TW202100629A - Thermosetting resin film, first protective film forming sheet, kit, and method for manufacturing first protective film-attached workpiece - Google Patents

Abstract

Provided is a thermosetting resin film for forming a first protective film on a surface, having a protruding electrode, of a workpiece by being attached to the surface and thermally cured, wherein the maximum bent amount of the entire periphery of the thermosetting resin film is 20 mm or less after the thermosetting resin film is adhered to a circular copper foil having a thickness of 35 [mu]m and a diameter of 8 inch, and is thermally cured and left cooled in a flat state while the copper foil faces downward.

Description

Method for manufacturing thermosetting resin film, sheet for forming first protective film, kit, and workpiece with first protective film

The present invention relates to a method for manufacturing a thermosetting resin film, a sheet for forming a first protective film, a kit, and a workpiece with a first protective film. This application claims priority based on Japanese Patent Application No. 2019-061707 filed in Japan on March 27, 2019, and the content of the application is cited herein.

Previously, when mounting a multi-pin LSI (Large Scale Integration; large integrated circuit) package used in MPU (Micro Processor Uint) or gate arrays on a printed wiring board, The following flip-chip mounting method is adopted: using a workpiece (such as a semiconductor wafer, etc.) with protruding electrodes (such as bumps, pillars, etc.), the workpiece is processed (such as a semiconductor wafer) by the so-called face down method. The protruding electrodes in the semiconductor wafers, etc.) of the wafer divisions are in opposed contact with the corresponding terminals on the substrate, and are melted/diffusion bonded.

In the case of this mounting method, for the purpose of protecting the circuit surface of the workpiece and the protruding electrode, a curable resin film is sometimes attached to the surface of the protruding electrode and the circuit surface of the workpiece to harden the film. A protective film is formed on the surface. In addition, in this specification, the surface of the protruding electrode and the circuit surface of the workpiece or workpiece may be collectively referred to as the "protruding electrode forming surface".

The curable resin film is usually affixed to the protruding electrode forming surface of the workpiece in a softened state by heating. Thereby, the upper part including the head part of the protruding electrode penetrates the curable resin film and protrudes from the curable resin film. On the other hand, the curable resin film spreads between the protruding electrodes in such a way as to cover the protruding electrodes of the workpiece, is in close contact with the circuit surface and covers the surface of the protruding electrodes, especially the surface of the vicinity of the circuit surface. The protruding electrode is buried. Then, the curable resin film cures to coat the circuit surface of the workpiece and the surface of the vicinity of the circuit surface of the protruding electrode, and becomes a protective film that protects these areas (in this specification, sometimes referred to as the "first protective film" ").

In the case of using a semiconductor wafer, the semiconductor wafer used in the mounting method is obtained, for example, by the following method: the surface of the semiconductor wafer on which the protruding electrode is formed on the circuit surface is opposite to the aforementioned circuit surface Divide by grinding or cutting. In the process of obtaining such a semiconductor wafer, usually for the purpose of protecting the circuit surface and the protruding electrode of the semiconductor wafer, a curable resin film is attached to the protruding electrode forming surface, and the curable resin film is cured to prevent the protrusion A first protective film is formed on the surface where the electrode is formed. The semiconductor wafer obtained here is sometimes referred to as a "semiconductor wafer with a first protective film". Furthermore, the semiconductor wafer with the first protective film is divided and finally becomes a semiconductor wafer with a protective film on the protruding electrode formation surface (in this specification, it may be referred to as "the semiconductor wafer with the first protective film") (refer to Patent Document 1).

This kind of workpiece processing product provided with a first protective film on the protruding electrode forming surface (in this specification, sometimes referred to as "the workpiece processing product with the first protective film") is mounted on a substrate to become a package, and then used This package constitutes the target device. When the semiconductor chip with the first protective film is mounted on the substrate, the semiconductor package obtained thereby is used to construct the target semiconductor device. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2017/078056.

[The problem to be solved by the invention]

In the case of using the conventional curable resin film represented by the curable resin film disclosed in Patent Document 1, the curable resin film is attached to the protruding electrode forming surface of the semiconductor wafer and then cured by heat In the process of forming the protective film on the protruding electrode formation surface of the semiconductor wafer, warpage may occur in the semiconductor wafer. In this way, if warpage occurs in the semiconductor wafer, for example, air leakage occurs when the semiconductor wafer is sucked by a vacuum device. Therefore, in the manufacturing steps of semiconductor wafers that use a vacuum method, there are semiconductor wafers. The problem of obstacles to the transportation.

Therefore, the object of the present invention is to provide a thermosetting resin film capable of forming a first protective film for protecting a wafer-shaped workpiece or a protruding electrode forming surface of a workpiece processed object, and the thermosetting resin film When the first protective film is formed by attaching it to the surface with the protruding electrode in the workpiece and thermally hardening it to form the first protective film, the first protective film can be formed in a state where the warpage of the wafer-shaped workpiece is suppressed. [Means to solve the problem]

The present invention provides a thermosetting resin film, which is used to adhere to a surface of a workpiece with protruding electrodes and heat-cured to form a first protective film on the surface, and to attach the thermosetting resin film to A round copper foil with a thickness of 35 μm and a diameter of 8 inches, with the copper foil on the lower side in a flat state, the thermosetting resin film is thermally cured and the maximum warpage of the entire circumference after cooling is 20 mm or less.

In addition, the present invention provides a thermosetting resin film, which is used to adhere to a surface of a workpiece with protruding electrodes and heat-cured to form a first protective film on the surface, and the thermosetting resin film contains For thermosetting components other than acrylic resin having epoxy groups with a weight average molecular weight greater than 10,000, for the thermosetting components contained in the thermosetting resin film, X calculated by the following formula is obtained for each type When the total value of the X value in all types of the thermosetting components contained in the thermosetting resin film is obtained, the total value becomes 300 g/eq or more. X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components].

In addition, the present invention provides a first protective film forming sheet including a first support sheet and the thermosetting resin film on one surface of the first support sheet.

In addition, the present invention provides a kit including the thermosetting resin film and a second protective film forming film for attaching to the inner surface of the workpiece opposite to the surface having the protruding electrode.

In addition, the present invention provides a method of manufacturing a workpiece with a first protective film, including: attaching the thermosetting resin film to the surface of the workpiece with protruding electrodes; and curing the attached heat The step of thermally curing the flexible resin film to form the first protective film; and the step of dividing the workpiece and cutting the first protective film. [Invention Effect]

According to the present invention, there is provided a thermosetting resin film capable of forming a first protective film for protecting a wafer-shaped workpiece or a protruding electrode forming surface of a workpiece processed object, and attaching the thermosetting resin film to When the surface of the wafer-shaped workpiece having protruding electrodes is thermally cured to form the first protective film, the first protective film can be formed in a state where the warpage of the wafer-shaped workpiece is suppressed.

◇ Sheet for forming thermosetting resin film and first protective film The thermosetting resin film of one embodiment of the present invention is used to stick to the surface of the workpiece with protruding electrodes and heat-cured to form a first protective film on the surface, and to paste the thermosetting resin film Attached to a round copper foil with a thickness of 35μm and a diameter of 8 inches, the copper foil is placed on the lower side in a flat state, and the thermosetting resin film is thermally cured and the maximum warpage of the entire circumference after cooling is 20mm or less .

The first protective film forming sheet includes a first support sheet, and the thermosetting resin film on one surface of the first support sheet. In the first protective film forming sheet, by making the maximum warpage of the thermosetting resin film 20 mm or less, the first protective film after heat curing protects the circuit surface and the protruding electrode of the workpiece At this time, the effect of suppressing the warpage of the wafer-shaped workpiece is excellent.

In addition, the thermosetting resin film of one embodiment of the present invention is used to adhere to the surface of the workpiece with protruding electrodes and heat-cured to form a first protective film on the surface, and the thermosetting resin film Contains thermosetting components other than acrylic resins with epoxy groups with a weight average molecular weight greater than 10,000. The thermosetting components contained in the thermosetting resin film are calculated by the following formula for each type The X value, when the total value of the X value in all types of the thermosetting components contained in the thermosetting resin film is obtained, the total value becomes 300 g/eq or more. X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components].

In addition, when the aforementioned first protective film formation sheet becomes 300 g/eq or more in the aforementioned total value, it can be cooled to room temperature after the thermosetting resin film is attached to the protruding electrode formation surface and thermally cured. The first protective film is formed in a state where the warpage of the wafer-shaped workpiece is suppressed. Here, the total value of the aforementioned X values defines the amount of thermosetting components per crosslinking point. The smaller the value, the greater the warpage after thermal curing. On the contrary, the greater the total value of the aforementioned X values, the wafer The warpage of the shape of the workpiece is suppressed more. In addition, it is believed that thin and easily bendable materials such as copper foil are easily affected. In addition, in this specification, the term "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, etc.

In addition, the first protective film forming sheet according to one embodiment of the present invention includes a first support sheet and the thermosetting resin film as described in claim 1 or 2 on one of the first support sheets. In the sheet for forming the first protective film, the "thermosetting resin film" may also be referred to as the "thermosetting resin layer".

In this embodiment, as the workpiece, for example, a semiconductor wafer or the like can be cited. As the workpiece to be processed, for example, a semiconductor wafer, which is a divided object of a semiconductor wafer, can be cited. The processing of the workpiece includes, for example, division. Examples of the protruding electrode include bumps and pillars. The protruding electrode is set on the connection pad of the workpiece, and is composed of eutectic solder, high temperature solder, gold or copper, etc.

The aforementioned first protective film forming sheet is attached to the projecting electrode forming surface of the workpiece (that is, the surface of the projecting electrode and the circuit surface of the workpiece) via the thermosetting resin film (thermosetting resin layer) of the sheet. use. Furthermore, the fluidity of the attached thermosetting resin film is increased by heating, and the protruding electrode, including the upper part of the head, penetrates the thermosetting resin film and protrudes from the thermosetting resin film. Furthermore, the thermosetting resin film spreads between the protruding electrodes so as to cover the protruding electrodes, is in close contact with the circuit surface, and covers the surface of the protruding electrode, especially the surface near the circuit surface, and the protrusion Shaped electrodes are buried. The thermosetting resin film in this state is further cured by heating, and finally a first protective film is formed, which is protected in a state where the first protective film is in close contact with the circuit surface and the protruding electrode. In this way, by using the thermosetting resin film of this embodiment, the circuit surface of the workpiece and the portion (base) near the circuit surface of the protruding electrode are sufficiently protected by the first protective film.

For the workpiece after the first protective film formation sheet is attached, for example, if necessary, the surface opposite to the aforementioned circuit surface is ground, and then the first support sheet is removed, and then heated by the thermosetting resin film The resulting protruding electrode is embedded and the first protective film is formed. Furthermore, the work is divided (that is, singulated into a work piece) and the first protective film is cut, and the work piece obtained by using the work piece having the cut first protective film on the protruding electrode forming surface ( In this specification, it may be referred to as "workpiece with a first protective film") to manufacture target substrate devices such as semiconductor devices. These steps will be described in detail later.

In addition, in this specification, unless otherwise specified, when only the "curable resin film" is described, it means "the curable resin film before curing", and when only the "curable resin layer" is described, it means "curing Front curable resin layer". For example, the "thermosetting resin film" means "the thermosetting resin film before curing", and the "first protective film" means the cured product of the thermosetting resin film.

[The ratio of the total content of all types of thermosetting components] In the aforementioned thermosetting resin film, the "thermosetting component" that defines the ratio of the above-mentioned total content is a component that shows a curing reaction by heating. In addition, polymer components with a weight average molecular weight (Mw) greater than 10,000 are not included in the thermosetting components. As a thermosetting component, the thermosetting component (B) mentioned later is mentioned, for example. Examples of the thermosetting component (B) include epoxy-based thermosetting resins, acrylic resins having epoxy groups having a weight average molecular weight of 10,000 or less, polyimide resins, unsaturated polyester resins, and the like. The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2), and both of these two components become the target of the above-mentioned total content ratio. On the other hand, as an acrylic resin having an epoxy group with a weight average molecular weight greater than 10,000 that is not contained in the thermosetting component, for example, the acrylic resin in the polymer component (A) described later has an epoxy group and has an average weight Acrylic resin with molecular weight greater than 10,000. For example, acrylic resins having glycidyl groups with a weight average molecular weight greater than 10,000 are included in acrylic resins having epoxy groups.

The said thermosetting component contained in the said thermosetting resin film is 2 or more types, and the combination and ratio of these can be selected arbitrarily.

The ratio of the total content of all types of thermosetting components in the thermosetting resin film to the total mass of the thermosetting resin film ([Total of all types of thermosetting components in the thermosetting resin film The content (parts by mass)]/[total mass (parts by mass) of the thermosetting resin film]×100) is preferably 40% by mass or more. Here, the total content (parts by mass) of all types of thermosetting components means the total content (parts by mass) of all types of thermosetting components of two or more types.

By satisfying the condition of the ratio of the aforementioned total content, the adhesion of the thermosetting resin film to the protruding electrode forming surface becomes good, and after being cured by heat to become the first protective film, the circuit can be protected well Surface and electrode base, and it is not easy to hinder the electrical connection between the electrode and the substrate.

In terms of obtaining the aforementioned advantageous effects more significantly, the ratio of the total content of all types of the thermosetting components in the thermosetting resin film to the total mass of the thermosetting resin film may be, for example, 50 mass. % Or more, 60% by mass or more, 70% by mass or more, and 80% by mass or more.

The upper limit of the ratio of the aforementioned total content is not particularly limited. For example, in terms of making the film forming properties of the thermosetting resin film more favorable, the ratio of the aforementioned total content is preferably 99% by mass or less.

The ratio of the aforementioned total content can be appropriately adjusted to be within a range set by arbitrarily combining the aforementioned lower limit and upper limit. For example, in one embodiment, the proportion of the aforementioned total content may be 40% to 99% by mass, 50% to 99% by mass, 60% to 99% by mass, 70% to 99% by mass, and 80% by mass. Any one to 99% by mass.

[Total value of X value] The aforementioned X value is calculated by the aforementioned formula for one type of thermosetting component contained in the aforementioned thermosetting resin film. The "thermosetting component" that is the calculation target of the aforementioned X value is the same as the "thermosetting component" that defines the ratio of the above-mentioned total content in the aforementioned thermosetting resin film.

The so-called "functional group related to the thermosetting reaction of the thermosetting component" used to calculate the X value is, for example, an epoxy group in the case of the epoxy resin (B1) described later, and the functional group of the thermosetting agent (B2) described later In the case, it is a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid group formed by anhydride, etc. However, these are examples of the aforementioned functional groups.

Consider the case where the aforementioned thermosetting resin film contains p types (p is an integer of 2 or more) of thermosetting components. _Let these thermosetting components be M ₁ and M _{p for} each type. In addition, the equivalent of the functional group of the thermosetting component M ₁ is m ₁ (g/eq), the equivalent of the functional group of the thermosetting component M _p is m _p (g/eq), and the thermal The content of the thermosetting component M ₁ of the curable resin film is C ₁ (parts by mass), and the content of the thermosetting component M _p of the thermosetting resin film is C _p (parts by mass). At this time, regarding the thermosetting component M ₁ , the aforementioned X value (hereinafter referred to as "X ₁ value") is calculated by the following formula.

[Number 1]

Similarly, regarding the thermosetting component M _p , the aforementioned X value (hereinafter referred to as "X _p value") is also calculated by the following formula.

[Number 2]

In addition, the total value of the aforementioned X values (X ₁ ,..., Xp) in all types of thermosetting components (M ₁ , ..., M _P ) contained in the aforementioned thermosetting resin film is as follows .

[Number 3]

When the equivalent weight (m ₁ , m _p (g/eq)) of the functional group of the thermosetting component is not specific to a fixed value, but is specified in a certain numerical range, as long as the lower value of the numerical range is used The average value calculated by the limit value and the upper limit value may be used as the equivalent of the functional group.

In the thermosetting resin film, the total value of the X value is preferably 300 g/eq or more. By satisfying the condition of the total value of the aforementioned X values, when the thermosetting resin film is attached to the protruding electrode forming surface and thermally cured and then left to cool to room temperature, the wafer-shaped workpiece can be warped The first protective film is formed in a state where kinks are suppressed.

In terms of obtaining the aforementioned advantageous effects more remarkably, in the thermosetting resin film, the total value of the aforementioned X values may be any of 305 g/eq or more and 315 g/eq or more, for example.

In order to heat the thermosetting resin film so that the first protective film can well protect the protruding electrode forming surface of the workpiece, the total value of the X value is preferably 3000 g/eq or less, more preferably 2000 g/eq or less , Particularly preferably 1500g/eq or less, for example, 500g/eq or less.

The total value of the aforementioned X values can be appropriately adjusted to be within a range set by arbitrarily combining the aforementioned lower limit and upper limit. For example, in one embodiment, the total value of the aforementioned X value may be 300g/eq to 3000g/eq, 305g/eq to 3000g/eq, 305g/eq to 1500g/eq, 315g/eq to 1500g/eq, 300g/eq Any one of to 500g/eq, and 315g/eq to 500g/eq.

In workpieces and workpieces with protruding electrodes on the circuit surface, the surface (inner surface) opposite to the circuit surface may be exposed. Therefore, a protective film containing an organic material may be formed on the inner surface (in this specification, to distinguish it from the first protective film, it may be referred to as a "second protective film"). The second protective film is used to prevent cracks in the workpiece after the workpiece is divided or packaged. Such a workpiece with a second protective film provided on the inner surface of the workpiece is finally incorporated into a target substrate device such as a semiconductor device. On the other hand, the second protective film is sometimes required to be able to use laser light to mark information related to the workpiece, or to conceal the inner surface of the workpiece. As a film satisfying such a requirement, a curable resin film capable of forming a second protective film by curing and adjusting light transmission characteristics is known. However, since the second protective film for protecting the inner surface of the workpiece and the first protective film for protecting the protruding electrode forming surface of the workpiece are formed at different positions in the workpiece, the required characteristics are Also different from each other. Therefore, it is generally difficult to directly use the thermosetting resin film capable of forming the second protective film for the purpose of forming the first protective film.

FIG. 1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a protruding electrode forming surface using a thermosetting resin film of this embodiment. In addition, in order to facilitate the understanding of the features of the present invention, and for convenience, the drawings used in the following description may be enlarged and displayed important parts, and are not limited to the size ratio of each component being the same as actually.

A plurality of protruding electrodes 91 are provided on the circuit surface 90a of the workpiece 90 shown here. In FIG. 1, the symbol 90b indicates the surface (inner surface) of the workpiece 90 on the opposite side to the circuit surface 90a. The protruding electrode 91 has a shape in which a part of the ball is cut off by a plane, and is in a state where the plane corresponding to the portion exposed by the cut is in contact with the circuit surface 90a of the workpiece 90. The shape of the protruding electrode 91 is substantially spherical.

The first protective film 12' is formed using the thermosetting resin film of this embodiment, and covers the circuit surface 90a of the workpiece 90, and further covers the surface 91a of the protruding electrode 91 except for the top 910 of the protruding electrode 91 and its vicinity Outside the area. In this way, the first protective film 12' is in close contact with the top 910 of the protruding electrode 91 and the surface 91a other than the vicinity thereof, and also in close contact with the circuit surface 90a of the workpiece 90, and the protruding electrode 91 is embedded. The substantially spherical shape of the protruding electrode 91 as described above is particularly advantageous for forming the first protective film using the thermosetting resin film.

The height H _{91 of the} protruding electrode 91 is not particularly limited, but is preferably 50 μm to 500 μm. Since the height H ₉₁ of the protruding electrode 91 is more than the aforementioned lower limit, the function of the protruding electrode 91 can be further improved. Since the height H ₉₁ of the protruding electrode 91 is below the aforementioned upper limit, the thermosetting resin film is applied to the protruding electrode forming surface of the workpiece 90 (that is, the surface 91a of the protruding electrode 91 and the circuit of the workpiece 90). When the surface 90a) is used, the effect of preventing the thermosetting resin film from remaining on the protruding electrode 91 including the top portion 910 becomes higher, and as a result, the effect of suppressing the formation of the first protective film 12' on the upper portion of the protruding electrode 91 becomes higher. Get higher. In addition, in this specification, the "height of the protruding electrode" means the height of the protruding electrode at the position (that is, the top of the head) that is highest from the circuit surface of the workpiece or workpiece.

The width W _{91 of the} protruding electrode 91 is not particularly limited, but is preferably 50 μm to 600 μm. When the width W ₉₁ of the protruding electrode 91 is greater than the aforementioned lower limit, the function of the protruding electrode 91 can be further improved. Since the width W ₉₁ of the protruding electrode 91 is below the aforementioned upper limit, the thermosetting resin film is attached to the protruding electrode forming surface of the workpiece 90 (that is, the surface 91a of the protruding electrode 91 and the circuit of the workpiece 90). When the surface 90a) is used, the effect of preventing the thermosetting resin film from remaining on the protruding electrode 91 including the top portion 910 becomes higher, and as a result, the effect of suppressing the formation of the first protective film 12' on the upper portion of the protruding electrode 91 becomes higher. Get higher. In addition, in this specification, the "width of the protruding electrode" means that when the protruding electrode is viewed from a direction perpendicular to the circuit surface of the workpiece or workpiece, the difference between the protruding electrode surface The maximum value of the line segment obtained by connecting two points with a straight line.

91 adjacent the protruding electrode distance D ₉₁ is not particularly limited, but is preferably 100μm to 800μm. 91 by the distance D between the protruding electrode _{91 is} not less than the lower limit, in the thermosetting resin film is attached to a protruding electrode forming surface of the workpiece 90 (i.e., the surface 91a of the protruding electrode 91 and the workpiece 90 In the case of the circuit surface 90a), the effect of suppressing the thermosetting resin film from remaining on the upper part of the protruding electrode 91 including the top part 910 becomes higher. As a result, the effect of suppressing the formation of the first protective film 12' on the upper part of the protruding electrode 91 Become higher. 91 by the distance D between the protruding electrode ₉₁ as the upper limit, the degree of freedom of shape protruding electrode 91 becomes higher. In addition, in this specification, the "distance between adjacent protruding electrodes" means the minimum value of the distance between the surfaces of adjacent protruding electrodes.

The thickness T ₉₀ of the part of the workpiece 90 other than the protruding electrode 91 may be appropriately selected according to the purpose of use of the workpiece 90 and is not particularly limited. For example, the aforementioned thickness T ₉₀ after grinding the inner surface 90 b of the workpiece 90 is preferably 50 μm to 500 μm. Since the thickness T ₉₀ of the workpiece 90 after grinding the inner surface 90b is more than the aforementioned lower limit, the effect of suppressing the damage of the workpiece when the workpiece 90 is divided (in other words, the workpiece is divided into pieces) higher. When the thickness T ₉₀ of the workpiece 90 after grinding the inner surface 90 b is not _more than the aforementioned upper limit value, a thin workpiece can be obtained. The aforementioned thickness T ₉₀ before grinding the inner surface 90 b of the workpiece 90 is preferably 250 μm to 1500 μm.

The workpiece to be used for the thermosetting resin film of the present embodiment is not limited to the workpiece shown in FIG. 1, and a part of the structure may be changed, deleted, or added within a range that does not impair the effects of the present invention.

For example, in Fig. 1, as the protruding electrode, a protruding electrode having a substantially spherical shape (a shape obtained by cutting a part of the ball in a plane) as described above is shown. In addition, the protruding electrode having a preferable shape can be listed as follows: This roughly spherical shape is elongated in the height direction (in FIG. 1, the direction orthogonal to the circuit surface 90a of the workpiece 90), that is, the shape of an ellipsoid as a roughly long sphere (in other words , As a protruding electrode of an ellipsoid of a long spheroid, a shape obtained by cutting off one end in the long axis direction by a plane); or a shape obtained by squashing the above-mentioned roughly spherical shape in the height direction, that is, as A protruding electrode that is roughly in the shape of an oblate ellipsoid (in other words, a shape in which the part of the oblate ellipsoid including one end in the minor axis direction is cut off by a plane). Such an approximately ellipsoid-shaped projecting electrode is also the same as the aforementioned approximately spherical projecting electrode, and is particularly advantageous for forming the first protective film using the thermosetting resin film of this embodiment. As the protruding electrode, in addition to these, for example, cylindrical, elliptic cylindrical, angular columnar, elliptical cone, pyramid, truncated cone, elliptical frustum or truncated pyramidal protruding electrode; A protruding electrode in the shape of a cylinder, an elliptic column, a corner column, a truncated cone, an elliptical frustum or a pyramid and the above-mentioned roughly spherical or roughly ellipsoidal body. In addition, the shape of the protruding electrode described above is only an example of a preferable shape when the thermosetting resin film of this embodiment is applied, and the shape of the protruding electrode is not limited to these in the present invention. Hereinafter, the structure of the present invention will be described in detail.

◎The first support piece The aforementioned first support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired. In addition, in this specification, it is not limited to the case of the first support sheet. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only some of the layers may be the same." , Furthermore, "a plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

As a preferred first support sheet, for example, a sheet having a first substrate and a first adhesive layer provided on the first substrate (in other words, the first substrate and the first adhesive layer are These layers are laminated in the thickness direction); a sheet comprising a first substrate, a first intermediate layer provided on the first substrate, and a first adhesive layer provided on the first intermediate layer (In other words, the first substrate, the first intermediate layer, and the first adhesive layer are laminated in the thickness direction of these layers in order); a sheet composed of only the first substrate, etc.

Hereinafter, for each type of such a first support sheet, an example of the first protective film forming sheet of this embodiment will be described while referring to the drawings.

Fig. 2 is a cross-sectional view schematically showing an example of the first protective film forming sheet of the present embodiment. The 1st protective film formation sheet 1 shown here uses the sheet which laminated|stacked the 1st base material and the 1st adhesive layer in the thickness direction of these layers as a 1st support sheet. That is, the first protective film forming sheet 1 includes a first substrate 11, a first adhesive layer 13 provided on one side of the first substrate 11, and a first adhesive layer 13 provided on one side of the first substrate 11 (The surface opposite to the side of the first base material 11) is formed by a thermosetting resin layer (thermosetting resin film) 12 on 13a. The first support sheet 101 is a laminate of the first base material 11 and the first adhesive layer 13. In addition, the first protective film forming sheet 1 can be said to include a first support sheet 101 and a thermosetting resin layer provided on one surface 101a of the first support sheet 101, in other words, on one surface 13a of the first adhesive layer 13 12.

The thermosetting resin layer 12 was attached to a round copper foil with a thickness of 35 μm and a diameter of 8 inches, and the copper foil was heated at 130°C for 2 hours in a flat state (to make the thermosetting resin layer 12 The maximum warpage of the entire circumference after thermal curing) and cooling may be 20 mm or less, and the total value of the above X values (the total value of X values in the thermosetting resin layer 12) may be 300 g/eq or less .

Fig. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet of the present embodiment. In addition, in the figures after FIG. 3, 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 components are omitted.

The first protective film forming sheet 2 shown here uses a first base material, a first intermediate layer, and a first adhesive layer that are laminated in the thickness direction of these layers as a first support sheet. That is, the first protective film forming sheet 2 includes a first base material 11, a first intermediate layer 14 provided on one side of the first base material 11, and a first intermediate layer 14 provided on one side (and the first 1) The first adhesive layer 13 on the substrate 11 side is the opposite side) and one of the surfaces of the first adhesive layer 13 (the surface opposite to the first intermediate layer 14 side) 13a. The curable resin layer (thermosetting resin film) 12 is formed. The first support sheet 102 is a laminate of the first base material 11, the first intermediate layer 14 and the first adhesive layer 13. In addition, it can be said that the first protective film forming sheet 2 includes a first support sheet 102, and a thermosetting resin layer 12 is provided on one surface 102a of the first support sheet 102 (in other words, on one surface 13a of the first adhesive layer 13) .

In other words, the first protective film forming sheet 2 is in the first protective film forming sheet 1 shown in FIG. 2, and the first intermediate layer 14 is further provided between the first base material 11 and the first adhesive layer 13 .

The thermosetting resin layer 12 was attached to a round copper foil with a thickness of 35 μm and a diameter of 8 inches, and the copper foil was heated at 130°C for 2 hours in a flat state (to make the thermosetting resin layer 12 The maximum warpage of the entire circumference after thermal curing) and cooling may be 20 mm or less, and the total value of the above X values (the total value of X values in the thermosetting resin layer 12) may be 300 g/eq or less .

4 is a cross-sectional view schematically showing still another example of the first protective film forming sheet of the present embodiment. The first protective film forming sheet 3 shown here uses a sheet composed of only the first base material as the first support sheet. That is, the first protective film forming sheet 3 is configured to include a first base material 11 and a thermosetting resin layer (thermosetting resin film) 12 provided on the first base material 11. The first support sheet 103 is composed of only the first base material 11. In addition, it can be said that the first protective film forming sheet 3 includes a first support sheet 103, and a thermosetting resin layer 12 is provided on one surface 103a of the first support sheet 103 (in other words, on one surface 11a of the first base material 11).

In other words, the first protective film forming sheet 3 is in the first protective film forming sheet 1 shown in FIG. 2, and the first adhesive layer 13 is omitted.

The thermosetting resin layer 12 was attached to a round copper foil with a thickness of 35 μm and a diameter of 8 inches, and the copper foil was heated at 130°C for 2 hours in a flat state (to make the thermosetting resin layer 12 The maximum warpage of the entire circumference after thermal curing) and cooling may be 20 mm or less, and the total value of the above X values (the total value of X values in the thermosetting resin layer 12) may be 300 g/eq or less .

Next, the structure of the first support piece will be described. In this embodiment, as the first support sheet, a known first support sheet can be used, and the first support sheet can be appropriately selected according to the purpose.

○The first base material The first substrate has a sheet shape or a film shape, and as a constituent material of the first substrate, various resins can be cited, for example.

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

The thickness of the first substrate is preferably 50 μm to 200 μm. Here, the "thickness of the first substrate" means the thickness of the entire first substrate. For example, the thickness of the first substrate composed of a plurality of layers means the total of all layers constituting the first substrate thickness.

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

The first substrate may be transparent or opaque, and may be colored according to the purpose, or other layers may be vapor-deposited. In the case where the first adhesive layer or the thermosetting resin layer described later has energy ray curability, the first base material preferably transmits energy rays.

The first base material may be, for example, a release film in which one side of a resin film as described in the following examples is peeled off by a silicone treatment or the like.

The first substrate can be manufactured by a known method. For example, the first substrate containing resin can be produced by molding a resin composition containing the aforementioned resin.

○The first adhesive layer The first adhesive layer has a sheet or film shape and contains an adhesive. Examples of the aforementioned adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates, and acrylic resins are preferred. .

In addition, in the present invention, the concept of "adhesive resin" includes both adhesive resins and adhesive resins. For example, it includes not only resins with adhesive properties, but also resins that are combined with additives and other components. Resin that exhibits adhesiveness, or resin that exhibits adhesiveness by the presence of heat or water triggers.

The first adhesive layer can be only one layer (single layer), or multiple layers of two or more layers. In the case of multiple layers, these multiple layers can be the same or different from each other. There is no special combination of these multiple layers limited.

The thickness of the first adhesive layer is preferably 3 μm to 40 μm. Here, the "thickness of the first adhesive layer" means the thickness of the entire first adhesive layer. For example, the thickness of the first adhesive layer composed of multiple layers means the thickness of the first adhesive layer. The total thickness of all layers.

The first adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. The first adhesive layer formed using an energy-ray curable adhesive can easily adjust the physical properties before and after curing. In this specification, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum, and examples of the energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can irradiate an electron beam generated by an electron beam accelerator or the like. . In the present invention, the "energy ray curability" refers to the property of curing by irradiation with energy rays, and the term "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

[First adhesive composition] The first adhesive layer can be formed using a first adhesive composition containing an adhesive. For example, by coating the first adhesive composition on the surface to be formed of the first adhesive layer, and drying it as necessary, the first adhesive layer can be formed on the target site. A more specific method of forming the first adhesive layer will be described in detail later together with methods of forming other layers.

The first adhesive composition can 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, touch coater, etc.

The drying conditions of the first adhesive composition are not particularly limited, and when the first adhesive composition contains a solvent, it is preferable to heat and dry. The first adhesive composition containing the solvent may be dried under the conditions of, for example, 70°C to 130°C and 10 seconds to 5 minutes.

When the first adhesive layer is energy ray curable, as the first adhesive composition containing energy ray curable adhesive (energy ray curable first adhesive composition), for example, the following 1 Adhesive composition, etc.: The first adhesive composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)" ) And an energy ray curable compound; the first adhesive composition (I-2) contains an energy ray curable adhesive resin (I) with unsaturated groups introduced into the side chain of the adhesive resin (I-1a) -2a) (hereinafter sometimes referred to as "adhesive resin (I-2a)"); the first adhesive composition (I-3), containing the aforementioned adhesive resin (I-2a) and energy-ray curable low molecular weight Compound.

[The first adhesive composition (I-1) to the first adhesive composition other than the first adhesive composition (I-3)] The ingredients contained in the first adhesive composition (I-1), the first adhesive composition (I-2), or the first adhesive composition (I-3) can also be used for these three types of first adhesives in the same way All the first adhesive composition other than the adhesive composition (in this specification, referred to as "the first adhesive composition (I-1) to the first adhesive composition other than the first adhesive composition (I-3)物").

As the first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3), in addition to the energy-ray curable adhesive composition, non-energy Linear hardening adhesive composition. As the non-energy-ray curable first adhesive composition, for example, the first adhesive composition (I-4) containing the aforementioned adhesive resin (I-1a) can be cited. The first adhesive composition (I-4) preferably contains an acrylic resin as the adhesive resin (I-1a), and more preferably further contains one or more crosslinking agents.

[First manufacturing method of adhesive composition] The aforementioned first adhesive composition such as the first adhesive composition (I-1) to the first adhesive composition (I-4) is used by mixing the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive. Obtained by each component constituting the first adhesive composition. The order of addition when formulating each component is not particularly limited, and two or more components may be added at the same time. In the case of using a solvent, it can be used in the following manner: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; or, pre-diluting any compounding component other than the solvent The solvent is mixed with these formulation ingredients. The method of mixing the ingredients during the preparation is not particularly limited, and can be appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves for mixing The method and so on. Regarding the temperature and time at the time of adding and mixing each component, the temperature and time are not particularly limited as long as each compounding component is not degraded, and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

○The first middle layer The first intermediate layer has a sheet shape or a film shape, and the constituent material of the first intermediate layer may be appropriately selected according to the purpose, and is not particularly limited. For example, when the purpose is to suppress the deformation of the first protective film due to the shape of the protruding electrode existing on the aforementioned circuit surface being reflected on the first protective film provided on the protruding electrode forming surface, it is regarded as the aforementioned first protective film. Preferred constituent materials of the intermediate layer include (meth)acrylate urethane and the like in terms of further improving the adhesion of the first intermediate layer.

The first intermediate layer may 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 the combination of these multiple layers is not particularly limited .

The thickness of the first intermediate layer can be suitably adjusted according to the height of the protruding electrode existing on the surface of the workpiece or workpiece to be protected. For example, the thickness of the first intermediate layer is preferably 50 μm to 600 μm in terms of being able to easily absorb the influence of the protruding electrode having a relatively high height. Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer. For example, the thickness of the first intermediate layer composed of a plurality of layers means the total of all the layers constituting the first intermediate layer thickness.

[First Intermediate Layer Formation Composition] The first intermediate layer can be formed using the first intermediate layer forming composition containing the constituent material of the first intermediate layer. For example, the first intermediate layer forming composition is applied to the surface to be formed of the first intermediate layer, dried as necessary or hardened by irradiating energy rays, whereby the first intermediate layer can be formed on the target site. A more specific method of forming the first intermediate layer will be described in detail later together with methods of forming other layers.

The composition for forming the first intermediate layer can be applied, for example, by the same method as in the case of the first adhesive composition.

The drying conditions of the first intermediate layer forming composition are not particularly limited, and, for example, may be the same as the drying conditions of the first adhesive composition. When the composition for forming the first intermediate layer has energy ray curability, it may be cured by irradiating energy ray after drying.

[Method for manufacturing first intermediate layer forming composition] The composition for forming the first intermediate layer can be manufactured by the same method as in the case of the first adhesive composition described above, except for the point that the compounding components are different, for example.

◎Thermosetting resin film (thermosetting resin layer) The aforementioned thermosetting resin film (thermosetting resin layer) is a film (layer) for protecting the circuit surface of the workpiece and the workpiece and the protruding electrode provided on the circuit surface. The thermosetting resin film is cured by heat to form a first protective film.

In addition, in this specification, even after the thermosetting resin film is cured (in other words, after the first protective film is formed), only the first support sheet and the cured product of the thermosetting resin film (in other words, the first support sheet and The layered structure of the first protective film) is still referred to as the "sheet for forming a first protective film".

The aforementioned thermosetting resin film may have or not have energy ray curability properties in addition to thermosetting properties. However, when the thermosetting resin film has the characteristics of energy ray curability, for the first protective film formed from the thermosetting resin film, the contribution of the thermosetting resin film is greater than the contribution of the energy ray curing .

The aforementioned thermosetting resin film may be composed of one layer (single layer) regardless of whether it has energy ray curability or not, or may be composed of two or more layers. When the thermosetting resin film is composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

The thickness of the thermosetting resin film is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and particularly preferably 5 μm to 60 μm, regardless of whether it has energy ray curability. When the thickness of the thermosetting resin film is greater than or equal to the aforementioned lower limit, it is possible to form a first protective film with higher protective ability. When the thickness of the thermosetting resin film is less than the aforementioned upper limit, when the thermosetting resin film is attached to the protruding electrode forming surface of the workpiece, the effect of preventing the thermosetting resin film from remaining on the protruding electrode Become higher. Furthermore, when the thickness of the thermosetting resin film is equal to or less than the aforementioned upper limit, the first protective film can be cut more satisfactorily when the work is divided. Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film. For example, the thickness of the thermosetting resin film composed of a plurality of layers means the thickness of the thermosetting resin film. The total thickness of all layers.

[Composition for forming thermosetting resin layer] The thermosetting resin film can be formed using a composition for forming a thermosetting resin layer containing the constituent material of the thermosetting resin film. For example, a thermosetting resin film can be formed by applying a composition for forming a thermosetting resin layer on the surface to be formed of the thermosetting resin film, and drying if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the composition for forming a thermosetting resin layer is usually the same as the ratio of the contents of the aforementioned components in the thermosetting resin film.

The composition for forming a thermosetting resin layer may be applied by a known method, for example, methods using various coating machines such as air knife coater, knife coater, bar coater, gravure coating Machine, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coating Machine waiting.

Regarding the drying conditions of the composition for forming a thermosetting resin layer, there is no particular limitation regardless of whether the thermosetting resin film has energy ray curability. However, when the composition for forming a thermosetting resin layer contains a solvent described later, it is preferable to heat and dry. The composition for forming a thermosetting resin layer containing a solvent may be dried under the conditions of, for example, 70°C to 130°C and 10 seconds to 5 minutes. However, the composition for forming a thermosetting resin layer is preferably heated and dried so that the composition itself and the thermosetting resin film formed from the composition are not thermally cured.

Regarding the curing conditions when the thermosetting resin film is thermally cured to form the first protective film, the curing conditions are not particularly limited as long as the first protective film has a degree of curing sufficient to perform the function of the first protective film. What is necessary is just to select suitably according to the kind of thermosetting resin film. For example, the heating temperature during thermal curing of the thermosetting resin film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. In addition, the heating time during the thermal curing is preferably 0.5 hour to 5 hours, more preferably 0.5 hour to 4 hours, and particularly preferably 1 hour to 3 hours.

As a preferable thermosetting resin film, a film containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component that can undergo a hardening (polymerization) reaction using heat as a trigger of the reaction. In addition, in this specification, the polycondensation reaction is also included in the polymerization reaction.

[Composition for forming thermosetting resin layer (III-1)] As a preferable composition for forming a thermosetting resin layer, for example, a composition for forming a thermosetting resin layer (III-1) containing the aforementioned polymer component (A) and a thermosetting component (B) (this In the specification, it may be simply referred to as "composition (III-1)").

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties and flexibility to the thermosetting resin film. The polymer component (A) has thermoplasticity and does not have thermosetting properties. The polymer component (A) contained in the composition (III-1) and the thermosetting resin film may be one type or two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary select.

Examples of the polymer component (A) include polyvinyl acetals, acrylic resins, urethane resins, phenoxy resins, polysiloxane resins, saturated polyester resins, and the like. Among these, the polymer component (A) is preferably polyvinyl acetal or acrylic resin.

As said polyvinyl acetal in a polymer component (A), a well-known polyvinyl acetal is mentioned. Among them, preferred polyvinyl acetals include polyvinyl formal, polyvinyl butyral, and the like, and polyvinyl butyral is more preferable. Examples of polyvinyl butyral include polyvinyl butyral having structural units represented by the following formula (i)-1, formula (i)-2, and formula (i)-3.

(式中，l、m及n分別獨立且為1以上之整數)[化1]

(In the formula, l, m and n are independent and an integer of 1 or more)

The weight average molecular weight (Mw) of polyvinyl acetal is preferably from 5,000 to 200,000, more preferably from 8,000 to 100,000. When the weight average molecular weight of polyvinyl acetal is in this range, when the thermosetting resin film is attached to the protruding electrode forming surface, the effect of suppressing the thermosetting resin film remaining on the protruding electrode becomes Get higher.

The glass transition temperature (Tg) of polyvinyl acetal is preferably 40°C to 80°C, more preferably 50°C to 70°C. When the Tg of polyvinyl acetal is in this range, when the thermosetting resin film is attached to the protruding electrode forming surface, the effect of suppressing the thermosetting resin film from remaining on the protruding electrode becomes more effective. high.

The ratio of three or more monomers constituting the polyvinyl acetal can be arbitrarily selected.

The acrylic resin in the polymer component (A) means a resin having a structural unit derived from (meth)acrylic acid or a derivative thereof. In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of "(meth)acrylic acid group" includes both "acrylic acid group" and "methacrylic acid group", and "(meth)acrylate" The concept includes both "acrylate" and "methacrylate". In addition, in this specification, the "derivative" of a specific compound means a compound having a structure in which one or more hydrogen atoms of the compound are replaced by groups (substituents) other than hydrogen atoms. For example, (meth)acrylate is a derivative of (meth)acrylic acid.

As the aforementioned acrylic resin in the polymer component (A), known acrylic polymers can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or greater than the aforementioned lower limit, the shape stability of the thermosetting resin film (stability with time during storage) is improved. When the weight average molecular weight of the acrylic resin is below the above upper limit, the thermosetting resin film can easily follow the uneven surface of the adherend, and the generation of voids between the adherend and the thermosetting resin film can be further suppressed Wait. In addition, in this specification, the "weight average molecular weight" means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is more than the aforementioned lower limit, for example, the adhesive force between the cured product of the thermosetting resin film and the support sheet is suppressed, and the releasability of the support sheet is appropriately improved. When the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit, the adhesion between the thermosetting resin film and its cured product and the adherend is improved.

As acrylic resins, for example, one or two or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxy Copolymers of two or more monomers in methacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate , N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, 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 Ester, 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 esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute one of the alkyl esters The alkyl group is a (meth)acrylic acid alkyl ester with a chain structure of carbon number 1 to 18; (meth)acrylic acid cycloalkyl group such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. Esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenoxy (meth)acrylate (Meth)acrylic acid cycloalkenyloxyalkyl esters such as ethyl ester; (meth)acrylimines; (meth)acrylic acid glycidyl esters and other glycidyl-containing (meth)acrylates; (meth) ) Hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxy-containing (meth)acrylates such as 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; N-methylaminoethyl (meth)acrylate containing substituted amino groups The (meth)acrylate and so on. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

Acrylic resins, for example, in addition to the aforementioned (meth)acrylates, may also copolymerize 1 selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide. One or more monomers.

The monomer constituting the acrylic resin 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 acrylic resin may also have functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional group of the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). The acrylic resin is bonded to other compounds via the aforementioned functional groups, and the reliability of the package obtained by using the first protective film forming sheet tends to be improved.

In the present invention, for example, as the polymer component (A), polyvinyl acetal and acrylic resin may not be used, but polyvinyl acetal and a thermoplastic resin other than acrylic resin may be used alone (hereinafter sometimes simply referred to as "thermoplastic resin"). ), can also be used in combination with polyvinyl acetal or acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the first protective film from the first support sheet may be improved, or the thermosetting resin film may easily follow the uneven surface of the adherend, and can further suppress the adhesion between the adherend and the There are voids between the thermosetting resin films.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

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

As said thermoplastic resin, polyester resin, polyurethane resin, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The aforementioned thermoplastic resin contained in the composition (III-1) and the thermosetting resin 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.

In the composition (III-1), regardless of the type of polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the ratio of the content in the thermosetting resin film) The ratio of the content of the polymer component (A) relative to the total mass of the thermosetting resin film), for example, can be 5 mass% to 60 mass%, 5 mass% to 45 mass%, 5 mass% to 30 mass%, and Any of 5 mass% to 15 mass%.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains such components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing polymer Material component (A) and thermosetting component (B).

[Thermosetting component (B)] The thermosetting component (B) is a component that has thermosetting properties and is used to thermally harden the thermosetting resin film to form a hard first protective film. In addition, in the thermosetting resin film, the thermosetting component (B) meets the ratio of the above-mentioned total content of the “thermosetting component” and the “thermosetting component” that is the calculation target of the aforementioned X value. .

The thermosetting component (B) contained in the composition (III-1) and the thermosetting resin 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 may be Arbitrary choice.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (B) is preferably an epoxy-based thermosetting resin.

[Epoxy-based thermosetting resin] The epoxy-based thermosetting resin is composed of epoxy resin (B1) and thermosetting agent (B2). In the thermosetting resin film, the epoxy resin (B1) and the thermosetting agent (B2) meet the requirements of the above-mentioned total content of the "thermosetting component" and the "thermosetting component" which is the calculation target of the aforementioned X value Sexual components" both.

The epoxy-based thermosetting resin contained in the composition (III-1) and the thermosetting resin 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 may be Arbitrary choice.

・Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins, such as 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, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Compound.

As the epoxy resin (B1), 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 workpiece with the first protective film obtained by using the first protective film forming sheet is improved.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound which converted a part of epoxy group of a polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group, for example is mentioned. 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 constituting the epoxy resin or the like 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 (Mn) of the epoxy resin (B1) is not particularly limited. In terms of the curability of the thermosetting resin film, and the strength and heat resistance of the cured resin film, it is preferably 300 to 8000 , More preferably 300 to 5500, particularly preferably 300 to 3500.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 970 g/eq, and still more preferably 200 g/eq to 600 g/eq.

The epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, these combination and ratio can be selected arbitrarily.

・Thermal hardener (B2) The thermal hardener (B2) functions as a hardener for the epoxy resin (B1). As a thermosetting agent (B2), 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 (B2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc. In the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyandiamide.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group. As the thermosetting agent (B2) 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 compound having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin Compounds etc. The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

When using a phenolic curing agent as the thermosetting agent (B2), in terms of improving the peelability of the first protective film from the first support sheet, the thermosetting agent (B2) is preferably a softening point or glass transition High temperature phenol hardener.

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 8000, and more It is preferably 300 to 5500, particularly preferably 300 to 3500. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited. For example, it is preferably 60 to 500.

A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, these combination and ratio can be selected arbitrarily.

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting agent (B2) relative to 100 parts by mass of the epoxy resin (B1) can be, for example, 0.1 parts by mass to 500 parts by mass, 1 part by mass Any one of parts to 250 parts by mass, 1 part by mass to 150 parts by mass, 1 part by mass to 100 parts by mass, 1 part by mass to 75 parts by mass, and 1 part by mass to 50 parts by mass. When the aforementioned content of the thermosetting agent (B2) is at least the aforementioned lower limit, the thermosetting resin film becomes easier to harden. When the aforementioned content of the thermosetting agent (B2) is below the aforementioned upper limit, the moisture absorption rate of the thermosetting resin film decreases, and the reliability of the package obtained using the first protective film forming sheet is further improved.

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer component ( The content of A) is 100 parts by mass, for example, 300 parts by mass to 1400 parts by mass, 400 parts by mass to 1300 parts by mass, 500 parts by mass to 1100 parts by mass, 600 parts by mass to 1000 parts by mass, and 700 parts by mass to 900 parts by mass Any kind. When the aforementioned content of the thermosetting component (B) is in this range, for example, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Hardening accelerator (C)] The composition (III-1) and the thermosetting resin film may contain a curing accelerator (C). The hardening accelerator (C) is a component used to adjust the hardening speed of the composition (III-1). As a preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 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 (one or more Phosphine in which hydrogen atoms are substituted by organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The curing accelerator (C) contained in the composition (III-1) and the thermosetting resin film may be only one type, or two or more types. When there are two or more types, the combination and ratio of these may be arbitrary select.

In the case of using the hardening accelerator (C), the content of the hardening accelerator (C) in the composition (III-1) and the thermosetting resin film is relative to 100 parts by mass of the thermosetting component (B), For example, it may be any of 0.01 parts by mass to 10 parts by mass, and 0.1 parts by mass to 7 parts by mass. When the aforementioned content of the hardening accelerator (C) is more than the aforementioned lower limit, the effect of using the hardening accelerator (C) can be more remarkably obtained. Since the content of the hardening accelerator (C) is below the aforementioned upper limit, for example, a high-polar hardening accelerator (C) will be bonded to the thermosetting resin film in the thermosetting resin film under high temperature and high humidity conditions. The adhesion interface side of the body moves and the effect of suppressing segregation becomes higher. As a result, the reliability of the workpiece with the first protective film obtained by using the first protective film forming sheet is further improved.

[Filling material (D)] The composition (III-1) and the thermosetting resin film may contain a filler (D). When the thermosetting resin film contains the filler (D), the first protective film obtained by curing the thermosetting resin film becomes easy to adjust the thermal expansion coefficient. In addition, by optimizing the thermal expansion coefficient to the object to be formed of the first protective film, the reliability of the workpiece with the first protective film obtained by using the first protective film forming sheet is further improved. In addition, when the thermosetting resin film contains the filler (D), the moisture absorption rate of the first protective film can also be reduced, or the heat dissipation can be improved.

The filling material (D) can be any one of organic filling material and inorganic filling material, preferably inorganic filling material. As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by spheroidizing Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, more preferably silica.

The average particle size of the filler (D) may be appropriately selected according to the purpose, and is not particularly limited. For example, it may be 0.02 μm to 2 μm. In addition, in this specification, the "average particle size" means 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. Value.

The filler (D) contained in the composition (III-1) and the thermosetting resin 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 .

In the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the content of the filler (D) in the thermosetting resin film relative to the thermosetting The ratio of the total mass of the resin film) can be, for example, 3 mass% to 60 mass%, 4 mass% to 40 mass%, 5 mass% to 30 mass%, 5 mass% to 20 mass%, and 5 mass% to 15 mass% Any of %. When the aforementioned ratio is in such a range, it becomes easier to adjust the thermal expansion coefficient of the aforementioned first protective film.

[Coupling agent (E)] The composition (III-1) and the thermosetting resin film may contain a coupling agent (E). By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the thermosetting resin film to the adherend can be improved. In addition, by using the coupling agent (E), the cured product of the thermosetting resin film does not impair heat resistance and improves water resistance.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A) and the thermosetting component (B), and more preferably a 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 Oxyoxysilane, 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, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (III-1) and the thermosetting resin film may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected .

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and thermosetting resin film is relative to the polymer component (A) and thermosetting component (B) The total content of 100 parts by mass can be, for example, any of 0.03 parts by mass to 20 parts by mass, 0.05 parts by mass to 10 parts by mass, and 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (E) is above the aforementioned lower limit, the following effects brought about by the use of the coupling agent (E) can be obtained more significantly: the dispersibility of the filler (D) in the resin is improved, Or the adhesion between the thermosetting resin film and the adherend is improved. When the aforementioned content of the coupling agent (E) is below the aforementioned upper limit value, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)] When using the above-mentioned acrylic resin with functional groups such as vinyl, (meth)acrylic acid group, amino group, hydroxyl group, carboxyl group, isocyanate group, etc., which can be bonded with other compounds, as the polymer component (A), the composition The compound (III-1) and the thermosetting resin film may contain a crosslinking agent (F). The cross-linking agent (F) is a component used to bond the aforementioned functional groups in the polymer component (A) with other compounds to perform cross-linking. By cross-linking in this way, the initial adhesion of the thermosetting resin film can be adjusted Strength and cohesion.

As the crosslinking agent (F), for example, organic polyisocyanate compound, organic polyimine compound, metal chelate crosslinking agent (crosslinking agent having a metal chelate structure), 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, isocyanurates and adducts of aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds and the like 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, etc. The reactant of low molecular 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-xylylene diisocyanate Diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Ketone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene is added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Compounds of any one or more of diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine methamide), 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 polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced into the In thermosetting resin film.

The crosslinking agent (F) contained in the composition (III-1) and the thermosetting resin 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 arbitrary select.

In the case of using the crosslinking agent (F), in the composition (III-1), the content of the crosslinking agent (F) relative to the content of the polymer component (A) is 100 parts by mass, for example, it can be 0.01 parts by mass to Any one of 20 parts by mass, 0.1 parts by mass to 10 parts by mass, and 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (F) is more than the aforementioned lower limit, the effect of using the cross-linking agent (F) can be more remarkably obtained. When the aforementioned content of the cross-linking agent (F) is below the aforementioned upper limit, excessive use of the cross-linking agent (F) is suppressed.

[Energy ray curable resin (G)] The composition (III-1) and the thermosetting resin film may contain energy ray-curable resin (G). The thermosetting resin film contains energy-ray-curable resin (G), so that its properties can be changed by energy-ray irradiation.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound. Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

Examples of the acrylate-based compounds include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates and other (meth)acrylates containing chain aliphatic skeletons; (meth)acrylates such as dicyclopentyl di(meth)acrylates containing cyclic aliphatic skeletons; polyethylene glycol Di(meth)acrylate and other polyalkylene glycol (meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (former Base) acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

The energy ray curable resin (G) contained in the composition (III-1) and the thermosetting resin 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 chosen arbitrarily.

In the case of using energy ray curable resin (G), the ratio of the content of energy ray curable resin (G) to the total mass of composition (III-1) in the composition (III-1) may be, for example Any one of 1% to 95% by mass, 5% to 90% by mass, and 10% to 85% by mass.

[Photopolymerization initiator (H)] When the composition (III-1) and the thermosetting resin film contain energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), it may also contain photopolymerization. Starter (H).

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin methyl benzoate. Esters, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethane-1-one; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide compounds such as phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzal; benzophenone; benzophenone ; 2,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2- Chloroanthraquinone and so on. In addition, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines.

The photopolymerization initiator (H) contained in the composition (III-1) and the thermosetting resin 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 chosen arbitrarily.

In the case of using the photopolymerization initiator (H), the content of the photopolymerization initiator (H) in the composition (III-1) is relative to 100 parts by mass of the energy ray curable resin (G), for example It can be any of 0.1 to 20 parts by mass, 1 to 10 parts by mass, and 2 to 5 parts by mass.

[Colorant (I)] The composition (III-1) and the thermosetting resin film may contain a coloring agent (I). As the colorant (I), for example, known coloring agents such as inorganic pigments, organic pigments, and organic dyes can be cited.

Examples of the aforementioned organic pigments and organic dyes include: ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, and azulene pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol Pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, etc.

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 (I) contained in the composition (III-1) and the thermosetting resin 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 .

When using the coloring agent (I), the content of the coloring agent (I) in the thermosetting resin film may be appropriately adjusted according to the purpose. For example, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, the content of the colorant (I) in the thermosetting resin film relative to the heat The ratio of the total mass of the curable resin film) may be 0.1% by mass to 5% by mass. When the aforementioned ratio is more than the aforementioned lower limit, the effect of using the colorant (I) can be more remarkably obtained. When the aforementioned ratio is equal to or less than the aforementioned upper limit, excessive decrease in the light transmittance of the thermosetting resin film is suppressed.

[General additives (J)] The composition (III-1) and the thermosetting resin film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention. The general additives (J) can be well-known compounds and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general additives (J) include, for example, plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) and so on.

The general additives (J) contained in the composition (III-1) and the thermosetting resin 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 content of the general additive (J) of the composition (III-1) and the thermosetting resin film is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent] The composition (III-1) preferably further contains a solvent. The operability of the solvent-containing composition (III-1) becomes better. The aforementioned solvent is not particularly limited. As preferred aforementioned solvents, for example, 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; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds )Wait. The solvent contained in the composition (III-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.

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like in terms of enabling the components contained in the composition (III-1) to be mixed more uniformly.

The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

As an example of a preferable thermosetting resin film of the present embodiment, the following thermosetting resin film can be cited: it is used to adhere to the surface of the workpiece with protruding electrodes and heat it to form on the surface The first protective film; and the thermosetting resin film is attached to a circular copper foil with a thickness of 35 μm and a diameter of 8 inches, and the copper foil is placed on the lower side in a flat state so that the thermosetting resin film is thermally cured and The maximum amount of warpage of the entire circumference after being left to cool is 20mm or less; the aforementioned thermosetting resin film contains thermosetting components other than acrylic resin with epoxy groups with a weight average molecular weight greater than 10,000; for the aforementioned thermosetting resin film For the thermosetting components contained, the X value calculated by the following formula is obtained for each type, and the X value in all types of the thermosetting components contained in the thermosetting resin film is obtained In the case of the total value of, the aforementioned total value becomes 300 g/eq or more. X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components].

As another example of the preferred thermosetting resin film of the present embodiment, the following thermosetting resin film can be cited: it is used to stick to the surface of the workpiece with protruding electrodes and heat-cured on the surface A first protective film is formed; and the thermosetting resin film contains a polymer component (A), an epoxy resin (B1), and a thermosetting agent (B2); in the thermosetting resin film, the polymer component (A) The ratio of the content relative to the total mass of the thermosetting resin film is 5% to 30% by mass; in the thermosetting resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) is relative to The content of the polymer component (A) in 100 parts by mass is 600 to 1000 parts by mass; in the thermosetting resin film, the content of the thermosetting agent (B2) is relative to the content of the epoxy resin (B1) 100 parts by mass is 1 part by mass to 100 parts by mass; the aforementioned thermosetting resin film is attached to a round copper foil with a thickness of 35 μm and a diameter of 8 inches, and the aforementioned copper foil is placed on the lower side in a flat state to heat-harden the aforementioned The maximum amount of warpage of the entire circumference of the flexible resin film after thermal curing and cooling is 20 mm or less.

As another example of the preferred thermosetting resin film of the present embodiment, the following thermosetting resin film can be cited: it is used to stick to the surface of the workpiece with protruding electrodes and heat-cured on the surface A first protective film is formed; and the aforementioned thermosetting resin film contains a polymer component (A) and a thermosetting component other than an epoxy-containing acrylic resin with a weight average molecular weight greater than 10,000; the aforementioned thermosetting component consists of a ring Composed of oxygen resin (B1) and thermosetting agent (B2); in the thermosetting resin film, the ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film is 5 mass% to 30% by mass; in the thermosetting resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) relative to the content of the polymer component (A) is 600 parts by mass to 1000 parts by mass Parts; In the thermosetting resin film, the content of the thermosetting agent (B2) relative to 100 parts by mass of the epoxy resin (B1) is 1 part by mass to 100 parts by mass; for the thermosetting resin film For the thermosetting components contained, the X value calculated by the following formula is obtained for each type, and the value of X among all the thermosetting components contained in the thermosetting resin film is obtained In the case of the total value, the aforementioned total value becomes 300 g/eq or more. X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components].

As another example of the preferred thermosetting resin film of the present embodiment, the following thermosetting resin film can be cited: it is used to stick to the surface of the workpiece with protruding electrodes and heat-cured on the surface A first protective film is formed; and the aforementioned thermosetting resin film contains a polymer component (A) and a thermosetting component other than an epoxy-containing acrylic resin with a weight average molecular weight greater than 10,000; the aforementioned thermosetting component consists of a ring Composed of oxygen resin (B1) and thermosetting agent (B2); in the thermosetting resin film, the ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film is 5 mass% to 30% by mass; in the thermosetting resin film, the total content of the epoxy resin (B1) and the thermosetting agent (B2) relative to the content of the polymer component (A) is 600 parts by mass to 1000 parts by mass Parts; in the thermosetting resin film, the content of the thermosetting agent (B2) relative to 100 parts by mass of the epoxy resin (B1) is 1 part by mass to 100 parts by mass; the thermosetting resin film is pasted Attached to a round copper foil with a thickness of 35μm and a diameter of 8 inches, the copper foil is placed on the lower side in a flat state, and the thermosetting resin film is thermally cured and the maximum warpage of the entire circumference after cooling is 20mm or less ; For the thermosetting components contained in the thermosetting resin film, the X value calculated by the following formula is calculated for each type, and when all types of heat contained in the thermosetting resin film are obtained In the case of the total value of the aforementioned X values in the curable component, the aforementioned total value becomes 300 g/eq or more. X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components].

[Method for manufacturing composition for forming thermosetting resin layer] The composition for forming a thermosetting resin layer, such as the composition (III-1), is obtained by blending each component for constituting the composition. The order of addition when formulating each component is not particularly limited, and two or more components may be added at the same time. In the case of using a solvent, it can be used in the following manner: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; or, pre-diluting any compounding component other than the solvent The solvent is mixed with these formulation ingredients. The method of mixing the ingredients during the preparation is not particularly limited, and can be appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves for mixing The method and so on. Regarding the temperature and time at the time of adding and mixing each component, the temperature and time are not particularly limited as long as each compounding component is not degraded, and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◇The manufacturing method of the first protective film forming sheet The sheet for forming the first protective film can be manufactured by sequentially stacking the respective layers in a corresponding positional relationship. The formation method of each layer is as described above. For example, in the case of laminating the first adhesive layer or the first intermediate layer on the first substrate when manufacturing the first support sheet, apply the above-mentioned first adhesive composition or the first intermediate layer on the first substrate The composition for layer formation may be dried or irradiated with energy rays as necessary, whereby the first adhesive layer or the first intermediate layer can be laminated.

On the other hand, for example, when a thermosetting resin layer (thermosetting resin film) is laminated on the first adhesive layer already laminated on the first substrate, heat can be applied to the first adhesive layer The composition for forming a curable resin layer directly forms a thermosetting resin layer. Similarly, when the first intermediate layer is laminated on the first substrate, and then the first adhesive layer is laminated, the first adhesive composition can be coated on the first intermediate layer to directly form the first adhesive Agent layer. In this way, when any composition is used to form a continuous two-layer laminated structure, another composition can be applied on the layer formed by the aforementioned composition to form a new layer. However, it is preferable that the latter layer of the two layers is formed in advance on the other release film using the aforementioned composition, so that the side of the formed layer contacting the release film is the exposed surface on the opposite side and the existing The exposed surfaces of the remaining layers that have been formed are bonded together to form a continuous 2-layer laminated structure. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. After the build-up structure is formed, the release film can be removed as necessary.

For example, a sheet for forming a first protective film (the first supporting sheet is the first base) is manufactured by laminating a first adhesive layer on a first substrate and laminating a thermosetting resin layer on the first adhesive layer. In the case of the first protective film forming sheet of the laminate of the first adhesive layer and the first adhesive layer, apply the first adhesive composition on the first substrate, and dry it if necessary, thereby applying it to the first substrate The first adhesive layer is preliminarily laminated on the release film, and the thermosetting resin layer forming composition is separately coated on the release film, and dried if necessary, thereby preliminarily forming a thermosetting resin layer on the release film to make the thermosetting The exposed surface of the resin layer is bonded to the exposed surface of the first adhesive layer laminated on the first substrate, and the thermosetting resin is laminated on the first adhesive layer to obtain the first protective film formation sheet.

In addition, for example, when manufacturing a first support sheet in which a first intermediate layer is laminated on a first substrate and a first adhesive layer is laminated on the first intermediate layer, the first substrate is coated with the first support sheet. The composition for forming an intermediate layer is dried or irradiated with energy rays as necessary, thereby pre-laminating the first intermediate layer on the first substrate, separately coating the first adhesive composition on the release film, and drying as necessary , Thereby forming a first adhesive layer on the release film in advance, so that the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer that has been laminated on the first substrate, and the first adhesive Laminated on the first intermediate layer, thereby obtaining the first supporting sheet. In this case, for example, a composition for forming a thermosetting resin layer is separately applied to the release film, and dried as necessary, thereby preliminarily forming a thermosetting resin layer on the release film to make the thermosetting resin layer The exposed surface is bonded to the exposed surface of the first adhesive layer laminated on the first intermediate layer, and the thermosetting resin is laminated on the first adhesive layer, thereby obtaining a first protective film forming sheet.

In addition, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, as described above, it can be used instead of coating the first adhesive composition or the first intermediate layer on the first substrate. The method of composition is to apply the first adhesive composition or the first intermediate layer forming composition on the release film, and dry it or irradiate energy rays as necessary to form the first adhesive on the release film in advance Layer or first intermediate layer, the exposed surfaces of these layers are bonded to one surface of the first substrate, thereby laminating the first adhesive layer or the first intermediate layer on the first substrate. In either method, the release film may be removed at any time after the target build-up structure is formed.

In this way, since the layers other than the first base material constituting the first protective film forming sheet can be laminated by a method of pre-formed on the release film and then bonded to the surface of the target layer, such layers are appropriately selected and used as needed For the layer of the step, the first protective film forming sheet can be manufactured.

In addition, the sheet for forming a first protective film is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, a thermosetting resin layer) on the opposite side of the sheet from the first support sheet. Therefore, the first protective film forming sheet can also be obtained by coating the release film (preferably the release treatment surface of the release film) with a composition for forming a thermosetting resin layer for forming The composition of the layer constituting the outermost layer is dried as necessary to form a layer constituting the outermost layer on the release film in advance, and the side of the layer that is in contact with the release film is exposed by any of the above methods. The remaining layers are laminated on the surface, and the peeling film is not removed and the attached state remains unchanged.

As the first support sheet, a commercially available product can also be used.

◇Second protective film formation film, second protective film formation sheet In one embodiment of the present invention, it is possible to provide a kit including the above-mentioned thermosetting resin film, and a second protective film for forming a second protective film for attaching to the inner surface of the workpiece opposite to the surface having the protruding electrode The following structure can be adopted: in addition to the first protective film forming sheet described above, the second protective film forming film as shown in FIG. 6A further serves as the second supporting sheet 801 on one surface 801a provided 2 The sheet 8 for forming a protective film is included in the film kit.

The second support sheet 801 is not particularly limited, and a sheet having the same material and thickness as the first support sheet 101, 102, or 103 provided in the above-mentioned first protective film forming sheet 1, 2 or 3 can be used . That is, as the second support sheet 801, a sheet composed of the second protective film forming film directly in contact with the second substrate may be used, or it may be used between the second substrate and the second protective film forming film. Furthermore, a sheet of the first intermediate layer or the first adhesive layer is provided in between.

The second protective film formation film is a film used to stick to the inner surface of the workpiece on the opposite side to the surface with the protruding electrode as described above, and it is directly on the workpiece and the workpiece on the opposite side to the circuit surface The "second protective film" on the surface (inner surface) may be composed of at least a curable component and cured to become the "second protective film".

In addition, as the second protective film forming film, it may be a structure having the same composition as the thermosetting resin film (thermosetting resin layer) described above, and may further be a structure containing a coloring agent. As such a coloring agent, organic or inorganic pigments and dyes can be used. As the dye, for example, any one of acid dyes, reactive dyes, direct dyes, disperse dyes, and cationic dyes can be used. In addition, the pigment is not particularly limited, and it can be appropriately selected from known pigments and used. Among these, it is preferable to use a black pigment from the viewpoint that the shielding properties of electromagnetic waves or infrared rays are good, and the recognizability by the laser marking method can be further improved. Examples of black pigments include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of semiconductor wafers, carbon black is preferred. Moreover, these coloring agents can be used individually or in combination of 2 or more types.

The content of the coloring agent in the second protective film formation film relative to the total amount (100 mass%) of the composition forming the second protective film formation film is preferably 0.01% to 30% by mass, more preferably 0.05 Mass% to 25% by mass, more preferably 0.1% to 15% by mass, and still more preferably 0.15% to 5% by mass.

In addition, the thickness of the film for forming the second protective film may be the same as the above-mentioned thermosetting resin film.

◇Manufacturing method of workpiece with first protective film A method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention includes a step of attaching the thermosetting resin film to the surface of the workpiece having the protruding electrode (that is, the protruding electrode forming surface) (In this manual, sometimes referred to as "attaching step"); the step of thermally curing the attached thermosetting resin film to form a first protective film (in this manual, sometimes referred to as "first protection Film formation step"); and divide the workpiece, and cut the first protective film, thereby obtaining a workpiece with a workpiece and a surface with the protruding electrode formed in the workpiece (ie, protruding electrode formation The step of the workpiece with the first protective film of the first protective film (in this manual, sometimes referred to as "dividing and cutting step"). Hereinafter, the aforementioned manufacturing method will be described in detail while referring to the drawings.

5A to 5C are enlarged cross-sectional views for schematically explaining the manufacturing method of the workpiece with the first protective film. Here, the manufacturing method in the case of using the 1st protective film formation sheet 1 shown in FIG. 2 is demonstrated.

[Attaching steps] In the aforementioned attaching step, as shown in FIG. 5A, the thermosetting resin film 12 is attached to the projecting electrode forming surface of the workpiece 90 (that is, the surface 91a of the projecting electrode 91 and the circuit surface 90a of the workpiece 90). By performing this step, the thermosetting resin film 12 spreads between the plurality of protruding electrodes 91, is in close contact with the protruding electrode formation surface, and covers the surface 91a of the protruding electrode 91, especially the circuit surface of the workpiece 90 The surface 91a in the vicinity of 90a can be in a state where the protruding electrode 91 is embedded and these regions are covered. Furthermore, by performing this step, the upper portion of the protruding electrode 91 including the top portion 910 penetrates the thermosetting resin film 12 and protrudes from the thermosetting resin film 12.

In the attaching step, for example, the thermosetting resin film 12 may be used alone, but it is preferable to use the thermosetting resin film 12 provided with the first support sheet 101 and the first support sheet 101 as shown here. The first protective film forming sheet 1 constituted. As described later, when grinding the inner surface 90b of the workpiece 90, a surface protection tape for back polishing can be used as the first support sheet 101.

In the attaching step, when the first protective film forming sheet 1 shown here is used, the thermosetting resin film 12 in the first protective film forming sheet 1 is attached to the projecting electrode of the work 90 The formation surface may be formed by attaching the first protective film forming sheet 1 itself to the projecting electrode formation surface of the workpiece 90.

In addition, in this specification, a laminated structure formed by attaching the first protective film forming sheet to the protruding electrode forming surface of the workpiece as shown here may be referred to as the "first laminated structure". In FIG. 5A, as the first laminated structure 201, a laminated structure formed by attaching the first protective film forming sheet 1 to the projecting electrode formation surface of the work 90 is shown.

In the attaching step, the exposed surface (in this specification, sometimes referred to as the "first surface") 12a of the thermosetting resin film 12 opposite to the workpiece 90 is pressed against the protruding electrode forming surface of the workpiece 90 (That is, the surface 91a of the protruding electrode 91 and the circuit surface 90a of the workpiece 90), whereby the thermosetting resin film 12 can be attached to the protruding electrode forming surface.

In the attaching step, it is preferable to attach the thermosetting resin film 12 to the protruding electrode forming surface while heating. Thereby, between the thermosetting resin film 12 and the protruding electrode formation surface (between the thermosetting resin film 12 and the circuit surface 90a of the workpiece 90), and the surface of the thermosetting resin film 12 and the protruding electrode 91 Any place between 91a can further suppress the generation of voids. In addition, it is possible to further suppress the thermosetting resin film 12 from remaining on the upper portion of the protruding electrode 91 including the top portion 910, and finally it is possible to further suppress the first protective film from remaining on the upper portion.

The heating temperature of the thermosetting resin film 12 at the time of sticking should just be not excessively high temperature, for example, 60 to 100 degreeC is preferable. Here, the term "excessive high temperature" means, for example, the temperature at which the thermosetting resin film 12 is thermally cured, etc., at which the thermosetting resin film 12 exhibits an off-target effect.

When the thermosetting resin film 12 is attached to the protruding electrode forming surface, the pressure applied to the thermosetting resin film 12 (in this specification, sometimes referred to as "attachment pressure") is preferably 0.3 MPa to 1MPa.

After the first layered structure 201 is formed by the attaching step, the first layered structure 201 can also be used directly in subsequent steps, and the workpiece 90 can be adjusted by grinding the inner surface 90b of the workpiece 90 if necessary. thickness of. In addition to the difference in the thickness of the workpiece 90, the first laminated structure 201 after the inner surface 90b of the workpiece 90 is ground is also in the state shown in FIG. 5A.

The inner surface 90b of the workpiece 90 can be ground by a known method such as a method using a grinder.

The thickness of the parts other than the protruding electrode 91 in the workpiece 90 before and after the inner surface 90b of the workpiece 90 is ground is as described above.

After the first laminated structure 201 is formed by the bonding step, the first support sheet 101 is removed from the thermosetting resin film 12 in the first laminated structure 201. In the case of grinding the inner surface 90b of the workpiece 90, it is preferable to remove the first support piece 101 after the grinding. By performing such steps, as shown in FIG. 5B, a second laminated structure (in other words, attached) is obtained, which is composed of the thermosetting resin film 12 on the projecting electrode forming surface of the workpiece 90 and does not include the first support sheet 101 Workpiece of thermosetting resin film) 202. In the second laminated structure 202, the upper part of the protruding electrode 91 including the head top 910 penetrates the thermosetting resin film 12 and protrudes and is exposed.

In the case where the first adhesive layer 13 is energy-ray curable, it is preferable to cure the first adhesive layer 13 by irradiating energy rays, and after the adhesiveness of the first adhesive layer 13 is reduced, the self-heat curable property The resin film 12 removes the first support sheet 101.

[First protective film formation step] In the aforementioned first protective film forming step, the attached thermosetting resin film 12 is thermally cured to form a first protective film 12' as shown in FIG. 5C. In the case of forming the first laminated structure 201, the first protective film forming step may be performed after the first supporting sheet 101 is removed. In addition, when grinding the inner surface 90b of the workpiece 90, the first protective film forming step may be performed after the grinding of the inner surface 90b. By performing this step, a third laminated structure (in other words, a workpiece with a first protective film) 203 formed by providing the first protective film 12' on the projecting electrode forming surface of the workpiece 90 is obtained. In FIG. 5C, the symbol 12a' indicates the contact surface of the first protective film 12' with the workpiece 90 (in this specification, it may be referred to as the "first surface").

Regarding the curing conditions of the thermosetting resin film 12, the curing conditions are not particularly limited as long as the first protective film 12' has a degree of curing that can sufficiently exhibit the function of the first protective film 12'. What is necessary is just to select the kind of resin film 12 suitably. For example, the heating temperature and heating time during the thermal curing of the thermosetting resin film 12 are as described above. When the thermosetting resin film 12 is thermally cured, the curable resin film 12 may be pressurized. In this case, the pressurizing pressure is preferably 0.3 MPa to 1 MPa.

By attaching a round copper foil with a thickness of 35μm and a diameter of 8 inches as a thermosetting resin film, the copper foil is heated in a flat state at 130°C for 2h (to make thermosetting The resin film is thermally cured) and the thermosetting resin film 12 with the maximum warpage of the entire circumference of 20mm or less after cooling forms the first protective film 12', and the third laminated structure (in other words, The workpiece with the first protective film 203 can maintain flatness with the warpage suppressed. In addition, the first protective film 12' is formed by the thermosetting resin film 12 whose total value of X value is 300g/eq or more, and the third laminated structure (in other words, with the first protective film Workpiece) 203 can maintain flatness in a state where warpage is suppressed.

In the second laminated structure (workpiece with thermosetting resin film) 202 shown in FIG. 5B, the thermosetting resin film 12 is suppressed from remaining on the protruding electrode 91 including the top portion 910. Therefore, after the end of this step, the first protective film 12 ′ is also suppressed from remaining on the upper part of the protruding electrode 91.

[Segmentation and cutting steps] In the aforementioned dividing and cutting step, as shown in FIG. 6A, it is preferable to apply a second protective film to the inner surface 90b of the workpiece 90 in the third laminated structure (work with the first protective film) 203 in advance. After the film.

In addition, in this specification, the layered structure formed by providing the first protective film on the projecting electrode forming surface of the workpiece and the second protective film forming sheet on the inner surface of the workpiece may be referred to as the "fourth layered structure body".

The second protective film forming sheet 8 shown here includes a second base material 81, a second adhesive layer 83 provided on the second base material 81, and a second adhesive layer 83 provided on the second adhesive layer 83. The protective film formation film 82 is comprised. The second support sheet 801 of the laminated system of the second base material 81 and the second adhesive layer 83. Therefore, it can be said that the second protective film formation sheet 8 includes a second support sheet 801 and a second protective film formed on one surface 801a of the second support sheet 801, in other words, on one surface 83a of the second adhesive layer 83 Use film 82.

The second protective film forming film 82 is used to form a second protective film on the inner surface 90 b of the work 90. The second protective film covers and protects the inner surface 90b of the workpiece 90. More specifically, the second protective film prevents cracks in the workpiece when the workpiece is divided or before the workpiece processed product obtained by the workpiece division is packaged to manufacture the target substrate device.

The film 82 for forming a second protective film may have only any of thermosetting properties and energy ray curability properties, may have both properties, or may not have both properties. When the second protective film formation film 82 is curable (that is, it has at least one of thermosetting and energy ray curability), the cured product of the second protective film formation film 82 is the second protective film . When the second protective film forming film 82 is non-curable (that is, it does not have the characteristics of both thermosetting and energy ray curability), it is regarded as being attached to the work 90 on the second protective film forming film 82 The second protective film is provided at the stage of the inner surface 90b of the slab.

The second adhesive layer 83 may be either energy ray curable or non-energy ray curable similarly to the first adhesive layer 13. The second adhesive layer 83, which is energy-ray curable, can easily adjust the physical properties of the second adhesive layer 83 before and after curing.

The second base material 81 may be the same as the first base material (for example, the first base material 11 in the first protective film formation sheet 1) in the first protective film formation sheet described above.

In the aforementioned manufacturing method, as the second protective film formation sheet, a protective film formation sheet other than the second protective film formation sheet 8 may be used. In the above-mentioned manufacturing method, the sheet 8 for forming a second protective film is not limited to, and as the sheet for forming a second protective film, a known sheet for forming a protective film can be used. Similarly, in the aforementioned manufacturing method, a known sheet for forming a protective film can be used as a dicing sheet instead of the second sheet for forming a protective film 8.

In the foregoing manufacturing method, it is shown that the second laminated structure (in other words, the workpiece with the thermosetting resin film) 202 undergoes the first protective film forming step to obtain the third laminated structure (in other words, the workpiece with the first protective film) ) 203, but it is not limited to this order. It is also possible to stick a dicing sheet or a second protective film on the inner surface 90b of the workpiece 90 in the second laminated structure (workpiece with thermosetting resin film) 202 After the sheeting, the thermosetting resin film 12 is thermally cured to form a first protective film on the surface of the workpiece.

In the aforementioned dividing and cutting step, next, the workpiece 90 of the fourth laminated structure 204 is divided, and the aforementioned first protective film 12' and the aforementioned second protective film forming film 82 are cut. As a result, as shown in FIG. 6B, a first electrode forming surface (that is, the surface 91a of the projecting electrode 91 and the circuit surface 9a of the workpiece 9) formed on the workpiece 9 and the projected electrode forming surface formed on the workpiece 9 is obtained as shown in FIG. 6B 1 Protective film (the first protective film 120' after cutting) of the workpiece 990 with the first protective film. The second protective film forming film 82 after cutting is further provided on the inner surface 9b of the workpiece 9 in the workpiece 990 with the first protective film (reference numeral 820 in FIG. 6B). By performing this step, a sixth layered structure in which the workpiece 990 with the first protective film has been cut and the second protective film forming film 820 is arranged on the second support sheet 801 in multiple (majority) states is obtained 206. In FIG. 6B, the symbol 120a' indicates the contact surface of the cut first protective film 120' with the workpiece 9 (in this specification, it may be referred to as the "first surface").

In the dividing and cutting steps, the method of dividing the workpiece 90 can be a well-known method, which can be blade cutting; or by irradiating the workpiece with laser light, while cutting off the workpiece at the irradiated part, the workpiece is removed from the workpiece. Laser cutting in which the surface is gradually cut off; it can also be a method called invisible cutting (registered trademark) in which a modified layer is preset inside the workpiece by laser light and force is applied to separate the workpiece.

Here is shown a case where the second protective film forming film 82 in the second protective film forming sheet 8 is also cut by performing the aforementioned dividing and cutting steps, but the cut of the second protective film forming film 82 The cutting can also be performed separately by a known method after the cutting and cutting steps. In addition, the case where the second protective film formation film 82 is cut is shown here, but the second protective film formation film may be cut instead of cutting at the stage of the second protective film formation film 82 82 second protective film obtained by curing.

In the aforementioned manufacturing method, the second protective film formation film 82 or the second protective film system is cut along the division portion of the workpiece 90 in the same manner as in the case of the first protective film 12'. In addition, in this specification, even after the second protective film formation film 82 or the second protective film is cut, the second support sheet and the second protective film formation film 82 or the second protective film (in other words, the second protective film The laminated structure of the support sheet and the cut second protective film forming film 82 or the second protective film) is still referred to as the "second protective film forming sheet".

◇Method of manufacturing substrate device After obtaining the workpiece with the first protective film (in other words, the sixth laminated structure) by the above-mentioned manufacturing method, the workpiece with the first protective film is flip-chip connected to the substrate by a known method After the circuit surface is formed, a package is made, and the target substrate device (not shown) can be manufactured by using the package. In the case of using a semiconductor wafer with a first protective film, after the semiconductor package is manufactured, the target semiconductor device can be manufactured by using the semiconductor package. [Example]

Hereinafter, the present invention will be described in more detail with specific examples. However, the present invention is not limited at all to the embodiments shown below. In addition, for each target manufactured in the comparative example shown below, for convenience, the same name as each manufactured target in the example is marked.

The components used to manufacture the composition for forming a thermosetting resin layer are shown below. [Polymer component (A)] (A)-1: Polyvinyl butyral ("S-LEC SV-10" manufactured by Sekisui Chemical Co., Ltd., weight average molecular weight 65,000, glass transition temperature 66°C)

[Thermosetting component (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A epoxy resin ("EPICLON EXA-4816" manufactured by DIC Corporation, epoxy equivalent 408g/eq) (B1)-2: Bisphenol A epoxy resin ("EPICLON EXA-4850" manufactured by DIC Corporation, epoxy equivalent 450g/eq) (B1)-3: Dicyclopentadiene epoxy resin ("EPICLON HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 265g/eq)

・Thermal hardener (B2) (B2)-1: Novolak type phenol resin ("Shonol BRG-556" manufactured by Showa Denko Corporation, hydroxyl equivalent 104g/eq) (B2)-2: Biphenyl type phenol resin ("MEH-7851H" manufactured by Meiwa Chemical Co., Ltd., solid dispersion type latent hardener, active hydrogen content 218g/eq)

[Hardening accelerator (C)] (C)-1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.)

[Filling material (D)] (D)-1: Silica filler ("YA050C-MKK" manufactured by Admatechs, with an average particle size of 0.05μm)

[Example 1] [Manufacturing of thermosetting resin film and first protective film forming sheet] [Manufacturing of composition for forming thermosetting resin layer] The polymer component (A)-1 (10 parts by mass), epoxy resin (B1)-2 (34.0 parts by mass), epoxy resin (B1)-3 (25.8 parts by mass), thermosetting agent (B2)- 1 (21.0 parts by mass), hardening accelerator (C)-1 (0.2 parts by mass) and filler (D)-1 (9.0 parts by mass) are mixed, and then diluted with methyl ethyl ketone, and carried out at 23°C By stirring, the composition (III-1) for forming a thermosetting resin layer having a total concentration of 55% by mass of 6 components other than the above-mentioned methyl ethyl ketone was prepared. These components and the contents of these components are shown in Table 1. In addition, when the column of contained components in Table 1 is described as "-", it means that the composition for forming a thermosetting resin layer does not contain the component. In addition, the "ratio of the total content of all types of thermosetting components (mass%)" in Table 1 means "the total content of all types of thermosetting components in the thermosetting resin film relative to the thermosetting The ratio of the total mass of the resin film.

[Manufacturing of thermosetting resin film] Use a peeling film made of polyethylene terephthalate on one side of the film that has been peeled off by silicone treatment ("SP-PET381031" made by Lindeco, thickness 38μm). The peeling treatment surface was coated with the composition (III-1) for forming a thermosetting resin layer obtained above, and dried at 110°C for 2 minutes to produce a thermosetting resin film with a thickness of 30 μm.

In addition, the ratio of the total content of all types of thermosetting components in the thermosetting resin film of Example 1 to the total mass of the thermosetting resin film was 80.8% by mass.

In Example 1, the total value of X values is 301 (={450×34.0/(34.0＋25.8＋21.0)}＋{265×25.8/(34.0＋25.8＋21.0)}＋{104×21.0/ (34.0＋25.8＋21.0)})g/eq.

[Measurement of Warpage of Copper Foil Laminated Products] Using a laminating device (manufactured by Royal Sovereign, RSL-382s), the thermosetting resin film (thickness 30μm) was attached to a copper foil with a thickness of 35μm and a diameter of 8 inches under the condition of the upper and lower rolls at 60°C. The exuded thermosetting resin film is removed to make a copper foil laminate product. With the copper foil of the copper foil laminate on the lower side, heat treatment (thermosetting the thermosetting resin film) was performed on a flat iron plate at 130°C for 2 hours. Although it was a flat state in the heating state at 130°C, when it was left to cool to 23°C for about 8 hours, warpage was observed. The maximum height of the entire circumference of the copper foil from the surface of the iron plate (that is, the amount of warpage of the copper foil laminate) was measured, and the result was 15 mm.

[Manufacture of the first protective film forming sheet] Next, the exposed surface of the thermosetting resin film formed on the release film (in other words, the side opposite to the side with the release film) was attached to a backside polishing surface protection tape (manufactured by Lindke) Adwill E-8180HR") to produce the first protective film forming sheet. The aforementioned surface protection tape corresponds to the first support sheet.

[Manufacture of semiconductor wafer with first protective film] The release film is removed from the thermosetting resin film in the first protective film forming sheet obtained above, and the exposed surface of the thermosetting resin film produced thereby (in other words, the side with the surface protection tape is The opposite side) is pressed against the bump formation surface of the semiconductor wafer, whereby the first protective film formation sheet is attached to the bump formation surface of the semiconductor wafer. At this time, the first protective film forming sheet is attached using an attaching device (roller type laminator, "RAD-3510 F/12" manufactured by Lindeco), at the attaching speed of 2mm/s, and It is carried out while heating the table to 90°C under the condition of 0.5MPa pressure. As a semiconductor wafer, the height of bumps is 210μm, the width of bumps is 250μm, the distance between adjacent bumps is 400μm, the thickness of parts other than bumps before grinding is 750μm, and the diameter is 8 inches. Semiconductor wafer. Through the above steps, a first build-up structure formed by attaching the first protective film forming sheet to the bump forming surface of the semiconductor wafer is obtained.

Then, using a grinder ("DGP8760" manufactured by DISCO), the surface (inner surface) of the semiconductor wafer on the opposite side to the bump formation surface in the obtained first laminated structure was ground. At this time, the inner surface was ground to a thickness of 280 μm in the semiconductor wafer except for bumps.

Then, the aforementioned surface protection tape (in other words, the first support sheet) is removed from the thermosetting resin film in the first laminated structure. Through the above steps, a second laminated structure (semiconductor wafer with thermosetting resin film) constituted by providing a thermosetting resin film on the bump formation surface of the semiconductor wafer is obtained.

Then, using a thermosetting device (“RAD-9100 m/12” manufactured by Lindeco Co., Ltd.), the thermosetting resin film in the second laminated structure obtained above was heated at a processing temperature of 130°C and a processing pressure of 0.5 MPa. , The heat and pressure treatment is performed under the condition of 2 hours of treatment time to thermally harden to form the first protective film. Then, the obtained first protective film was left to cool to 23°C over about 8 hours. Through the above steps, a third layered structure (in other words, a semiconductor wafer with a first protective film) formed by having a first protective film on the bump formation surface of the semiconductor wafer is obtained.

Then, the presence or absence of warpage of the obtained third laminated structure was observed over the entire circumference, but no warpage was observed (that is, the amount of warpage of the actual laminated wafer product was 0 mm).

[Example 2] In Example 1, the mixing ratio of the polymer component (A), epoxy resin (B1), thermosetting agent (B2), curing accelerator (C) and filler (D) was changed as shown in Table 1. The composition (III-1) for forming a thermosetting resin layer was prepared in the same manner as in Example 1, and the thermosetting resin film of Example 2 was produced.

In the thermosetting resin film of Example 2, the ratio of the total content of all types of thermosetting components was 80.8% by mass, and the total value of X values was 321 g/eq.

In the thermosetting resin film of Example 2, the amount of warpage of the copper foil laminated product measured in the same manner as in Example 1 was 10 mm.

In the thermosetting resin film of Example 2, the amount of warpage of the actual laminated wafer measured in the same manner as in Example 1 was 0 mm.

[Example 3] In Example 1, the mixing ratios of polymer component (A), epoxy resin (B1), thermosetting agent (B2), curing accelerator (C) and filler (D) were changed as shown in Table 1. Except for this, the composition (III-1) for forming a thermosetting resin layer was prepared in the same manner as in Example 1, and the thermosetting resin film of Example 3 was produced.

In the thermosetting resin film of Example 3, the ratio of the total content of all types of thermosetting components was 80.8% by mass, and the total value of the X value was 349 g/eq.

In the thermosetting resin film of Example 3, the amount of warpage of the copper foil laminated product measured in the same manner as in Example 1 was 0 mm.

In the thermosetting resin film of Example 3, the amount of warpage of the actual laminated wafer measured in the same manner as in Example 1 was 0 mm.

[Comparative Example 1] In Example 1, the mixing ratios of polymer component (A), epoxy resin (B1), thermosetting agent (B2), curing accelerator (C) and filler (D) were changed as shown in Table 1. Except that, in the same manner as in Example 1, a composition (III-1) for forming a thermosetting resin layer was prepared, and a thermosetting resin film of Comparative Example 1 was produced.

In the thermosetting resin film of Comparative Example 1, the ratio of the total content of all types of thermosetting components was 80.8% by mass, and the total value of X values was 245 g/eq.

In the thermosetting resin film of Comparative Example 1, the amount of warpage of the copper foil laminated product measured in the same manner as in Example 1 was 35 mm.

In the thermosetting resin film of Comparative Example 1, the amount of warpage of the actual laminated wafer product measured in the same manner as in Example 1 was 15 mm.

[Comparative Example 2] In Example 1, the mixing ratios of polymer component (A), epoxy resin (B1), thermosetting agent (B2), curing accelerator (C) and filler (D) were changed as shown in Table 1. Except this, the composition (III-1) for forming a thermosetting resin layer was prepared in the same manner as in Example 1, and the thermosetting resin film of Comparative Example 2 was produced.

In the thermosetting resin film of Comparative Example 2, the ratio of the total content of all types of thermosetting components was 80.8% by mass, and the total value of the X value was 266 g/eq.

In the thermosetting resin film of Comparative Example 2, the amount of warpage of the copper foil laminated product measured in the same manner as in Example 1 was 30 mm.

In the thermosetting resin film of Comparative Example 2, the amount of warpage of the actual laminated wafer measured in the same manner as in Example 1 was 10 mm.

[Table 1] Example 1 Example 2 Example 3 Components (content (parts by mass)) of the composition for forming a thermosetting resin layer Polymer component (A) (A)-1 10.0 10.0 10.0 Epoxy resin (B1) (B1)-1 - 41.0 65.0 (B1)-2 34.0 - - (B1)-3 25.8 10.8 - Thermal hardener (B2) (B2)-1 21.0 - 15.8 (B2)-2 - 29.0 - Hardening accelerator (C) (C)-1 0.2 0.2 0.5 Filling material (D) (D)-1 9.0 9.0 9.0 Ratio of total content of all types of thermosetting components (mass%) 80.8 80.8 80.8 Total value of X value (g/eq) 301 321 349 Evaluation results of the first protective film Warpage of copper foil laminated product (mm) 15 10 0 The amount of warpage of the actual laminated product (mm) 0 0 0

[Table 2] Comparative example 1 Comparative example 2 Components (content (parts by mass)) of the composition for forming a thermosetting resin layer Polymer component (A) (A)-1 10.0 10.0 Epoxy resin (B1) (B1)-1 - 12.0 (B1)-2 - - (B1)-3 45.8 34.8 Thermal hardener (B2) (B2)-1 - - (B2)-2 35.0 34.0 Hardening accelerator (C) (C)-1 0.2 0.2 Filling material (D) (D)-1 9.0 9.0 Ratio of total content of all types of thermosetting components (mass%) 80.8 80.8 Total value of X value (g/eq) 245 266 Evaluation results of the first protective film Warpage of copper foil laminated product (mm) 35 30 The amount of warpage of the actual laminated product (mm) 15 10

From the above results, it is obvious that the thermosetting resin film of Examples 1 to 3 has a copper foil laminate product with a warpage of 20 mm or less, so the thermosetting resin film is attached to the protruding electrode to form When the surface is thermally cured and then left to cool to room temperature, a protective film can be formed in a state where the warpage of the actual laminated wafer is suppressed, and it has better characteristics.

In addition, since the total value of the X value of the thermosetting resin films of Examples 1 to 3 is 300 g/eq or more, the thermosetting resin film was attached to the protruding electrode forming surface and thermally cured When left to cool to room temperature, a protective film can be formed in a state where the warpage of the actual laminated wafer is suppressed, and it has better characteristics.

In contrast, the thermosetting resin film of Comparative Example 1 to Comparative Example 2 had a copper foil laminate with a warpage of more than 20 mm. Therefore, the thermosetting resin film was attached to the protruding electrode forming surface and heated When it is left to cool to room temperature after hardening, large warpage occurs.

In addition, since the total value of the X value of the thermosetting resin film of Comparative Example 1 to Comparative Example 2 was less than 300 g/eq, the thermosetting resin film was attached to the protruding electrode forming surface and thermally cured When left to cool to room temperature, large warpage occurs. [Industry Availability]

The present invention can be used to manufacture workpieces and the like having protruding electrodes in the connection pads used in the flip chip mounting method.

1,2,3: The first protective film formation sheet 8: The second protective film formation sheet 9: Workpiece 9a: Circuit surface of the workpiece 9b: Inner surface of the workpiece 11: First base material 11a : One side of the first substrate 12: Thermosetting resin layer (thermosetting resin film) 12a: The first side of the thermosetting resin layer (thermosetting resin film) 12': The first protective film 12a': The first surface of the first protective film 13: the first adhesive layer 13a: one side of the first adhesive layer 14: the first intermediate layer 81: the second substrate 82: the second protective film forming film 83: the second Adhesive layer 83a: one surface of the second adhesive layer 90: workpiece 90a: circuit surface of the workpiece 90b: inner surface of the workpiece 91: protruding electrode 91a: the surface of the protruding electrode 101, 102, 103: the first support sheet 101a, 102a, 103a: the surface of the first support sheet 120': the first protective film after cutting 120a': the first surface of the first protective film after cutting 201: the first laminated structure 202: the second laminated structure 203: the third Laminated structure 204: 4th laminated structure 206: 6th laminated structure 801: Second support sheet 801a: One side of the second support sheet 820: Second protective film formation film 910 after cutting: Head top 990: Workpiece D ₉₁ : Distance H ₉₁ : Height T ₉₀ : Thickness W ₉₁ : Width

Fig. 1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a protruding electrode forming surface using a thermosetting resin film according to an embodiment of the present invention. Fig. 2 is a cross-sectional view schematically showing an example of a first protective film forming sheet according to an embodiment of the present invention. Fig. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet according to the embodiment of the present invention. Fig. 4 is a cross-sectional view schematically showing another example of the first protective film forming sheet according to one embodiment of the present invention. [Fig. 5A] is an enlarged cross-sectional view for schematically explaining a method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention. [Fig. 5B] is an enlarged cross-sectional view for schematically explaining a method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention. [FIG. 5C] is an enlarged cross-sectional view for schematically explaining a method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention. [Fig. 6A] is an enlarged cross-sectional view for schematically explaining a method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention. [Fig. 6B] is an enlarged cross-sectional view for schematically explaining a method of manufacturing a workpiece with a first protective film according to an embodiment of the present invention.

1: Sheet for forming the first protective film

11: The first substrate

12: Thermosetting resin layer (thermosetting resin film)

13: The first adhesive layer

13a: One side of the first adhesive layer

101: The first support piece

101a: Surface of the first support sheet

Claims (5)

A thermosetting resin film for attaching to the surface of the workpiece with protruding electrodes and curing to form a first protective film on the surface; Attach the aforementioned thermosetting resin film to a round copper foil with a thickness of 35 μm and a diameter of 8 inches, and place the aforementioned copper foil on the lower side in a flat state so that the aforementioned thermosetting resin film is thermally cured and placed on the entire circumference after cooling The maximum amount of warpage is 20mm or less. A thermosetting resin film for attaching to the surface of the workpiece with protruding electrodes and curing to form a first protective film on the surface; The aforementioned thermosetting resin film contains thermosetting components other than the epoxy-containing acrylic resin with a weight average molecular weight greater than 10,000; For the thermosetting components contained in the thermosetting resin film, the X value calculated by the following formula is calculated for each type, and when all types of the thermosetting components contained in the thermosetting resin film are obtained In the case of the total value of the aforementioned X value in the sexual component, the aforementioned total value becomes 300 g/eq or more; X=[The equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)]×[The content of the thermosetting component (parts by mass) of the thermosetting resin film]/[Thermosetting resin film Total content (parts by mass) of all types of thermosetting components]. A first protective film forming sheet, including: The first support piece; and The thermosetting resin film as described in claim 1 or 2 on one side of the aforementioned first support sheet. A kit with: The thermosetting resin film as described in claim 1 or 2; and A film for forming a second protective film to be attached to the inner surface of the workpiece on the opposite side to the surface with the protruding electrode. A method for manufacturing a workpiece with a first protective film, including: The step of attaching the thermosetting resin film as described in claim 1 or 2 to the surface with protruding electrodes in the workpiece; The step of thermally curing the attached thermosetting resin film to form a first protective film; and The step of dividing the aforementioned workpiece and cutting the aforementioned first protective film.

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