short time, even if the maximum cross-sectional height (Rt) of the surface (β) may change, the hardening is completed before the excessive change. In this way, the increase in the maximum cross-sectional height (Rt) of the surface (β) during curing is suppressed, and the maximum cross-sectional height (Rt) of the surface (β) before curing is as small as described above, so the protective film formed by curing The maximum profile height (Rt) of the surface (β') becomes smaller. In addition, during curing, the deterioration of the protective film forming film and the constituent components of the protective film, such as adversely affecting the visibility of printing, is also suppressed.

The gloss value of the surface (β) of the film for forming a protective film is preferably 45 or more, more preferably 50 or more, and may be 60 or more, 70 or more, for example.

The upper limit of the gloss value of the surface (β) is not particularly limited. For example, the gloss value of the surface (β) may be 95 or less.

The film for forming the protective film of the present invention needs to be energy ray curable and When the protective film is formed by irradiating energy rays, the maximum cross-sectional height (Rt) of the surface (β') is less than 10 μm, and the effect of the present invention can be exerted.

On the other hand, regarding the thermally curable protective film formation film, when the protective film is formed by heating, the above-mentioned energy ray curable protective film formation film of the present invention suppresses the defects related to the surface shape Not suppressed. In addition, during thermal curing, as described above, not only the surface shape is easily deformed, but also the protective film forming film and the constituent components of the protective film are easily deteriorated due to the long heating time, which adversely affects the visibility of printing. For example, even if the maximum cross-sectional height (Rt) on the surface of the protective film is less than 10 μm, the printing visibility of the protective film may be poor. In this way, when a thermally curable protective film formation film is used, various factors in the thermal curing will cause the printing visibility of the protective film to deteriorate.

The film for protective film formation can be manufactured by applying the composition for protective film formation mentioned later to the formation target surface of the film for protective film formation, and drying the composition for protective film formation as needed. In addition, the maximum cross-sectional height (Rt) and gloss value of the surface (β) of the protective film formation film, and the maximum cross-sectional height (Rt) and gloss value of the surface (β') of the protective film can be formed, for example, by adjusting the protective film The maximum cross-sectional height (Rt) of the coating surface of the composition (the surface to be formed of the protective film forming film) is appropriately adjusted.

As described later, for example, when the protective film forming film is provided with a release film on both sides, the coating surface of the protective film forming composition can be the surface of any one of these release films (preferably the release treatment surface). ). On the other hand, Yu Bao When the film for forming a protective film is provided on a support sheet described later, the coating surface of the composition for forming a protective film may be the surface of the aforementioned support sheet.

As described above, when the surface of the release film is used as the coating surface of the protective film formation composition, it is preferable to set the maximum cross-sectional height (Rt) of the coating surface of the protective film formation composition in the release film ) Is set to, for example, the value of the target maximum cross-sectional height (Rt) relative to the surface (β) is only a value smaller than 0.5 to a value larger than 0.5. Thereby, the maximum cross-sectional height (Rt) of the surface (β) can be adjusted to the target value more easily.

On the other hand, the maximum cross-sectional height (Rt) of the surface other than the coating surface of the protective film forming composition in the release film is not particularly limited, and may be the same as the coating surface of the protective film forming composition, for example.

When the surface of the release film is not used as the coating surface of the composition for forming a protective film, the maximum cross-sectional height (Rt) of the surface of the release film (the surface facing the film for forming a protective film) is not particularly limited.

The maximum cross-sectional height (Rt) of the surface of the release film can be adjusted by a known method.

For example, as a method of reducing the maximum cross-sectional height (Rt) by smoothing the surface of the release film as the uneven surface, the following so-called die press method can be cited: the surface of the release film used as the raw material is pressed against the smooth surface. The smooth shape is transferred to the aforementioned surface. In this molding method, by adjusting the smooth The smoothness of the surface can be adjusted to the maximum cross-sectional height (Rt) of the surface of the release film. The mold used to transfer the smooth shape can be any shape such as roll shape (smooth surface is roll surface), plate shape (smooth surface is flat), block shape (smooth surface is flat).

On the other hand, as a method of increasing the maximum cross-sectional height (Rt) by performing uneven treatment on the smooth surface of the release film, the following molding method can be cited: pressing the uneven surface on the surface of the release film used as the raw material The uneven shape is transferred to the aforementioned surface. In this molding method, the maximum cross-sectional height (Rt) of the surface of the release film can be adjusted by adjusting the degree of unevenness in the uneven surface. The mold used to transfer the concave and convex shape can be any shape such as roll shape (concave and convex surface is roll surface), plate shape (concave and convex surface is flat), block shape (concave and convex surface is flat).

In addition, as a method of increasing the maximum cross-sectional height (Rt) of the smooth surface of the release film, in addition to the above-mentioned die press method, for example, a sandblasting method, a solvent treatment method, etc. may be cited.

The protective film formation film can be only one layer (single layer), or multiple layers of two or more layers; in the case of multiple layers, these multiple layers may be the same or different from each other, and there is no combination of these multiple layers Specially limited.

In addition, in this specification, it is not limited to the case of the protective film forming film. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, and only a part of the layers may be the same. "Furthermore, the so-called "multiple layers are different from each other" means "the material and thickness of each layer At least one is different from each other."

The thickness of the protective film formation film is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the protective film forming film is more than the aforementioned lower limit, a protective film with higher protective ability can be formed. In addition, when the thickness of the film for forming a protective film is not more than the aforementioned upper limit, it is possible to suppress excessive thickness.

Here, the "thickness of the protective film forming film" means the overall thickness of the protective film forming film. For example, the thickness of the protective film forming film composed of a plurality of layers means the thickness of all the layers constituting the protective film forming film Total thickness.

Regarding the curing conditions when the protective film forming film is cured to form the protective film, as long as the protective film has a degree of curing sufficient to fully exhibit the function of the protective film, there are no particular restrictions, and it is appropriately selected according to the type of the protective film forming film That's it.

For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably 4 mW/cm ² to 280 ^{mW/cm 2} . In addition, during the aforementioned curing, the amount of light of the energy ray is preferably 3 mJ/cm ² to 1000 mJ/cm ² .

The thickness of the semiconductor wafer or the semiconductor wafer used as the protective film formation film is not particularly limited, but in terms of obtaining more significant effects of the present invention, it is preferably 30 μm to 1000 μm, more preferably 100 μm to 300 μm.

Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film forming film of the present invention. Furthermore, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, the main parts may be enlarged for convenience, and the size ratios of the constituent elements are not limited to the actual size ratios.

The protective film forming film 13 shown here is provided with a first release film 151 on one surface 13a of the protective film forming film 13 and a second release film 151 on the other surface 13b on the opposite side to the aforementioned surface 13a. Release film 152.

Such a protective film formation film 13 is suitable for storage in a roll shape, for example.

The film 13 for protective film formation can be formed using the composition for protective film formation mentioned later.

In the film 13 for forming a protective film, either or both of the surface 13a and the surface 13b are the surface (β).

Both the first release film 151 and the second release film 152 may be known release films, and as described above, they may be release films in which the maximum cross-sectional height (Rt) of the surface is adjusted.

The first peeling film 151 and the second peeling film 152 may be the same or different from each other, for example, the peeling force required for peeling from the protective film forming film 13 Different from each other and so on.

The protective film formation film 13 shown in FIG. 1 is attached to the back surface of a semiconductor wafer (not shown) on the exposed surface produced by removing any one of the first release film 151 and the second release film 152. And, the exposed surface produced by removing the remaining other of the first release film 151 and the second release film 152 becomes the attachment surface of the support sheet.

<<Protective film forming composition>>

The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, by coating the protective film forming composition on the surface to be formed of the protective film forming film, and drying the protective film forming composition as necessary, the protective film forming film can be formed on the target site. Generally, the content ratio of the components that do not vaporize at room temperature in the protective film formation composition is the same as the content ratio of the aforementioned components in the protective film formation film. In addition, in this specification, the "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, and for example, a temperature of 15°C to 25°C, etc. can be mentioned.

The composition for forming a protective film may be applied by a known method, for example, methods using various coating machines such as air knife coater, knife coater, bar coater, gravure coater, roll Type coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, contact coater Cloth machine and so on.

The drying conditions of the composition for forming a protective film are not particularly limited, and when the composition for forming a protective film contains a solvent described later, it is preferable to heat and dry. The composition for forming a protective film containing a solvent is preferably dried under conditions of, for example, 70°C to 130°C and 10 seconds to 5 minutes.

<Composition for Forming Protective Film (IV-1)>

As the protective film forming composition, for example, the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) can be cited.

[Energy ray hardening component (a)]

The energy-ray curable component (a) is a component that is cured by irradiation of energy rays, and the component is used to impart film-forming properties, flexibility, etc., 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 a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be cross-linked at least partially by the cross-linking agent (f) described later, or may not be cross-linked.

In addition, in this specification, the weight average molecular weight means the polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method, unless otherwise stated.

(Having an energy ray hardening base and a weight average molecular weight of 80,000 to 2,000,000 polymer (a1))

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 acrylic resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). ) Is polymerized with an energy ray curable compound (a12), the aforementioned acrylic polymer (a11) has a functional group capable of reacting with groups possessed by other compounds, and the aforementioned energy ray curable compound (a12) has a functional group with the aforementioned functional group Energy ray hardening groups such as reaction bases and energy ray hardening double bonds.

Examples of the functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Group), epoxy group and the like. Among them, in terms of preventing corrosion of circuits such as semiconductor wafers or semiconductor wafers, the aforementioned functional group is preferably a group other than a carboxyl group.

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

.Acrylic polymers with functional groups (a11)

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

In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of the aforementioned acrylic monomer having a functional group include: hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amine group-containing monomers, epoxy group-containing monomers, etc. .

Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylic acid Esters and the like carboxyalkyl (meth)acrylates and the like.

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

The aforementioned functional group constituting the aforementioned acrylic polymer (a11) The acrylic monomer may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

As the aforementioned acrylic monomer having no functional group, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), ( Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The group is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

In addition, as the aforementioned acrylic monomer having no functional group, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate can also be cited. (Meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate, etc.; those containing aryl (meth)acrylates such as phenyl (meth)acrylate, etc., have aromatic groups Of (methyl) Acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-dimethylaminopropyl Non-crosslinkable (meth)acrylates with tertiary amino groups such as esters.

The aforementioned acrylic monomer having no functional group constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected .

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

The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group to the total mass of the structural units constituting the acrylic polymer (a11) It is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% by mass to 30% by mass. With the aforementioned ratio in this range, the energy-ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray-curable compound (a12) The content of is easily adjusted to a better range for the degree of hardening of the protective film.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

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

‧Energy ray hardening compound (a12)

The aforementioned energy ray-curable compound (a12) preferably has one or more selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as those that can be combined with the aforementioned acrylic polymer (a11). The functional group reaction group preferably has an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

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

Examples of the energy ray curable compound (a12) include: 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid Base isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; an acrylic monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound and hydroxyethyl (meth)acrylate; Acrylic monoisocyanate compounds etc. obtained by the reaction of diisocyanate compounds or polyisocyanate compounds, polyol compounds and hydroxyethyl (meth)acrylate.

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

The aforementioned energy ray curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can 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 functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in this range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the energy ray curable compound (a12) is a monofunctional (having one group in one molecule) compound, the upper limit of the ratio of the content becomes 100 mol%, but it is less than the energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the aforementioned content ratio may exceed 100 mol%.

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

When at least a part of the aforementioned polymer (a1) is cross-linked by a cross-linking agent (f), the aforementioned polymer (a1) can make any one of the aforementioned acrylic polymers (a11) that does not meet the above description It is a monomer and a monomer having a group reactive with the crosslinking agent (f) is polymerized, and crosslinking is performed in the group reactive with the crosslinking agent (f). It may also be derived from the aforementioned energy ray curable compound (a12) Cross-linking is carried out in the group that reacts with the aforementioned functional group.

The aforementioned polymer (a1) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these The combination and ratio can be selected arbitrarily.

(Compound (a2) with energy ray hardening group and molecular weight of 100 to 80,000)

As the aforementioned energy-ray-curable group in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000, a group containing an energy-ray-curable double bond can be cited; as a preferable group, (former) Base) acryloyl, vinyl and the like.

If the aforementioned compound (a2) satisfies the above conditions, it is not particularly limited. Examples include low-molecular-weight compounds having energy ray-curable groups, Epoxy resin with curable base for measuring line, phenol resin with curable base for energy line, etc.

Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and preferably acrylate-based compounds having a (meth)acryloyl group.

Examples of the acrylate-based compound include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxy Bisphenol A bis(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) )Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] 茀, 2,2-bis[4-((meth) propylene oxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di(meth)acrylate (three Cyclodecane dimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) ) Allyloxyethoxy) phenyl) propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis( 2-functional (meth)acrylates such as meth)acryloxypropane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified isocyanuric acid three -(2-(meth)acryloxyethyl) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylic acid Ester, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, two Multifunctional (meth)acrylates such as pentaerythritol hexa(meth)acrylate; Multifunctional (meth)acrylate oligomers such as (meth)acrylate urethane oligomers, etc.

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

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

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

[Polymer without energy ray curable base (b)]

When the protective film forming composition (IV-1) and the protective film forming film contain the aforementioned compound (a2) as the aforementioned energy-ray curable component (a) In this case, it is preferable to further contain a polymer (b) that does not have an energy-ray curable group.

The aforementioned polymer (b) may be cross-linked at least partially by the cross-linking agent (f), or may not be cross-linked.

Examples of the polymer (b) that does not have an energy-ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins. , Polyvinyl alcohol (PVA), butyraldehyde resin, polyester urethane resin, etc.

Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

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

Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth)acrylates containing glycidyl groups. (Methyl)acrylate, hydroxyl-containing (meth)acrylate, substituted amine-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

Examples of the aforementioned alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylate Base) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute the alkyl group of the alkyl ester It is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms, etc.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenoxyethyl (meth)acrylate, etc. (Meth) acrylate cycloalkenyloxy alkyl ester and the like.

As the aforementioned (meth)acrylate containing glycidyl groups, for example, Examples include glycidyl (meth)acrylate and the like.

As the aforementioned hydroxyl group-containing (meth)acrylates, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

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

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

Examples of the polymer (b) that is at least partly cross-linked by the cross-linking agent (f) and does not have the aforementioned energy-ray curable group include: the reactive functional group in the aforementioned polymer (b) and the cross-linking agent (f) Reactive polymer.

The aforementioned reactive functional group may be appropriately selected according to the kind of crosslinking agent (f), etc., and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be mentioned; among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent (f) is an epoxy compound, the reactive functional group may include a carboxyl group, an amino group, an amide group, etc.; among these, the reaction with an epoxy group is preferred Highly carboxyl group. Among them, in terms of preventing the corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the aforementioned reaction The sexual functional group is preferably a group other than a carboxyl group.

As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of acrylic polymer (b-1), either or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) It is sufficient to use a monomer having the aforementioned reactive functional group. As the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate may be mentioned. In addition to this, the above-mentioned polymer may also be mentioned. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer is substituted with the aforementioned reactive functional group.

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

In terms of better film forming properties of the protective film forming composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) that does not have an energy ray curable group is preferably 10,000 to 2,000,000, More preferably, it is 100,000 to 1,500,000.

The composition for forming protective film (IV-1) and the polymer (b) having no energy ray curable group contained in the film for forming protective film may be only one type, or two or more types; in two types In the above case, the combination and ratio of these can be arbitrarily selected.

As the composition (IV-1) for forming a protective film, a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the protective film forming composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group. In this case, it is also more It is preferable to further contain the aforementioned (a1). In addition, the composition (IV-1) for forming a protective film may not contain the compound (a2), and may also contain the polymer (a1) and the polymer (b) that does not have an energy ray curable group.

When the protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the polymer (b) without an energy-ray curable group, the protective film forming composition ( In IV-1), the content of the aforementioned compound (a2) is 100 parts by mass relative to the total content of the aforementioned polymer (a1) and the polymer (b) without an energy-ray curable group, preferably 10 parts by mass to 400 Parts by mass, more preferably 30 parts by mass to 350 parts by mass.

In the composition for forming a protective film (IV-1), the total content of the aforementioned energy-ray curable component (a) and the polymer (b) that does not have an energy-ray curable group corresponds to The ratio of the total content of components other than the solvent (that is, the total content of the aforementioned energy ray curable component (a) and the polymer (b) without energy ray curable group in the film for forming a protective film) is preferable It is 5 mass% to 90 mass%, more preferably 10 mass% to 80 mass%, particularly preferably 15 mass% to 70 mass%, for example, it can be 20 mass% to 60 mass% and 25 mass% to 50 mass% Either. When the ratio of the aforementioned total content is in such a range, the energy ray curability of the protective film formation film becomes better.

When the protective film forming composition (IV-1) contains the aforementioned energy ray curable component (a) and the polymer (b) without an energy ray curable group, the protective film forming composition (IV-1) ) And the protective film forming film, the content of the aforementioned polymer (b) relative to 100 parts by mass of the energy ray curable component (a), preferably 3 parts by mass to 160 parts by mass, more preferably 6 parts by mass To 130 parts by mass, for example, it may be any of 15 parts by mass to 130 parts by mass, 40 parts by mass to 130 parts by mass, 65 parts by mass to 130 parts by mass, and 90 parts by mass to 130 parts by mass. When the content of the polymer (b) is in this range, the energy ray curability of the protective film formation film becomes more favorable.

The composition (IV-1) for forming a protective film may contain a photopolymerization initiator according to the purpose in addition to the energy-ray curable component (a) and the polymer (b) without an energy-ray curable group (c), filler (d), coupling agent (e), crosslinking agent (f), coloring agent (g), thermosetting component (h), hardening accelerator (i) and general additives (z) 1 or 2 types in the group on.

For example, by using the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) and thermosetting component (h), the formed protective film forming film is heated against the substrate The adhesive force of the adhering body is improved, and the strength of the protective film formed of the protective film forming film is also improved.

[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 methyl benzoate, benzoin dimethyl ketal, etc. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds ; Sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene And other titanocene compounds; thioxanthone and other thioxanthone compounds; benzophenone, 2-(dimethylamino)-1-(4-morpholine (morpholine) phenyl)-2-benzyl- 1-Butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Benzophenone compounds; peroxide compounds; diketone compounds such as diacetin; benzil; benzil; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2 -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone and the like.

In addition, as the photopolymerization initiator (c), for example, 1-chloroanthracene can also be used Quinone compounds such as quinones; light sensitizers such as amines, etc.

The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be Free to choose.

In the case of using the photopolymerization initiator (c), in the protective film forming composition (IV-1), the content of the photopolymerization initiator (c) is relative to the content of the energy ray curable compound (a) 100 Parts by mass, preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Filling material (d)]

When the protective film forming film contains the filler (d), the protective film obtained by curing the protective film forming film can easily adjust the thermal expansion coefficient. In addition, by optimizing the thermal expansion coefficient for the object to be formed of the protective film, the reliability of the package obtained by using the composite sheet for forming the protective film is further improved. In addition, when the protective film forming film contains the filler (d), the moisture absorption rate of the protective film can be reduced, or the heat dissipation can be improved.

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

The filling material (d) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material.

As preferred inorganic fillers, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by spheroidizing these inorganic fillers. Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

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

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

_{In addition, in this specification, the "average particle size" means the value of the particle size (D 50} ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. .

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

When the filler (d) is used, in the protective film forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the protective film is formed) The content of the filler (d) in the film) is preferably 5 mass% to 83 mass%, more preferably 7 mass% to 78% by mass, for example, can be any of 10% to 73% by mass, 25% to 68% by mass, and 40% to 63% by mass. With the content of the filler (d) in this range, it is easier to adjust the above-mentioned coefficient of thermal expansion.

[Coupling agent (e)]

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

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the energy-ray curable component (a), polymer (b) without an energy-ray curable group, etc., more preferably silane Coupling agent.

As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3- Mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, Vinyl triacetoxysilane, imidazole silane, etc.

The protective film forming composition (IV-1) and the protective film forming film may contain only one type of coupling agent (e), or two or more types; in the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

When the coupling agent (e) is used, in the protective film forming composition (IV-1) and the protective film forming film, the content of the coupling agent (e) is relative to the energy ray curable component (a) and does not have The total content of the polymer (b) of the energy ray curable base is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, particularly preferably 0.1 parts by mass to 5 parts by mass . With the aforementioned content of the coupling agent (e) above the aforementioned lower limit, the following more significant effects brought about by the use of the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, or The adhesion between the protective film forming film and the adherend is improved. In addition, when the aforementioned content of the coupling agent (e) is not more than the aforementioned upper limit value, the generation of outgassing can be further suppressed.

[Crosslinking agent (f)]

By using a crosslinking agent (f) to crosslink the above-mentioned energy ray curable component (a) or polymer (b) without an energy ray curable group, the initial adhesive force of the protective film formation film can be adjusted And cohesion.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. The reactant of low-molecular-weight active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane etc. mentioned later can be mentioned. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; diphenyl Methane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; two Cyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added toluene diisocyanate, hexamethylene Compounds of any one or more of diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinemethamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinylmethamine) triethylene Based on melamine and so on.

When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl-containing polymer as the energy-ray curable component (a) or polymer (b) that does not have an energy-ray curable group . When the crosslinking agent (f) has an isocyanate group and the energy ray curable component (a) or the polymer (b) without an energy ray curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) that does not have an energy-ray curable group can easily introduce a cross-linked structure into the protective film forming film.

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

In the case of using the crosslinking agent (f), the content of the crosslinking agent (f) in the protective film forming composition (IV-1) is relative to the energy ray curable component (a) and does not have energy ray curability The total content of the base polymer (b) is 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is above the aforementioned lower limit, more significant effects brought about by the use of the cross-linking agent (f) can be obtained. In addition, when the aforementioned content of the crosslinking agent (f) is below the aforementioned upper limit, excessive use of the crosslinking agent (f) can be suppressed.

[Colorant (g)]

As a coloring agent (g), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, an organic type dye, etc. are mentioned, for example.

Examples of the aforementioned organic pigments and organic dyes include: ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squalilium-based pigments, and azulenium-based pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, indigo Pigment, perinone pigment, perylene pigment, dioxane pigment, quinacridone pigment, isoindolinone pigment, quinophthalone pigment, pyrrole Pigment, thio Indigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes , Methine azo pigments, benzimidazolone pigments, pyranthrone pigments and threne pigments.

Examples of the aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) based pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) based pigments, etc.

The coloring agent (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

In the case of using a coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted according to the purpose. For example, when adjusting the content of the coloring agent (g) and adjusting the light transmittance of the protective film to adjust the visibility of printing, the content of the coloring agent (g) in the composition for forming a protective film (IV-1) The ratio with respect to the total content of all components other than the solvent (that is, the content of the coloring agent (g) in the protective film forming film) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass % By mass, and more preferably 0.8% by mass to 5% by mass. By the aforementioned content of the colorant (g) being above the aforementioned lower limit, a more significant effect caused by the use of the colorant (g) can be obtained effect. In addition, since the aforementioned content of the coloring agent (g) is not more than the aforementioned upper limit, the excessive use of the coloring agent (g) can be suppressed.

[Thermosetting component (h)]

The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these The combination and ratio can be chosen arbitrarily.

As the thermosetting component (h), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc. can be cited, and preferred are Epoxy-based thermosetting resin.

(Epoxy-based thermosetting resin)

The epoxy-based thermosetting resin system 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 protective film forming film may be only one type or two or more types; in the case of two or more types, these The combination and ratio can be chosen arbitrarily.

‧Epoxy resin (h1)

As the epoxy resin (h1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, Epoxy compounds with more than two functions, such as bisphenol F type epoxy resin and phenylene skeleton type epoxy resin.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.

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

In addition, as an epoxy resin having an unsaturated hydrocarbon group, for example, 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 can be cited.

The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic, The (meth)acrylamido group, etc., is preferably an acrylamido group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited. In terms of the curability of the protective film forming film, and the strength and heat resistance of the protective film, it is preferably 300 to 30,000, more preferably 400 to 10000, especially Preferably, it is 500 to 3000.

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

The epoxy resin (h1) may be used alone or in combination of two or more; when two or more of them are used in combination, the combination and ratio of these can be arbitrarily selected.

‧Thermal hardener (h2)

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

As a thermosetting agent (h2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride The formed group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), as phenolic curing agents having phenolic hydroxyl groups, for example, polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene phenol resins, and aralkylphenols can be cited Resin etc.

In the thermosetting agent (h2), examples of the amine-based curing agent having an amine group include dicyandiamine (hereinafter, abbreviated as "DICY") and the like.

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

As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin Compounds and so on.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

When a phenolic hardener is used as the thermosetting agent (h2), in terms of improving the peelability of the protective film from the supporting sheet, the thermosetting agent (h2) is preferably a phenol with a high softening point or glass transition temperature. Department of hardener.

In the thermosetting agent (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene-based phenol resin, aralkylphenol resin, etc. is preferably 300 to 30,000, more preferably It is 400 to 10,000, particularly preferably 500 to 3,000.

In the thermosetting agent (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited. For example, it is preferably 60 to 500.

The thermosetting agent (h2) may be used alone or in combination of two or more; when two or more of them are used in combination, the combination and ratio of these can be arbitrarily selected.

In the case of using the thermosetting component (h), the content of the thermosetting agent (h2) in the protective film formation composition (IV-1) and the protective film formation film With respect to 100 parts by mass of the content of the epoxy resin (h1), it is preferably 0.01 parts by mass to 20 parts by mass.

In the case of using the thermosetting component (h), the content of the thermosetting component (h) in the protective film forming composition (IV-1) and the protective film forming film (for example, epoxy resin (h1) And the total content of the thermosetting agent (h2)) relative to 100 parts by mass of the polymer (b) that does not have an energy ray curable group, preferably 1 part by mass to 500 parts by mass.

[Hardening accelerator (i)]

The curing accelerator (i) is a component for adjusting the curing speed of the protective film forming film.

Examples of preferable hardening accelerators (i) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one The hydrogen atoms are substituted by organic groups to form phosphines); tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

The hardening accelerator (i) can be used singly, or two or more of them can be used in combination. When two or more of them are used in combination, the combination and ratio of these can be arbitrarily selected select.

In the case of using the hardening accelerator (i), the content of the hardening accelerator (i) in the protective film forming composition (IV-1) and the protective film forming film is not particularly limited, and is appropriately selected according to the components used in combination That's it.

[General additives (z)]

The general additives (z) can be well-known general additives, and can be arbitrarily selected according to the purpose, and are not particularly limited; as preferred general additives, for example, plasticizers, antistatic agents, antioxidants, getters, etc. .

The protective film forming composition (IV-1) and the general additive (z) contained in the protective film forming film may be only one type or two or more types; in the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

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

[Solvent]

The composition (IV-1) for forming a protective film preferably further contains a solvent. The solvent-containing protective film forming composition (IV-1) has good operability.

The aforementioned solvent is not particularly limited. Preferred examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; dimethylformamide, N-methyl Pyrrolidone and other amides (compounds with amide bonds) and the like.

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

The solvent contained in the protective film forming composition (IV-1) is preferably methyl ethyl ketone in terms of allowing the components contained in the protective film forming composition (IV-1) to be more uniformly mixed. , Toluene or ethyl acetate, etc.

<<Production method of protective film forming composition>>

The composition for protective film formation, such as the composition for protective film formation (IV-1), is obtained by mixing each component which comprises this composition for protective film formation.

The order of addition when preparing 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 the following method: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used by the following method: not adding any one other than the solvent The compounding components are diluted in advance, and the solvent is mixed with these compounding components.

The method of mixing each component during compounding is not particularly limited, and can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; mixing by applying ultrasonic waves The method and so on.

Regarding the temperature and time when adding and mixing each component, as long as each There is no particular limitation on the deterioration of the compounding components, as long as they are adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◇Method of manufacturing protective film forming film

The film for forming a protective film of the present invention can be produced by applying a composition for forming a protective film on a release film (preferably the release-treated surface of the release film), and if necessary, using the composition for forming a protective film dry. At this time, by adjusting the maximum cross-sectional height (Rt) of the coating surface of the protective film forming composition in the release film, a protective film forming film having the aforementioned surface (β) can be formed.

In addition, as shown in FIG. 1, the film for protective film formation is usually stored in a state where a release film is attached to both sides of the film for protective film formation. Therefore, on the exposed surface of the protective film formation film formed on the release film as described above (the side opposite to the side with the release film), a release film is further bonded (preferably the release treatment of the release film) Noodles).

◇How to use the protective film formation film

As described above, by providing the protective film forming film of the present invention on the support sheet, a composite sheet for forming a protective film can be constructed. The composite sheet for forming a protective film is used by attaching the film for forming a protective film of the composite sheet for forming a protective film to the back surface (the surface opposite to the electrode forming surface) of the semiconductor wafer. Hereinafter, using the same method as in the case of the composite sheet for forming a protective film described later, the protective film is formed by curing the film for forming a protective film. Slicing, picking up of semiconductor wafers with protective films, etc. can be used to manufacture the target semiconductor device.

On the other hand, the protective film forming film of the present invention can also be provided on the back surface of the semiconductor wafer first, instead of being provided on the support sheet. That is, the film for forming a protective film is attached to the back surface of the semiconductor wafer. Next, the protective film formation film is irradiated with energy rays to harden the protective film formation film to become a protective film. Next, a support sheet is attached to the exposed surface of the protective film (the side opposite to the side attached to the semiconductor wafer), thereby forming a protective film forming composite in which the protective film forming film becomes a protective film sheet. Hereinafter, in the same manner as described above, dicing, picking up of a protective film-attached semiconductor wafer, etc. may be performed to manufacture the target semiconductor device.

In addition, this article describes the case of bonding the protective film to the support sheet after curing the protective film forming film to become a protective film. However, when the protective film forming film of the present invention is used, these are carried out. The order of the steps can also be reversed. That is, after the protective film forming film is attached to the back surface of the semiconductor wafer, the support sheet is attached to the exposed surface of the protective film forming film (the side opposite to the side attached to the semiconductor wafer), by This is a composite sheet for forming a protective film in which the film for forming a protective film is in an uncured state. Next, the protective film formation film is irradiated with energy rays to harden the protective film formation film to become a protective film. Hereinafter, in the same manner as described above, dicing, picking up of a protective film-attached semiconductor wafer, etc. may be performed to manufacture the target semiconductor device.

◇Composite sheet for forming protective film

The composite sheet for forming a protective film of the present invention is provided with a support sheet, the film for forming the protective film is provided on the support sheet, and the surface (β) of the film for forming the protective film faces the support sheet, and the surface (β) ) When the film for forming a protective film is irradiated with energy rays to become a protective film, it becomes the surface (β') of the protective film.

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

In the composite sheet for forming a protective film, the surface (β) of the film for forming a protective film faces the support sheet, and the surface (β') of the protective film is irradiated with energy rays.

The composite sheet for forming a protective film includes the film for forming a protective film, whereby the laser printing on the surface (β') of the protective film becomes clear, and the visibility of the printing is excellent.

In the present invention, even after the protective film formation film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film formation film (in other words, the support sheet and the protective film) is maintained, the laminated structure is also referred to as " Composite sheet for forming protective film".

The thickness of the semiconductor wafer or the semiconductor wafer used as the object of the composite sheet for forming a protective film of the present invention is not particularly limited. In terms of obtaining more significant effects of the present invention, it is preferably 30 μm to 1000 μm, more preferably It is 100μm to 300μm.

Hereinafter, the structure of the composite sheet for protective film formation is demonstrated in detail.

◎Support film

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

As a preferable support sheet, for example, a support sheet composed only of a base material can be cited.

Hereinafter, examples of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings.

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

In addition, in the figures after FIG. 2, the same components as those shown in the previously described figures are assigned the same symbols as in the previously described figures, and detailed descriptions of the symbols are omitted.

The composite sheet 1C for forming a protective film shown here is equipped with the film 13 for forming a protective film on the base material 11. The support sheet 10 is composed of only the base material 11; in other words, the protective film forming composite sheet 1C has a configuration in which the protective film forming film 13 is laminated on one surface 10a of the support sheet 10. In addition, protect The composite sheet 1C for film formation further includes a release film 15 on the film 13 for protective film formation.

In the protective film forming composite sheet 1C, the protective film forming film 13 is laminated on one surface 11a of the substrate 11 (the one surface 10a of the support sheet 10), and the protective film forming film 13 is laminated on one surface (this In the specification, sometimes referred to as the "first surface") 13a, that is, the area near the peripheral edge, is laminated with an adhesive layer 16 for jigs. The surface (first surface) 13a of the protective film forming film 13 is not The area of the adhesive layer 16 for laminated jigs and the surface 16a (upper surface and side surface) of the adhesive layer 16 for jigs are laminated with a release film 15.

In the composite sheet 1C for forming a protective film, the other surface of the film 13 for forming a protective film (sometimes referred to as the "second surface" in this specification), that is, the AND in the film 13 for forming a protective film The opposing surface 13b of the support sheet 10 is the aforementioned surface (β), and the first surface 13a of the protective film forming film 13 is the aforementioned surface (β).

The composite sheet 1C for forming a protective film shown in FIG. 2 is used in the following manner: with the release film 15 removed, a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film The upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.

Figure 3 schematically shows the composite for forming a protective film of the present invention A cross-sectional view of another embodiment of the sheet.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 2 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is laminated on one surface 11a of the base material 11, and a release film 15 is laminated on the entire area of the first surface 13a of the film 13 for forming a protective film .

The composite sheet 1D for forming a protective film shown in FIG. 3 is used in the following manner: with the release film 15 removed, a semiconductor is attached to a partial area on the central side of the first surface 13a of the film 13 for forming a protective film On the back surface of the wafer (not shown), the area near the peripheral edge is attached to a jig such as a ring frame.

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 3, and within the scope that does not impair the effect of the present invention, the ones shown in FIGS. 2 to 3 can be changed or deleted A part of the composite sheet for forming a protective film, or another structure is added to the composite sheet for forming a protective film described above.

For example, regarding the composite sheet for forming a protective film shown in FIGS. 2 to 3, as long as the effect of the present invention is not impaired, a supporting sheet, a film for forming a protective film, an adhesive layer for jigs, and a layer other than the release film can be provided In any part.

In addition, the composite sheet for forming a protective film of the present invention may also be peeled off There is a gap between the film and the layer directly in contact with the release film.

In addition, 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.

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

Among them, in the present invention in which the film for forming a protective film has energy ray curability, the support sheet preferably allows energy ray to pass through.

For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the aforementioned light transmittance in this range, when energy rays (ultraviolet rays) are irradiated to the protective film forming film through the support sheet, the degree of curing of the protective film forming film is further improved.

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

In addition, in the support sheet, the transmittance of light with a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.

On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 532 nm is not particularly limited. For example, the transmittance of the aforementioned light can be above 95% under.

In addition, in the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.

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

As in the manufacturing method described later, when the protective film forming composition is coated on the surface of the support sheet and dried as necessary to form the protective film forming film, it is preferable to use the protective film in the support sheet The maximum cross-sectional height (Rt) of the coating surface of the forming composition is set to, for example, the target maximum cross-sectional height (Rt) with respect to the surface (β) is within a range of only 0.5 to a value greater than 0.5. Thereby, the maximum cross-sectional height (Rt) of the surface (β) can be adjusted to the target value more easily.

Examples of the coating surface of the protective film forming composition in the support sheet include the surface of the aforementioned substrate.

As in the manufacturing method described later, when the protective film formation composition is not applied to the surface of the support sheet, and the protective film formation film is formed, the surface of the support sheet (the surface facing the protective film formation film, and Phase with the surface The maximum cross-sectional height (Rt) of the surface on the opposite side) is not particularly limited, and may be the same as the coating surface of the composition for forming a protective film described above, for example.

The maximum cross-sectional height (Rt) of the surface of the support sheet can be adjusted by the same method as the case of the above-mentioned maximum cross-sectional height (Rt) of the surface of the release film, for example.

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

○Substrate

The substrate is in a sheet shape or a film shape, and as a constituent material of the substrate, various resins can be cited, for example.

Examples of the aforementioned resin include polyethylenes such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and bornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-( Vinyl copolymers such as meth)acrylate copolymers and ethylene-bornene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using vinyl chloride as a monomer) Resin obtained from monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate , Polyethylene 2,6-naphthalene dicarboxylate, wholly aromatic polyesters with aromatic cyclic groups in all structural units; among two or more of the aforementioned polyesters Copolymer; Poly(meth)acrylate; Polyurethane; Polyacrylate urethane; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene Ether; polyphenylene sulfide; polysulfide; polyether ketone, etc.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.

In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins as exemplified above; and ionic polymerization using one or more of the aforementioned resins exemplified in the foregoing Modified resin such as materials.

Furthermore, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

The resin constituting the substrate may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

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

The thickness of the substrate is preferably 50 μm to 300 μm, more preferably 60 μm To 100μm. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to the semiconductor wafer or the 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 base material preferably has high thickness accuracy, that is, thickness unevenness can be suppressed at any part. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness precision include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. Things and so on.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

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

Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the base material transmits energy rays.

The base material can be manufactured by a known method. For example, a resin-containing substrate can be manufactured by molding a resin composition containing the aforementioned resin Made.

◇Method for manufacturing composite sheet for protective film formation

The composite sheet for forming a protective film of the present invention can be produced by sequentially stacking the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

In the case of manufacturing a composite sheet for forming a protective film formed by laminating a film for forming a protective film on a support sheet, for example, a composition for forming a protective film is coated on the support sheet, and the composition for forming a protective film is dried as necessary, and In this way, the aforementioned composite sheet for forming a protective film was obtained. At this time, by adjusting the maximum cross-sectional height (Rt) of the coating surface of the protective film forming composition in the support sheet as described above, a protective film forming film having the aforementioned surface (β) can be formed.

In addition, in the case of manufacturing a composite sheet for forming a protective film formed by laminating a film for forming a protective film on a support sheet, the composite sheet for forming a protective film can also be obtained by the following method: on a release film (preferably The protective film forming composition is applied to the peeling treatment surface of the peeling film, and the protective film forming composition is dried if necessary, thereby forming a protective film forming film on the peeling film in advance, and the protective film forming film The exposed surface of the support sheet is attached to the surface of one side of the support sheet. However, at this time, the maximum cross-sectional height (Rt) of the exposed surface of the protective film forming film (the surface opposite to the side where the release film is provided) is the maximum cross-sectional height (Rt) of the aforementioned surface (β) Make adjustments.

The release film may be removed at any point after the protective film formation film is formed.

In addition, the composite sheet for forming a protective film is usually stored in a state in which a release film is attached to the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side of the supporting sheet in the composite sheet for forming a protective film. status. Therefore, a composite sheet for forming a protective film can also be obtained by coating the release film (preferably the release-treated surface of the release film) with a composition for forming a protective film, etc., to form the most The composition of the surface layer layer, and drying the composition as necessary, to form the outermost layer on the release film, and the remaining layer is laminated on the exposed surface of the layer opposite to the side in contact with the release film Each layer does not remove the release film and keeps the state of being attached.

◇How to use the composite sheet for protective film formation

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

That is, the composite sheet for protective film formation is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface) through the protective film formation film of the composite sheet for protective film formation. Next, the protective film formation film is irradiated with energy rays to harden the protective film formation film to become a protective film. Then, by dicing, the semiconductor wafer and the protective film are divided together to form a semiconductor wafer. Then, the semiconductor wafer is directly pulled away from the support sheet for picking up while maintaining the state where the protective film is attached (that is, in the form of a semiconductor wafer with a protective film).

Hereinafter, using the same method as the previous method, the obtained semiconductor wafer of the semiconductor wafer with a protective film is flip-chip connected to the circuit surface of the substrate, thereby forming a semiconductor package. Then, the semiconductor package can be used to manufacture the target semiconductor device.

In addition, this article describes the case where the protective film formation film is cured to become a protective film and then cut. However, when the composite sheet for protective film formation of the present invention is used, the order of performing these steps may be reversed. . That is, after attaching the protective film forming composite sheet to the back surface of the semiconductor wafer, the semiconductor wafer is divided together with the protective film forming film by dicing to produce a semiconductor wafer. Next, the divided film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film to become a protective film. Hereinafter, 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 the target semiconductor device.

[Example]

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

The components used to manufacture the protective film forming composition are shown below.

‧Energy ray hardening ingredients

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

‧Polymer without energy ray hardening base

(b)-1: Make butyl acrylate (hereinafter referred to as "BA") (10 parts by mass), methyl acrylate (hereinafter referred to as "MA") (70 parts by mass), and glycidyl methacrylate ( Hereinafter referred to as "GMA") (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) copolymerized acrylic polymer (weight average molecular weight 300,000) , Glass transition temperature -1℃).

(b)-2: Acrylic polymer obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass) (weight average molecular weight 370,000, glass transition temperature 6°C).

‧Photopolymerization initiator

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

(c)-2: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) ("Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).

‧Filler

(d)-1: Silica filler (fused silica filler, average particle size 8μm).

(d)-2: Spherical silica filler ("SC2050MA" manufactured by Admatechs, with an average particle size of 0.5μm).

‧Coupling agent

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

(e)-2: 3-Aminopropyltrimethoxysilane (Nippon Unicar) Manufactured "A-1110", silane coupling agent).

‧Colorant

(g)-1: 32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and anthraquinone-based red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass, and pigmenting so that the total amount of the aforementioned 3 kinds of pigments/the amount of styrene acrylic resin=1/3 (mass ratio).

(g)-2: Carbon black ("#MA650" manufactured by Mitsubishi Chemical Corporation, with an average particle size of 28nm).

‧Epoxy resin

(h1)-1: Bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184g/eq to 194g/eq).

(h1)-2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq).

(h1)-3: Dicyclopentadiene epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255g/eq to 260g/eq).

‧Thermal hardener

(h2)-1: Dicyandiamine (thermally active latent hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, with active hydrogen content of 21 g/eq).

‧Hardening accelerator

(i) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.).

The base material used for manufacturing the composite sheet for forming a protective film is shown below.

‧Substrate (11)-1: A base made of polypropylene film with a thickness of 80μm, one surface with a maximum cross-sectional height (Rt) of 0.9μm, and the other surface with a maximum cross-sectional height (Rt) of 1.5μm material.

‧Substrate (11)-2: A base made of polypropylene film with a thickness of 80μm, one surface with a maximum cross-sectional height (Rt) of 8.0μm, and the other surface with a maximum cross-sectional height (Rt) of 1.5μm material.

‧Substrate (91)-1: A base made of polypropylene film with a thickness of 80μm, one surface with a maximum cross-sectional height (Rt) of 12.0μm, and the other surface with a maximum cross-sectional height (Rt) of 1.5μm material.

‧Substrate (91)-2: A base made of polypropylene film with a thickness of 80μm, one surface with a maximum cross-sectional height (Rt) of 16.0μm, and the other surface with a maximum cross-sectional height (Rt) of 1.5μm material.

Hereinafter, the release film used for manufacturing the film for protective film formation or the composite sheet for protective film formation is shown.

‧Release film (15)-1: Polyethylene terephthalate film made of polyethylene terephthalate, one side of which is peeled off by silicone treatment ("SP-PET381031" made by Lintec, thickness 38μm).

‧Release film (15)-3: The thickness is 80μm, the maximum cross-sectional height (Rt) of one surface is 0.9μm, and the maximum cross-sectional height (Rt) of the other surface is 1.5μm using polyethylene terephthalate Ester peeling film.

‧Release film (15)-4: The thickness is 80μm, the maximum cross-sectional height (Rt) of one surface is 8.0μm, and the maximum cross-sectional height (Rt) of the other surface 1.5μm peeling film using polyethylene terephthalate.

‧Release film (95)-1: The thickness is 80μm, the maximum cross-sectional height (Rt) of one surface is 12.0μm, and the maximum cross-sectional height (Rt) of the other surface is 1.5μm using polyethylene terephthalate Ester peeling film.

‧Release film (95)-2: The thickness is 80μm, the maximum cross-sectional height (Rt) of one surface is 16.0μm, and the maximum cross-sectional height (Rt) of the other surface is 1.5μm using polyethylene terephthalate Ester peeling film.

[Example 1]

<Production of protective film formation film and protective film formation composite sheet>

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

Make energy ray curable component (a2)-1, polymer (b)-1, photopolymerization initiator (c)-1, photopolymerization initiator (c)-2, filler (d)-1, Coupling agent (e)-1 and coloring agent (g)-1 are dissolved or dispersed in methyl ethyl ketone so that their content (solid content, parts by mass) becomes the value shown in Table 1 By stirring at 23° C., a protective film forming composition (IV-1) having a solid content concentration of 50% by mass was prepared. In addition, the description of "-" in the column of contained components in Table 1 means that the protective film forming composition (IV-1) does not contain the component.

(Manufacturing of protective film forming film and protective film forming composite sheet)

The protective film forming composition (IV-1) obtained above was applied to the surface of the substrate (11)-1 with a maximum cross-sectional height (Rt) of 0.9 μm by a knife coater, and Dry for 2 minutes at 100°C to produce a thickness of 25μm The energy-ray curable protective film formation film (13)-1.

Next, the exposed surface of the protective film formation film (13)-1 obtained above was bonded to the peeling treatment surface of the peeling film (15)-1 to produce a composite sheet for forming a protective film, the composite sheet for forming a protective film The base material (11)-1, the protective film forming film (13)-1, and the release film (15)-1 are laminated in this order in the thickness direction. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of Protective Film>

(The maximum cross-sectional height (Rt) of the surface of the protective film on the opposite side to the attachment surface to the semiconductor wafer)

An ultraviolet irradiation apparatus (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm ^2, light quantity of 170mJ / cm condition ^2, the above obtained the protective film is formed by a composite sheet from the support sheet is irradiated with ultraviolet rays, by This hardens the film (13)-1 for forming a protective film to form a protective film.

Next, the support sheet was peeled off from the formed protective film, and the exposed surface of the protective film was measured in accordance with JIS B 0601:2013, that is, the surface of the protective film on the opposite side to the surface of the semiconductor wafer (and the substrate (11 )-1 The maximum section height (Rt) of the opposite surface). The results are shown in Table 2. In Table 2, the values shown in the "Rt" column are the above-mentioned measured values.

(The gloss value of the surface of the protective film on the opposite side to the surface attached to the semiconductor wafer)

When measuring the above-mentioned maximum cross-sectional height (Rt), a gloss meter (gloss meter "VG 2000" manufactured by Nippon Denshoku Co., Ltd.) is used. According to JIS K 7105, the protective film is measured from the side opposite to the side where the semiconductor wafer is attached. The attaching surface of the wafer is the 60° specular gloss of the surface on the opposite side, and the above-mentioned measured value is taken as the gloss value of the above-mentioned surface of the protective film. The results are shown in Table 2.

(Visibility of laser printing on protective film)

In the composite sheet for protective film formation obtained above, the protective film formation film (13)-1 was cured by the same method as when measuring the maximum cross-sectional height (Rt) to form a protective film.

Next, using a printing device ("MD-S9910A" manufactured by KEYENCE), under the conditions of an output of 1.2W, a frequency of 40kHz, and a scanning speed of 100mm/sec, from the protective film on the opposite side of the semiconductor wafer attachment surface The surface of the protective film is irradiated with laser light with a wavelength of 532nm to perform laser printing.

Through the substrate (11)-1, visually observe the printing on the protective film, and when all the printing is clearly read, the laser printing visibility is judged as "A"; at least part of the printing cannot be clearly read In this case, the visibility of laser printing is judged as "B". The results are shown in Table 2.

<Production of protective film formation film and protective film formation composite sheet, and evaluation of protective film>

[Example 2]

Use base material (11)-2 instead of base material (11)-1, in addition to this, it is advantageous The protective film formation film and the protective film formation composite sheet were manufactured by the same method as Example 1, and the protective film was evaluated. The composition (IV-1) for forming a protective film was applied to the surface of the substrate (11)-2 with a maximum cross-sectional height (Rt) of 8.0 μm. The results are shown in Table 2.

[Example 3]

<Production of protective film forming film>

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

By the same method as in Example 1, a composition (IV-1) for forming a protective film was produced.

(Manufacturing of protective film forming film)

The protective film forming composition (IV-1) obtained above was applied to the surface of the release film (15)-3 with the maximum cross-sectional height (Rt) of 0.9 μm by a knife coater, and By drying at 100°C for 2 minutes, a film (13)-1 for forming an energy ray curable protective film with a thickness of 25 μm was produced.

Next, the exposed surface of the protective film formation film (13)-1 obtained above was bonded to the peeling treatment surface of the peeling film (15)-1 to produce a laminate sheet, which is a peeling film (15)-3 , The protective film formation film (13)-1 and the release film (15)-1 are laminated in this order in the thickness direction. The composition of the obtained laminated sheet is shown in Table 2.

<Evaluation of protective film formation film and protective film>

(The maximum cross-sectional height (Rt) of the surface of the protective film formation film on the opposite side to the surface of the semiconductor wafer attached to it)

The release film (15)-3 is removed from the laminated sheet obtained above, and the exposed surface of the protective film formation film (13)-1, that is, the protective film formation film (13)-1, and the semiconductor wafer The attached surface is the opposite surface, and the maximum section height (Rt) is measured in accordance with JIS B 0601:2013. The results are shown in Table 2. In Table 2, the values shown in the "Rt" column are the above-mentioned measured values.

(The gloss value of the surface of the film for forming a protective film on the opposite side to the surface attached to the semiconductor wafer)

Using a gloss meter (gloss meter "VG 2000" manufactured by Nippon Denshoku Co., Ltd.), in accordance with JIS K 7105, the obtained protective film formation film (13)-1 was measured from the side opposite to the side where the semiconductor wafer was attached. Regarding the attachment surface of the semiconductor wafer, the 60° specular gloss of the surface on the opposite side, and the measured value was taken as the gloss value of the aforementioned surface of the protective film formation film (13)-1. The results are shown in Table 2.

(The maximum cross-sectional height (Rt) of the surface of the protective film on the opposite side to the attachment surface to the semiconductor wafer)

An ultraviolet irradiation apparatus (manufactured by the Lintec Company "RAD2000m / 8"), at 170mJ / cm Condition ² is to the illuminance of 195mW / cm ^2, light amount obtained as described above the protection film forming film (13) -1 irradiated with ultraviolet rays, This hardens the film (13)-1 for forming a protective film to form a protective film.

Next, for the formed protective film, according to JIS B 0601: 2013 The maximum cross-sectional height (Rt) of the surface on the opposite side to the surface to which the semiconductor wafer is attached is measured. The results are shown in Table 2.

(The gloss value of the surface of the protective film on the opposite side to the surface attached to the semiconductor wafer)

When measuring the above-mentioned maximum cross-sectional height (Rt), a gloss meter (gloss meter "VG 2000" manufactured by Nippon Denshoku Co., Ltd.) is used. According to JIS K 7105, the protective film is measured from the side opposite to the side where the semiconductor wafer is attached. The attaching surface of the wafer is the 60° specular gloss of the surface on the opposite side, and the measured value is taken as the gloss value of the aforementioned surface of the protective film. The results are shown in Table 2.

(Visibility of laser printing on protective film)

In the laminated sheet obtained above, the protective film formation film (13)-1 was cured by the same method as in the case of Example 1 to form a protective film.

Next, using a printing device ("MD-S9910A" manufactured by KEYENCE), under the conditions of an output of 1.2W, a frequency of 40kHz, and a scanning speed of 100mm/sec, from the protective film on the opposite side of the semiconductor wafer attachment surface The surface of the protective film is irradiated with laser light with a wavelength of 532nm to perform laser printing.

The printing on the protective film was visually observed through the release film (15)-3, and the laser printing visibility of the protective film was evaluated by the same method as in the case of Example 1. The results are shown in Table 2.

<Production of protective film formation film, and protective film formation film and protection Evaluation of protective film>

[Example 4]

The release film (15)-4 was used instead of the release film (15)-3. Except for this point, the same method as in Example 3 was used to produce a protective film forming film and a laminate sheet, and the protective film forming film and protective The film is evaluated. The composition for forming a protective film (IV-1) was applied to the surface of the release film (15)-4 where the maximum cross-sectional height (Rt) was 8.0 μm. In addition, the exposed surface of the film (13)-1 for forming a protective film was bonded to the peeling treatment surface of the peeling film (15)-1. The results are shown in Table 2.

<Production of protective film formation film and protective film formation composite sheet, and evaluation of protective film formation film and protective film>

[Comparative Example 1]

The base material (91)-1 was used instead of the base material (11)-1. Except for this point, the protective film formation film and the protective film formation composite sheet were manufactured by the same method as in Example 1, and the protective film Evaluate with film and protective film. The composition (IV-1) for forming a protective film was applied to the surface of the substrate (91)-1 with a maximum cross-sectional height (Rt) of 12.0 μm. The results are shown in Table 3.

[Comparative Example 2]

The base material (91)-2 was used instead of the base material (11)-1. Except for this point, the protective film formation film and the protective film formation composite sheet were produced by the same method as in Example 1, and the protective film Evaluate with film and protective film. The composition for forming a protective film (IV-1) is the largest one applied to the substrate (91)-2 The cross-sectional height (Rt) is one surface of 16.0 μm. The results are shown in Table 3.

<Production of protective film formation film, and evaluation of protective film formation film and protective film>

[Comparative Example 3]

The release film (95)-1 was used instead of the release film (15)-3. Except for this point, the same method as in Example 3 was used to produce a protective film forming film and a laminate sheet, and the protective film forming film and protective The film is evaluated. The composition (IV-1) for forming a protective film was applied to the surface of the release film (95)-1 where the maximum cross-sectional height (Rt) was 12.0 μm. In addition, the exposed surface of the film (13)-1 for forming a protective film was bonded to the peeling treatment surface of the peeling film (15)-1. The results are shown in Table 3.

[Comparative Example 4]

The release film (95)-2 was used instead of the release film (15)-3. Except for this point, the same method as in Example 3 was used to produce a protective film forming film and a laminate sheet, and the protective film forming film and protective The film is evaluated. The composition (IV-1) for forming a protective film was applied to the surface of the release film (95)-2 with a maximum cross-sectional height (Rt) of 16.0 μm. In addition, the exposed surface of the film (13)-1 for forming a protective film was bonded to the peeling treatment surface of the peeling film (15)-1. The results are shown in Table 3.

[Reference example 1]

<Production of protective film forming film>

(Manufacturing of protective film forming composition)

Make polymer (b)-2, epoxy resin (h1)-1, epoxy resin (h1)-2, epoxy resin (h1)-3, thermosetting agent (h2)-1, hardening accelerator (i) )-1, filler (d)-2, coupling agent (e)-2, and coloring agent (g)-2, so that the content of these (solid content, parts by mass) becomes the value shown in Table 1 , Dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to prepare a protective film forming composition with a solid content of 50% by mass. Epoxy resin (h1)-1, epoxy resin (h1)-2, epoxy resin (h1)-3, and thermosetting agent (h2)-1 are thermosetting components (h), and the obtained composition It is a composition for forming a thermosetting protective film.

Using the thermosetting protective film forming composition obtained above, except for this point, the protective film forming film (93)-1 and the laminated sheet were produced by the same method as in Example 3.

<Evaluation of protective film formation film and protective film>

Using the same method as in the case of Example 3, the maximum cross-sectional height (Rt) of the protective film formation film and the protective film on the opposite side to the surface of the semiconductor wafer and the protective film formation film were measured And the gloss value of the surface of the protective film on the opposite side to the surface attached to the semiconductor wafer. The results are shown in Table 3.

In the laminated sheet obtained above, the protective film forming film (93)-1 was heated at 130°C for 2 hours to harden the protective film forming film (93)-1 to form Into a protective film.

Next, using the same method as in the case of Example 3, laser printing was performed on the protective film, and the visibility of the laser printing was evaluated. The results are shown in Table 3.

It is clear from the above results that when the protective film formation films of Examples 1 to 4 are used, when the maximum cross-sectional height (Rt) of the surface (β') of the protective film is 7.5 μm or less, the protective film The visibility of laser printing is excellent. It was confirmed that the maximum cross-sectional height (Rt) of the surface (β) of the protective film formation films of Examples 3 to 4 was as small as 7.7 μm or less.

In addition, when the protective film formation films of Examples 1 to 4 are used, the maximum cross-sectional height (Rt) of the surface (β') of the protective film is as small as 0.8 μm to 7.5 μm. , The gloss value of the surface (β') of the protective film is sufficiently large, ranging from 50 to 90.

In contrast, when the protective film formation films of Comparative Examples 1 to 4 are used, the maximum cross-sectional height (Rt) of the surface (β') of the protective film is 11.4μm or more, so the laser printing of the protective film The visibility is poor. It was confirmed that the surface (β) of the protective film formation film of Comparative Example 3 to Comparative Example 4 was the most The large section height (Rt) is large, 11.5 μm or more.

In addition, when the protective film formation film of Comparative Example 1 to Comparative Example 4 is used, the maximum cross-sectional height (Rt) of the surface (β') of the protective film is as large as 11.4 μm to 15.1 μm. , The surface (β') of the protective film has a small gloss value of 23-30.

On the other hand, the maximum cross-sectional height (Rt) of the surface (β) of the film for forming a protective film of Reference Example 1 was as small as 0.8 μm. However, since the protective film is hardened by heating to form a protective film, although the maximum cross-sectional height (Rt) of the surface (β') of the protective film is limited to 5.5 μm, the gloss value is as small as 40, so The visibility of the laser printing on the protective film is poor. The reason is that defects (including the deterioration of constituent components, etc.) occur in the protective film due to heat curing as described above.

(Industrial availability)

The present invention can be used to manufacture semiconductor devices.

1C‧‧‧Composite sheet for forming protective film

10‧‧‧Support film

10a‧‧‧(supporting film) surface

11‧‧‧Substrate

11a‧‧‧(of the substrate) surface

13‧‧‧Film for forming protective film

13a‧‧‧(The surface of the protective film forming film) (1st side)

13b‧‧‧(The surface of the protective film forming film)

15‧‧‧Peeling film

16‧‧‧Adhesive layer for fixture

16a‧‧‧(Adhesive layer for jig) surface

Claims (3)

A film for forming a protective film, which is an energy-ray curable protective film forming film; the maximum cross-sectional height of at least one surface (β') of the protective film when the film for forming a protective film is irradiated with energy rays to become a protective film (Rt) is less than 10 μm; the gloss value of the aforementioned surface (β') is 45 or more. The film for forming a protective film according to claim 1, wherein the maximum cross-sectional height (Rt) of at least one surface (β) of the film for forming a protective film is less than 10 μm, and the surface (β) is formed on the protective film When the film is irradiated with energy rays to become a protective film, it becomes the surface (β') of the protective film. A composite sheet for forming a protective film, which is provided with a supporting sheet and the protective film forming film as described in claim 1 or 2 on the supporting sheet; the surface (β) of the protective film forming film is opposed to the supporting sheet The surface (β) is a surface that becomes the surface (β′) of the protective film when the film for forming a protective film is irradiated with energy rays to become a protective film.

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