JPWO2020175421A1 - Thermosetting resin film and first protective film forming sheet - Google Patents

Abstract

The thermosetting resin film of the present embodiment is a thermosetting resin film for forming a first protective film on the surface by attaching the thermosetting resin film to a surface of the work having a protruding electrode and heat-curing the film. The thermosetting resin film contains two or more kinds of thermosetting components other than the acrylic resin having an epoxy group, and all kinds of the above-mentioned heats with respect to the total mass of the thermosetting resin film in the thermosetting resin film. The ratio of the total content of the curable components is 40% by mass or more, and the X value is obtained for each type of the thermosetting components contained in the thermosetting resin film, and all types of the thermosetting components are obtained. When the total value of the X values in the above is obtained, the total value is 400 g / eq or less.

Description

The present invention relates to a thermosetting resin film and a first protective film forming sheet.
This application claims priority based on Japanese Patent Application No. 2019-032828 filed in Japan on February 26, 2019, the contents of which are incorporated herein by reference.

Conventionally, when a multi-pin LSI package used for an MPU, a gate array, or the like is mounted on a printed wiring board, a work (for example, a semiconductor wafer or the like) provided with a protruding electrode (for example, a bump, a pillar, etc.) is used. By the so-called face-down method, a projecting electrode in a workpiece (for example, a semiconductor chip which is a divided piece of a semiconductor wafer) is brought into contact with a phase-corresponding terminal portion on a substrate in a face-to-face contact, and fusion / diffusion bonding is performed. , Flip chip mounting method has been adopted.

When this mounting method is adopted, a curable resin film is attached to the surface of the protruding electrode and the circuit surface of the work in order to protect the circuit surface of the work and the circuit surface of the work, and the film is cured to obtain these. A protective film may be formed on the surface of the surface.
In addition, in this specification, a combination of a surface of a projecting electrode and a circuit surface of a work or a workpiece may be referred to as a “projecting electrode forming surface”.

The curable resin film is usually attached to the projecting electrode forming surface of the work in a state of being softened by heating. By doing so, the upper portion including the crown 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 projecting electrodes so as to cover the projecting electrodes of the work, adheres to the circuit surface, and covers the surface of the projecting electrodes, particularly the surface of the vicinity of the circuit surface. And embed a protruding electrode. After that, the curable resin film is further cured to cover the circuit surface of the work and the surface of the vicinity of the circuit surface of the projecting electrode to become a protective film that protects these regions.

When a semiconductor wafer is used, the semiconductor chip used in this mounting method is divided by, for example, grinding or dicing the surface of the semiconductor wafer having a protruding electrode formed on the circuit surface on the side opposite to the circuit surface. Obtained by doing.
In the process of obtaining such a semiconductor chip, usually, for the purpose of protecting the circuit surface and the projecting electrode of the semiconductor wafer, a curable resin film is attached to the projecting electrode forming surface, and this film is cured to project. A protective film is formed on the shaped electrode forming surface.
Further, the semiconductor wafer is divided into semiconductor chips, and finally, a semiconductor chip having a protective film on the projecting electrode forming surface (in the present specification, it may be referred to as a "semiconductor chip with a protective film"). (See Patent Document 1).

A work workpiece having a protective film on such a protruding electrode forming surface (in this specification, it may be referred to as a “work workpiece with a protective film”) is further mounted on a substrate to form a package. Further, using this package, a target device is configured. When a semiconductor chip with a protective film is mounted on a substrate, the semiconductor package obtained by this is used to configure a target semiconductor device.

Japanese Patent No. 5515811

When a conventional curable resin film such as that disclosed in Patent Document 1 is used, the division of the work (for example, division of a semiconductor wafer into semiconductor chips) is usually performed by blade dicing using a dicing blade. Was done by. However, although this method is the most widely used, it is not suitable for manufacturing a work piece having a small size or a work piece having a thin thickness, for example. This is because such a workpiece is likely to be cracked or chipped.

Therefore, the present invention is a resin film capable of forming a protective film for protecting the projecting electrode forming surface of the work or the workpiece, and a novel method for dividing the work by using this resin film. It is an object of the present invention to provide a resin film to which the above is applicable. In particular, when such a new method is applied, the residual film on the upper part of the projecting electrode is suppressed when the film is attached to the projecting electrode forming surface, and the protective film which is a cured product is satisfactorily obtained when the work is divided. It is an object of the present invention to provide a resin film that can be cut.

The present invention is a thermosetting resin film for forming a first protective film on the surface by attaching the work to a surface having a protruding electrode and thermosetting the surface. The thermosetting resin film is a thermosetting resin film. , A thermosetting component other than an acrylic resin having an epoxy group, and all kinds of the thermosetting components with respect to the total mass of the thermosetting resin film in the thermosetting resin film. The ratio of the total content is 40% by mass or more, and the thermosetting component contained in the thermosetting resin film has the following formula for each type:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 is obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film is obtained, the total value is 400 g / eq or less. A curable resin film is provided.
The present invention also provides a first protective film forming sheet provided with the first support sheet and the thermosetting resin film on one surface of the first support sheet.

According to the present invention, it is a resin film capable of forming a protective film for protecting a projecting electrode forming surface of a work or a workpiece, and by using this resin film, a novel method for dividing a work is performed. A resin film is provided that makes the method applicable. In particular, when such a new method is applied, the residual film on the upper part of the projecting electrode is suppressed when the film is attached to the projecting electrode forming surface, and the protective film which is a cured product is satisfactorily obtained when the work is divided. A resin film that can be cut is provided.

It is sectional drawing which shows typically an example of the state which formed the 1st protective film on the projecting electrode forming surface using the curable resin film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the 1st protective film formation sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the other example of the 1st protective film formation sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows still another example of the 1st protective film forming sheet which concerns on one Embodiment of this invention. It is an enlarged cross-sectional view for schematically explaining the manufacturing method of the work workpiece with the 1st protective film in the case of using the 1st protective film forming sheet which concerns on one Embodiment of this invention. It is an enlarged cross-sectional view for schematically explaining the manufacturing method of the work workpiece with the 1st protective film in the case of using the 1st protective film forming sheet which concerns on one Embodiment of this invention. It is an enlarged cross-sectional view for schematically explaining the manufacturing method of the work workpiece with the 1st protective film in the case of using the 1st protective film forming sheet which concerns on one Embodiment of this invention. It is an enlarged cross-sectional view for schematically explaining the manufacturing method of the work workpiece with the 1st protective film in the case of using the 1st protective film forming sheet which concerns on one Embodiment of this invention. It is an enlarged cross-sectional view for schematically explaining the manufacturing method of the work workpiece with the 1st protective film in the case of using the 1st protective film forming sheet which concerns on one Embodiment of this invention.

-The thermosetting resin film, the sheet for forming the first protective film The thermosetting resin film according to one embodiment of the present invention is attached to the surface of the work having the projecting electrode (that is, the surface on which the projecting electrode is formed). A thermosetting resin film for forming a first protective film on the surface by thermosetting, the thermosetting resin film is thermosetting of two or more types other than an acrylic resin having an epoxy group. The ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film in the thermosetting resin film containing the sex component is 40% by mass or more, and the heat. Regarding the thermosetting component contained in the curable resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 is obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film is obtained, the total value is 400 g / eq or less.

Further, the first protective film forming sheet according to the embodiment of the present invention includes a first support sheet, and the thermosetting resin film is provided on one surface of the first support sheet. .. In the first protective film forming sheet, the "thermosetting resin film" may be referred to as a "thermosetting resin layer".

In the present embodiment, examples of the work include semiconductor wafers and the like.
Examples of the workpiece include a semiconductor chip which is a divided product of a semiconductor wafer.
Machining of the work includes, for example, division.
Examples of the projecting electrode include bumps, pillars and the like. The projecting electrode is provided on the connection pad portion of the work, and is composed of eutectic solder, high temperature solder, gold, copper, or the like.

The first protective film forming sheet is attached to the projecting electrode forming surface of the work (that is, the surface of the projecting electrode and the circuit surface of the work) via the thermosetting resin film (thermosetting resin layer). And used. The fluidity of the thermosetting resin film after the application is increased by heating, and the upper portion including the crown of the projecting electrode penetrates the thermosetting resin film and protrudes from the thermosetting resin film. Further, the thermosetting resin film spreads between the projecting electrodes so as to cover the projecting electrodes, adheres to the circuit surface, and covers the surface of the projecting electrodes, particularly the surface of the portion near the circuit surface. Embed a protruding electrode. The thermosetting resin film in this state is further cured by heating to finally form a first protective film, and protects the circuit surface and the projecting electrode in a state of being in close contact with them. As described above, by using the thermosetting resin film of the present embodiment, the circuit surface of the work and the portion near the circuit surface of the projecting electrode, that is, the base portion are sufficiently protected by the first protective film. ..

In the work after the first protective film forming sheet is attached, for example, the surface opposite to the circuit surface is ground if necessary, then the first support sheet is removed, and then the thermosetting resin is applied. By heating the film, the protruding electrodes are embedded and the first protective film is formed. Further, the work was divided (that is, individualized into a workpiece) and the first protective film was cut, and the obtained first protective film after cutting was provided on the projecting electrode forming surface. A target substrate device such as a semiconductor device is manufactured by using a workpiece (sometimes referred to as a "work workpiece with a first protective film" in the present specification). These steps will be described in detail later.

In the present specification, unless otherwise specified, the description of a mere "curable resin film" means a "curable resin film before curing", and the description of a mere "curable resin layer" is used. , Means "curable resin layer before curing". For example, the "thermosetting resin film" means a "thermosetting resin film before curing", and the "first protective film" means a cured product of a thermosetting resin film.

The thermosetting resin film of the present embodiment is suitable for applying a method different from the conventional method as a method for dividing (in other words, individualizing) the work into workpieces. Here, as the "method different from the conventional method", for example, the following method can be mentioned.
That is, a modified layer is formed inside the work by irradiating the work provided with the first protective film formed from the thermosetting resin film on the projecting electrode forming surface with laser light. Next, a force is applied to the work after forming this modified layer. More specifically, in the present embodiment, the work is expanded in a direction parallel to the circuit plane. As a result, the work is divided at the site of the modified layer. At this time, by applying a force to the first protective film, more specifically, by expanding the first protective film in a direction parallel to the surface to be attached to the work, the first protective film is also formed at the same time. Disconnect. At this time, the first protective film is cut along the divided portion of the work. As described above, the workpiece with the first protective film including the workpiece and the first protective film after cutting formed on the projecting electrode forming surface of the workpiece is manufactured. At the time of manufacturing such a workpiece, the first protective film is a cured product of the thermosetting resin film, so that the workpiece can be satisfactorily divided into the workpiece. Further, since the first protective film itself is a cured product of the thermosetting resin film, it can be easily cut along the divided portion of the work when the work is divided.

The method of dividing the work with the formation of such a modified layer is called stealth dicing (registered trademark), and by irradiating the work with laser light, the work is scraped off from the irradiated part and the work is surfaced. It is essentially completely different from laser dicing, which cuts from the ground.

<< Ratio of total content of all types of thermosetting components >>
In the thermosetting resin film, the "thermosetting component" that defines the ratio of the total content described above is a component that exhibits a curing reaction by heating. However, the acrylic resin having an epoxy group is not included in this thermosetting component. Examples of the thermosetting component include a thermosetting component (B) described later.
Examples of the thermosetting component (B) include epoxy-based thermosetting resins, 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 are subject to the above-mentioned regulation of the total content ratio.
On the other hand, examples of the acrylic resin having an epoxy group, which is not included in the thermosetting component, include those having an epoxy group among the acrylic resins in the polymer component (A) described later. For example, an acrylic resin having a glycidyl group is included in an acrylic resin having an epoxy group.

The thermosetting component contained in the thermosetting resin film is two or more kinds, and the combination and ratio thereof can be arbitrarily selected.

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

By satisfying the condition of the ratio of the total content, the thermosetting resin film can suppress the residue on the upper part including the crown of the projecting electrode when the work is attached to the projecting electrode forming surface. It has appropriate properties as a resin film for forming the first protective film. In this way, when the thermosetting resin film is attached to the projecting electrode forming surface, the thermosetting resin film does not remain on the upper part of the projecting electrode, in other words, the upper part of the projecting electrode is thermally cured. By projecting through the sex resin film, the finally obtained workpiece can be sufficiently electrically bonded to the substrate by the protruding electrode when the flip chip is mounted. That is, unless the thermosetting resin film can suppress the residue on the upper part of the projecting electrode, the workpiece cannot be put into practical use.

The ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film in the thermosetting resin film is, for example, in that the above-mentioned advantageous effects can be obtained more remarkably. , 50% by 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 total content is not particularly limited. For example, in terms of improving the film-forming property of the thermosetting resin film, the ratio of the total content is preferably 90% by mass or less.

The ratio of the total content can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and upper limit value. For example, in one embodiment, the proportion of the total content is any of 40-90% by mass, 50-90% by mass, 60-90% by mass, 70-90% by mass, and 80-90% by mass. You may.

<< Total value of X values >>
The X value is calculated by the above formula for one kind of thermosetting component contained in the thermosetting resin film.
The "thermosetting component" for which the X value is calculated is the same as the "thermosetting component" that defines the ratio of the total content in the thermosetting resin film.

The "functional group involved in the thermosetting reaction of the thermosetting component" for calculating the X value is, for example, an epoxy group in the case of the epoxy resin (B1) described later, and the thermosetting agent (B2) described later. ), A phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anodized, or the like. However, these are examples of the functional groups.

Consider a case where the thermosetting resin film contains a type p (p is an integer of 2 or more) thermosetting component. These thermosetting components are designated as M ₁ and M _p for each type. Then, an equivalent amount of the functional groups of the thermosetting component _{M 1 m} 1 and (g / eq), the equivalent of the functional groups of the thermosetting component _{M p} and _m p (g / eq), a thermosetting resin The content of the thermosetting component M _{1 of the 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, for the thermosetting component M ₁ , the X value (hereinafter referred to as "X ₁ value") is calculated by the following formula.

Similarly, for the thermosetting component M _p , the X value (hereinafter referred to as “X _p value”) is calculated by the following formula.

Then, the full range of the thermosetting component thermosetting resin film contains _{(M 1, ···, M P} ) wherein the X value in the _(X 1, · · ·, Xp) sum of the following It will be as it is.

The equivalence of the functional groups of the thermosetting component _{(m 1, m p (g} / eq)) is not identified by a constant value, identified in the numerical range with a width lower limit of the numerical range The average value calculated from the value and the upper limit value may be adopted as the equivalent of the functional group.

In the thermosetting resin film, the total value of the X values is 400 g / eq or less.
By satisfying the condition of the total value of the X values, the first protective film, which is a cured product of the thermosetting resin film, can be easily cut when the work is divided. As a result, a workpiece having a first protective film after cutting on the projecting electrode forming surface can be manufactured with high efficiency.

In the thermosetting resin film, the total value of the X values is, for example, 375 g / eq or less, 350 g / eq or less, and 325 g / eq or less, in that the above-mentioned advantageous effects can be obtained more remarkably. May be.

The lower limit of the total value of the X values is not particularly limited. For example, in the thermosetting resin film, the total value of the X values is preferably 100 g / eq or more in that the decrease in flexibility due to the excessive crosslinking reaction is suppressed.

The total value of the X values can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and upper limit value. For example, in one embodiment, the total value of the X values may be any of 100 to 400 g / eq, 100 to 375 g / eq, 100 to 350 g / eq, and 100 to 325 g / eq.

<< Light transmittance of thermosetting resin film >>
The transmittance of light having a wavelength of 1342 nm in the one-layer thermosetting resin film having a thickness of 200 μm is preferably 50% or more.
Further, the laminated film having a total thickness of 200 μm, which is formed by laminating two or more layers of the thermosetting resin film having a thickness of less than 200 μm, has a light transmittance of 50% or more at a wavelength of 1342 nm. Is preferable.

When the method described above involving the formation of a modified layer inside the work is applied as a method of dividing the work to produce a work piece, the work is modified by irradiating the work with a laser beam having a wavelength of 1342 nm. A layer can be formed. At this time, the laser beam may be applied to the work from the circuit surface side thereof or from the back surface side thereof. However, when the laser light is irradiated to the work from the circuit surface side, the laser light is irradiated through the first protective film formed on the circuit surface.
On the other hand, the thermosetting resin film and the cured product thereof (for example, the first protective film) have almost or exactly the same transmittance of light having the same wavelength. Therefore, when the transmittance of the light having a wavelength of 1342 nm of the one-layer thermosetting resin film having a thickness of 200 μm is 50% or more, the transmittance of the cured product of the light having a wavelength of 1342 nm is also 50% or more. It becomes. Similarly, when the transmittance of light having a wavelength of 1342 nm of the laminated film is 50% or more, the transmittance of light having a wavelength of 1342 nm of the cured product is also 50% or more. That is, the first protective film formed by using the thermosetting resin film having the same composition as that satisfying the condition of the light transmittance is satisfactorily transmitted the laser light having a wavelength of 1342 nm. Therefore, a work provided with such a first protective film on the circuit surface is suitable for irradiating a laser beam from the circuit surface side to form a modified layer inside the work.

In that the above-mentioned effect becomes more remarkable, the transmittance of light having a wavelength of 1342 nm of a single-layer thermosetting resin film having a thickness of 200 μm or a laminated film having a total thickness of 200 μm is, for example, , 60% or more, 70% or more, 80% or more, and 85% or more.

The upper limit of the transmittance of light having a wavelength of 1342 nm in a single-layer thermosetting resin film having a thickness of 200 μm or a laminated film having a total thickness of 200 μm is not particularly limited, and the higher the value, the more preferable. For example, the transmittance of the light is preferably 95% or less in that the thermosetting resin film is relatively easy to manufacture.

The light transmittance can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and upper limit value. In one embodiment, the light transmittance is preferably 50 to 95%, for example, 60 to 95%, 70 to 95%, 80 to 95%, and 85 to 95%. May be good.

If the components contained in the one-layer thermosetting resin film having a thickness of 200 μm and the laminated film having a total thickness of 200 μm are the same, these (one-layer thermosetting resin film). And the laminated film), the light transmittance is not limited to the case where the wavelength of the light is 1342 nm, but is the same as each other.

The number of layers of the thermosetting resin film having a thickness of less than 200 μm constituting the laminated film is not particularly limited, but is preferably 2 to 6. With such a number of layers, the laminated film can be produced more easily.

The thicknesses of the thermosetting resin films having a thickness of less than 200 μm constituting the laminated film may be all the same, all may be different, or only a part thereof may be the same. ..

In the present embodiment, the reason why the thickness of the one-layer thermosetting resin film or laminated film, which is the object of specifying the light transmittance, is specified to be 200 μm is that the thermosetting resin having such a thickness is specified. This is because the transmittance of the light can be measured more accurately and easily by using the film or the laminated film.
In the present embodiment, the thickness of the one-layer thermosetting resin film and the thermosetting resin film composed of two or more layers is not limited to 200 μm, as will be described later.

The light transmittance is determined by, for example, the type and content of components contained in the thermosetting resin film such as the colorant (I) and the filler (D) described later, and the surface state of the thermosetting resin film. It can be adjusted by adjusting the like.

<< Breaking strength of the first protective film >>
The breaking strength of the first protective film having a size of 20 mm × 130 mm and a thickness of 40 μm, measured by the following method, is preferably 55 MPa or less. The first protective film having the same composition as the first protective film having a breaking strength of not less than the upper limit value can be easily cut by the expand described later.
As for the breaking strength of the first protective film, the distance between the gripping devices in the first protective film is 80 mm, the tensile speed of the first protective film is 200 mm / min, and the first protective film is attached to the surface by the gripping device. The maximum stress measured when pulled in parallel directions can be adopted.
As the first protective film to be measured for the maximum stress, a film obtained by heat-curing a thermosetting resin film at 130 ° C. for 2 hours can be used.

From the point that the above-mentioned effect becomes more remarkable, the breaking strength of the first protective film may be, for example, 52.5 MPa or less, 50 MPa or less, and 47.5 MPa or less.

The lower limit of the breaking strength of the first protective film is not particularly limited. In terms of increasing the protective ability of the first protective film, the breaking strength of the first protective film is preferably 0.1 MPa or more.

The breaking strength of the first protective film can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and upper limit value. In one embodiment, the breaking strength of the first protective film is preferably 0.1 to 55 MPa, for example, 0.1 to 52.5 MPa, 0.1 to 50 MPa, and 0.1 to 47.5 MPa. It may be either.

The breaking strength of the first protective film is, for example, the components contained in the composition for forming a thermosetting resin layer described later, particularly the polymer component (A), the coupling agent (E), the filler (D) and the like. It can be adjusted by adjusting the type and content, the thickness of the first protective film (in other words, the thickness of the thermosetting resin film), and the like.

In a work or work workpiece having a protruding electrode on the circuit surface, the surface (rear surface) opposite to the circuit surface may be exposed. Therefore, a protective film containing an organic material (in the present specification, it may be referred to as a "second protective film" to distinguish it from the first protective film) may be formed on the back surface. .. The second protective film is used to prevent cracks from occurring in the workpiece after the workpiece is divided or packaged. The workpiece with the second protective film having the second protective film on the back surface is finally incorporated into a target substrate device such as a semiconductor device.
On the other hand, the second protective film may be required to have a function of marking information about the workpiece with a laser and concealing the back surface of the workpiece. As a film that satisfies such a requirement, a curable resin film having an adjusted light transmission characteristic, which can form a second protective film by curing, is known.
However, since the formation position of the workpiece is different between the second protective film for protecting the back surface of the workpiece and the first protective film for protecting the projecting electrode forming surface of the workpiece. The required characteristics are also different from each other. Therefore, it is usually difficult to immediately use a thermosetting resin film capable of forming a second protective film for 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 projecting electrode forming surface using the thermosetting resin film of the present embodiment. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged and shown, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

A plurality of protruding electrodes 91 are provided on the circuit surface 90a of the work 90 shown here. In FIG. 1, reference numeral 90b indicates a surface (back surface) of the work 90 opposite to the circuit surface 90a.
The projecting electrode 91 has a shape in which a part of the sphere is cut off by a flat surface, and the flat surface corresponding to the cut and exposed portion is in contact with the circuit surface 90a of the work 90. ..
The shape of the projecting electrode 91 is substantially spherical.

The first protective film 12'is formed by using the thermosetting resin film of the present embodiment, covers the circuit surface 90a of the work 90, and further has a protruding shape among the surface 91a of the protruding electrode 91. It covers a region other than the crown 910 of the electrode 91 and its vicinity. In this way, the first protective film 12'is in close contact with the surface 91a other than the crown 910 of the protruding electrode 91 and its vicinity, and is also in close contact with the circuit surface 90a of the work 90 to embed the protruding electrode 91. I'm out.
The substantially spherical shape of the projecting electrode 91 as described above is particularly advantageous for forming the first protective film using the curable resin film.

The height _{H 91} of the projecting electrode 91 is not particularly limited, is preferably 50 to 500 [mu] m. When the height H ₉₁ of the projecting electrode 91 is at least the above lower limit value, the function of the projecting electrode 91 can be further improved. By the height _{H 91} of the projecting electrode 91 is not more than the upper limit, the protruding electrode forming surface of the workpiece 90 (i.e., the surface 91a of the projecting electrodes 91, the circuit surface 90a of the workpiece 90) thermal curing of the When the sex resin film is attached, the effect of suppressing the residual thermosetting resin film on the upper part including the crown 910 of the protruding electrode 91 becomes higher, and as a result, the first protective film 12 on the upper part of the protruding electrode 91 The effect of suppressing the formation of'is higher.
In the present specification, the "height of the protruding electrode" means the height of the protruding electrode at the highest position (that is, the crown) from the circuit surface of the work or the workpiece. means.

The width W ₉₁ of the projecting electrode 91 is not particularly limited, but is preferably 50 to 600 μm. When the width W ₉₁ of the projecting electrode 91 is equal to or larger than the lower limit, the function of the projecting electrode 91 can be further improved. By the width _{W 91} of the projecting electrode 91 is not more than the upper limit, the protruding electrode forming surface of the workpiece 90 (i.e., the surface 91a of the projecting electrodes 91, the circuit surface 90a of the workpiece 90) thermoset to When the resin film is attached, the effect of suppressing the residual thermosetting resin film on the upper part including the crown 910 of the protruding electrode 91 becomes higher, and as a result, the first protective film 12'on the upper part of the protruding electrode 91 The effect of suppressing the formation of is higher.
In the present specification, the "width of the projecting electrode" is defined as the "width of the projecting electrode" on the surface of the projecting electrode when viewed in a plan view from a direction perpendicular to the circuit surface of the work or the workpiece. It means the maximum value of a line segment obtained by connecting two different points with a straight line.

Distance _{D 91} between the adjacent projecting electrode 91 is not particularly limited, is preferably 100 to 800. By the distance _{D 91} between the projecting electrode 91 is not less than the lower limit, the protruding electrode forming surface of the workpiece 90 (i.e., the surface 91a of the projecting electrodes 91, the circuit surface 90a of the workpiece 90) thermal curing of the When the sex resin film is attached, the effect of suppressing the residual thermosetting resin film on the upper part including the crown 910 of the protruding electrode 91 becomes higher, and as a result, the first protective film 12 on the upper part of the protruding electrode 91 The effect of suppressing the formation of'is higher. By the distance D ₉₁ between the projecting electrode 91 is not more than the upper limit, the degree of freedom of arrangement of the projecting electrode 91 becomes higher.
In the present specification, the "distance between adjacent projecting electrodes" means the minimum value of the distance between the surfaces of adjacent projecting electrodes.

_{The thickness T 90} of the portion of the work 90 excluding the protruding electrode 91 may be appropriately selected according to the purpose of use of the work 90, and is not particularly limited.
_{For example, the thickness T 90} after grinding the back surface 90b of the work 90 is preferably 50 to 500 μm. _{When the thickness T 90} of the work 90 after grinding the back surface 90b is equal to or more than the lower limit value, the work work is damaged when the work 90 is divided (in other words, individualized into the work work). The effect of suppressing becomes higher. _{When the thickness T 90} of the work 90 after grinding the back surface 90b is not more than the upper limit value, a thin workpiece work piece can be obtained.
_{The thickness T 90} before grinding the back surface 90b of the work 90 is preferably 250 to 1500 μm.

The work to which the thermosetting resin film of the present embodiment is used is not limited to the one shown in FIG. 1, and some configurations have been changed, deleted or added within the range not impairing the effect of the present invention. It may be a thing.

For example, FIG. 1 shows a projecting electrode having an almost spherical shape (a shape in which a part of a sphere is cut off by a plane) as described above, and such a substantially spherical shape has a height. A shape stretched in a direction (in FIG. 1, a direction orthogonal to the circuit surface 90a of the work 90), that is, a shape of a spheroid that is almost a long sphere (in other words, a spheroid that is a long sphere). A spheroid that is a shape formed by crushing a protruding electrode (a shape in which a part including one end in the long axis direction is cut off by a flat surface) or an almost spherical shape as described above in the height direction, that is, a spheroid that is almost oblate. A projecting electrode having a body shape (in other words, a shape in which a portion including one end of a spheroid, which is a tongue, in the minor axis direction is cut off by a flat surface) is also mentioned as a projecting electrode having a preferable shape. Similar to the above-mentioned substantially spherical protruding electrode, such a substantially spheroid-shaped protruding electrode can also be used to form the first protective film by using the thermosetting resin film of the present embodiment. Especially advantageous.
In addition to these, the projecting electrodes include, for example, a cylinder, an elliptical column, a prism, an elliptical cone, a cone, a cone, a cone, or a cone; a cylinder, an ellipse. , A square column, a truncated cone, an elliptical cone or a square cone, and the above-mentioned substantially sphere or substantially rotating ellipsoid have a shape in combination.
The shape of the projecting electrode described so far is only an example of a preferable one when the thermosetting resin film of the present embodiment is applied, and the shape of the projecting electrode is not limited to these in the present invention.
Hereinafter, the configuration of the present invention will be described in detail.

(1) First support sheet The 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 a plurality of layers, the constituent materials and the thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.
In the present specification, not only in the case of the first support sheet, but also in the case of the first support sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers". May be different, and only some of the layers may be the same. ”Furthermore,“ multiple layers are different from each other ”means“ at least one of the constituent materials and thicknesses of each layer is different from each other. It means that.

The preferred first support sheet includes, for example, a first base material and a first pressure-sensitive adhesive layer provided on the first base material (in other words, a first base material and a first pressure-sensitive adhesive). The layers are laminated in these thickness directions), the first base material, the first intermediate layer provided on the first base material, and the first intermediate layer provided on the first intermediate layer. Only the first base material provided with the pressure-sensitive adhesive layer (in other words, the first base material, the first intermediate layer and the first pressure-sensitive adhesive layer are laminated in this order in the thickness direction). Those consisting of, etc. can be mentioned.

An example of the first protective film forming sheet of the present embodiment will be described below with reference to the drawings for each type of the first support sheet.

FIG. 2 is a cross-sectional view schematically showing an example of the first protective film forming sheet of the present embodiment.
As the first protective film forming sheet 1 shown here, a sheet obtained by laminating a first base material and a first pressure-sensitive adhesive layer in the thickness direction thereof is used as the first support sheet. That is, the first protective film forming sheet 1 includes the first base material 11, the first pressure-sensitive adhesive layer 13 provided on one surface of the first base material 11, and the first of the first pressure-sensitive adhesive layer 13. It is configured to include a thermosetting resin layer (thermosetting resin film) 12 provided on a surface 13a on the side opposite to the base material 11 side.
The first support sheet 101 is a laminate of the first base material 11 and the first pressure-sensitive adhesive layer 13. The first protective film forming sheet 1 is provided on the first support sheet 101 and one surface 101a of the first support sheet 101, in other words, on one surface 13a of the first pressure-sensitive adhesive layer 13. It can be said that the thermosetting resin layer 12 is provided.

In the thermosetting resin layer 12 in the first protective film forming sheet 1, the ratio of the total content of the above-mentioned thermosetting components is 40% by mass or more, and the total value of the above-mentioned X values is 400 g / eq or less. Is.

FIG. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet of the present embodiment.
In the drawings after FIG. 3, the same components as those shown in the already explained figures are designated by the same reference numerals as in the case of the already explained figures, and detailed description thereof will be omitted.

The first protective film forming sheet 2 shown here is a first support sheet in which a first base material, a first intermediate layer, and a first adhesive layer are laminated in this order in the thickness direction. I am using it. That is, the first protective film forming sheet 2 includes the first base material 11, the first intermediate layer 14 provided on one surface of the first base material 11, and the first base material of the first intermediate layer 14. The first pressure-sensitive adhesive layer 13 provided on the surface opposite to the 11 side and the thermosetting resin provided on the surface 13a on the side opposite to the first intermediate layer 14 side of the first pressure-sensitive adhesive layer 13. A layer (thermosetting resin film) 12 is provided and configured.
The first support sheet 102 is a laminate of the first base material 11, the first intermediate layer 14, and the first pressure-sensitive adhesive layer 13. The first protective film forming sheet 2 includes a first support sheet 102 and is thermosetting on one surface 102a of the first support sheet 102, in other words, on one surface 13a of the first pressure-sensitive adhesive layer 13. It can be said that the sex resin layer 12 is provided.

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

In the thermosetting resin layer 12 in the first protective film forming sheet 2, the ratio of the total content of the above-mentioned thermosetting components is 40% by mass or more, and the total value of the above-mentioned X values is 400 g / eq or less. Is.

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

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

In the thermosetting resin layer 12 in the first protective film forming sheet 3, the ratio of the total content of the above-mentioned thermosetting components is 40% by mass or more, and the total value of the above-mentioned X values is 400 g / eq or less. Is.

Next, the configuration of the first support sheet will be described.
In the present embodiment, a known one may be used as the first support sheet, and the first support sheet can be appropriately selected according to the purpose.

○ First base material The first base material is in the form of a sheet or a film, and examples of the constituent materials thereof include various resins.

The resin constituting the first base material may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The first base material may be only one layer (single layer), may be two or more layers, or may be a plurality of layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and a combination of the plurality of layers may be used. Is not particularly limited.

The thickness of the first base material is preferably 50 to 200 μm.
Here, the "thickness of the first base material" means the thickness of the entire first base material, and for example, the thickness of the first base material composed of a plurality of layers is all that constitute the first base material. Means the total thickness of the layers of.

The first base material contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the resin. You may be doing it.

The first base material may be transparent, opaque, colored depending on the intended purpose, or may have another layer vapor-deposited.
When the first pressure-sensitive adhesive layer or the thermosetting resin layer, which will be described later, has energy ray curability, the first substrate is preferably one that allows energy rays to pass through.

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

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

○ First Adhesive Layer The first adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, and polycarbonate, and acrylic resin is preferable.

In the present invention, the "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, and for example, the resin itself is not limited to having adhesiveness. It also includes a resin that exhibits adhesiveness when used in combination with other components such as additives, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.

The first pressure-sensitive adhesive layer may be only one layer (single layer), may be a plurality of layers of two or more, and when there are a plurality of layers, the plurality of layers may be the same or different from each other. Often, the combination of these multiple layers is not particularly limited.

The thickness of the first pressure-sensitive adhesive layer is preferably 3 to 40 μm.
Here, the "thickness of the first pressure-sensitive adhesive layer" means the thickness of the entire first pressure-sensitive adhesive layer, and for example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers is the thickness of the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.

The first pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive or may be formed by using a non-energy ray-curable pressure-sensitive adhesive. The first pressure-sensitive adhesive layer formed by using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
In the present specification, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. ..

<First Adhesive Composition>
The first pressure-sensitive adhesive layer can be formed by using the first pressure-sensitive adhesive composition containing the pressure-sensitive adhesive. For example, the first pressure-sensitive adhesive layer can be formed on a target portion by applying the first pressure-sensitive adhesive composition to the surface to be formed of the first pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the first pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers.

The coating of the first pressure-sensitive adhesive composition may be carried out by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like. A method using various coaters such as a screen coater, a Meyer bar coater, and a knife coater can be mentioned.

The drying conditions of the first pressure-sensitive adhesive composition are not particularly limited, but when the first pressure-sensitive adhesive composition contains a solvent, it is preferably heat-dried. The first pressure-sensitive adhesive composition containing the solvent may be dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example.

When the first pressure-sensitive adhesive layer is energy ray-curable, the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable first pressure-sensitive adhesive composition is, for example, non-energy. A first pressure-sensitive adhesive composition containing a linearly curable adhesive resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound. (I-1); An energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) (hereinafter, "adhesive resin (I-2a)". ) ”) In the first pressure-sensitive adhesive composition (I-2); the first pressure-sensitive adhesive containing the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low-molecular-weight compound. Examples thereof include the agent composition (I-3).

<First pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3)>
The components contained in the first pressure-sensitive adhesive composition (I-1), the first pressure-sensitive adhesive composition (I-2), or the first pressure-sensitive adhesive composition (I-3) are these three first pressure-sensitive adhesive compositions. Other general first pressure-sensitive adhesive compositions (referred to in the present specification as "first pressure-sensitive adhesive compositions other than the first pressure-sensitive adhesive compositions (I-1) to (I-3)") may also be used. It can be used in the same way.

As the first pressure-sensitive adhesive composition other than the first pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable pressure-sensitive adhesive composition, a non-energy ray-curable pressure-sensitive adhesive composition Can also be mentioned.
Examples of the non-energy ray-curable first pressure-sensitive adhesive composition include the first pressure-sensitive adhesive composition (I-4) containing the pressure-sensitive adhesive resin (I-1a).
The first pressure-sensitive adhesive composition (I-4) preferably contains an acrylic resin as the pressure-sensitive adhesive resin (I-1a), and more preferably contains one or more cross-linking agents. ..

<Manufacturing method of the first pressure-sensitive adhesive composition>
The first pressure-sensitive adhesive composition such as the first pressure-sensitive adhesive compositions (I-1) to (I-4) is a first pressure-sensitive adhesive containing the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive. It is obtained by blending each component for constituting a composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving it.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

○ First Intermediate Layer The first intermediate layer is in the form of a sheet or a film, and the constituent material thereof may be appropriately selected depending on the intended purpose and is not particularly limited.
For example, the first protective film provided on the projecting electrode forming surface reflects the shape of the projecting electrode existing on the circuit surface, thereby suppressing the deformation of the first protective film. For the purpose, a preferable constituent material of the first intermediate layer is urethane (meth) acrylate or the like from the viewpoint of further improving the adhesiveness of the first intermediate layer.

The first intermediate layer may be only one layer (single layer), may be a plurality of layers of two or more, and when there are a plurality of layers, the plurality of layers may be the same or different from each other. , The combination of these multiple layers is not particularly limited.

The thickness of the first intermediate layer can be appropriately adjusted according to the height of the protruding electrode present on the surface of the work to be protected or the work piece to be protected. For example, the thickness of the first intermediate layer is preferably 50 to 600 μm in that the influence of the protruding electrode having a relatively high height can be easily absorbed.
Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer, and for example, the thickness of the first intermediate layer composed of a plurality of layers is all that constitute the first intermediate layer. Means the total thickness of the layers of.

<< Composition for forming the first intermediate layer >>
The first intermediate layer can be formed by using a composition for forming a first intermediate layer containing the constituent material. For example, the composition for forming the first intermediate layer is applied to the surface to be formed of the first intermediate layer, dried as necessary, or cured by irradiation with energy rays, so that the first intermediate is applied to the target portion. Layers can be formed. A more specific method for forming the first intermediate layer will be described in detail later together with a method for forming the other layers.

The composition for forming the first intermediate layer can be applied, for example, in the same manner as in the case of the first pressure-sensitive adhesive composition.

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

<Method for Producing Composition for Forming First Intermediate Layer>
The composition for forming the first intermediate layer can be produced, for example, by the same method as in the case of the first pressure-sensitive adhesive composition, except that the compounding components are different.

◎ Thermosetting resin film (thermosetting resin layer)
The thermosetting resin film (thermosetting resin layer) is a film (layer) for protecting a circuit surface of a work and a workpiece and a projecting electrode provided on the circuit surface.
The thermosetting resin film forms a first protective film by thermosetting.

In the present specification, even after the thermosetting resin film is cured (in other words, after the first protective film is formed), the cured product of the first support sheet and the thermosetting resin film (in other words, after forming the first protective film). Then, as long as the laminated structure of the first support sheet and the first protective film) is maintained, this laminated structure is referred to as a "first protective film forming sheet".

The thermosetting resin film may or may not have an energy ray curable property in addition to the thermosetting property.
However, when the thermosetting resin film has the property of energy ray curability, the contribution of the thermosetting of the thermosetting resin film to the formation of the first protective film from the thermosetting resin film is the energy ray. It shall be larger than the contribution of curing.

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

The thickness of the thermosetting resin film is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 60 μm, regardless of the presence or absence of energy ray curability. When the thickness of the thermosetting resin film is at least the above lower limit value, a first protective film having higher protective ability can be formed. When the thickness of the thermosetting resin film is not more than the upper limit, the thermosetting resin film remains on the upper part of the projecting electrode when the thermosetting resin film is attached to the projecting electrode forming surface of the work. The effect of suppressing is higher. Further, when the thickness of the thermosetting resin film is not more than the upper limit value, the first protective film can be better cut when the work is divided.
Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film, and for example, the thickness of the thermosetting resin film composed of a plurality of layers means the thermosetting resin film. It means the total thickness of all the layers that make up.

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

The composition for forming a thermosetting resin layer may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, and the like. A method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater can be mentioned.

The drying conditions of the composition for forming a thermosetting resin layer are not particularly limited regardless of whether or not 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-dry it. The composition for forming a thermosetting resin layer containing a solvent may be dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example. However, it is preferable that the composition for forming a thermosetting resin layer is heat-dried so that the composition itself and the thermosetting resin film formed from the composition do not heat-cure.

The curing conditions when the thermosetting resin film is thermally cured to form the first protective film are not particularly limited as long as the degree of curing is such that the first protective film sufficiently exerts its function, and heat is not limited. It may be appropriately selected according to the type of the curable resin film.
For example, the heating temperature of the thermosetting resin film at the time of heat curing is preferably 100 to 200 ° C, more preferably 110 to 180 ° C, and particularly preferably 120 to 170 ° C. The heating time at the time of heat curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.

Preferred thermosetting resin films include, for example, those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component that can be regarded as being formed by a polymerization reaction of the polymerizable compound. Further, the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a trigger for the reaction. In the present specification, the polymerization reaction also includes a polycondensation reaction.

<Composition for forming a thermosetting resin layer (III-1)>
As a preferable composition for forming a thermosetting resin layer, for example, the composition for forming a thermosetting resin layer (III-1) containing the polymer component (A) and the thermosetting component (B) (the present specification). In the book, it may be simply abbreviated as "composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming property, flexibility and the like to a thermosetting resin film. The polymer component (A) has thermoplasticity and does not have thermosetting property.
The polymer component (A) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, when it is two or more kinds. The combination and ratio thereof can be arbitrarily selected.

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

Examples of the polyvinyl acetal in the polymer component (A) include known ones.
Among them, preferable polyvinyl acetals include, for example, polyvinyl formal, polyvinyl butyral and the like, and polyvinyl butyral is more preferable.
Examples of polyvinyl butyral include those having a structural unit represented by the following formulas (i) -1, (i) -2 and (i) -3.

（式中、ｌ、ｍ及びｎは、それぞれ独立に１以上の整数である。）

(In the equation, l, m, and n are each independently an integer of 1 or more.)

The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5000 to 20000, more preferably 8000 to 100,000. When the weight average molecular weight of polyvinyl acetal is in such a range, when the thermosetting resin film is attached to the projecting electrode forming surface, the residual thermosetting resin film on the upper part of the projecting electrode is suppressed. The effect will be higher.

The glass transition temperature (Tg) of polyvinyl acetal is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. When the Tg of polyvinyl acetal is in such a range, the effect of suppressing the residual of the thermosetting resin film on the upper part of the projecting electrode when the thermosetting resin film is attached to the projecting electrode forming surface is effective. It will be higher.

The ratio of three or more kinds of 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, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid. For example, "(meth) acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group", and "(meth) acrylate". "" Is a concept that includes both "acrylate" and "methacrylate".
Further, in the present specification, the "derivative" of a specific compound means a compound having a structure in which one or more hydrogen atoms of the compound are substituted with a group (substituent) other than the hydrogen atom. For example, (meth) acrylic acid ester is a derivative of (meth) acrylic acid.

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 1000 to 2000000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (stability over time during storage) of the thermosetting resin film is improved. When the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the thermosetting resin film easily follows the uneven surface of the adherend, and voids or the like are formed between the adherend and the thermosetting resin film. Occurrence is more suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, for example, the adhesive force between the cured product of the thermosetting resin film and the support sheet is suppressed, and the peelability of the support sheet is appropriately improved. When the Tg of the acrylic resin is not more than the above upper limit value, the adhesive force between the thermosetting resin film and the cured product thereof with the adherend is improved.

The acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like 2 Examples thereof include copolymers of monomers of more than one species.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth). N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylate Heptyl, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate , (Meta) hexadecyl acrylate ((meth) palmityl acrylate), (meth) heptadecyl acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), etc., the alkyl group constituting the alkyl ester is carbon. (Meta) acrylic acid alkyl ester having a chain structure of 1 to 18;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) Acrylic acid imide;
A glycidyl group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylic acid;
(Meta) hydroxymethyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) 3-hydroxypropyl acrylate, (meth) 2-hydroxybutyl acrylate, (meth) ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylic acid;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom.

The acrylic resin may be, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like, in addition to the (meth) acrylic acid ester. It may be copolymerized.

The monomer constituting the acrylic resin may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound without a cross-linking agent (F). When the acrylic resin is bonded to another compound by the functional group, 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), a thermoplastic resin other than the polyvinyl acetal and the acrylic resin (hereinafter, may be simply abbreviated as “thermoplastic resin”) is used as the polyvinyl acetal and the acrylic resin. It may be used alone or in combination with polyvinyl acetal or an acrylic resin. By using the thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, and the thermosetting resin film easily follows the uneven surface of the adherend, so that the adherend and the heat are generated. The generation of voids and the like may be further suppressed with the curable resin film.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80000.

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

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

The thermoplastic resin contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, if they are two or more kinds. The combination and ratio can be selected arbitrarily.

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

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is used. , The polymer component (A) and the thermosetting component (B) are considered to be contained.

[Thermosetting component (B)]
The thermosetting component (B) is a component for having a thermosetting property and heat-curing a thermosetting resin film to form a hard first protective film.
Further, in the thermosetting resin film, both the "thermosetting component" that defines the ratio of the total content described above and the "thermosetting component" for which the X value is calculated are thermosetting. Component (B) is applicable.

The thermosetting component (B) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.

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

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
In the thermosetting resin film, the epoxy resin (B1) is used for both the "thermosetting component" that defines the ratio of the total content described above and the "thermosetting component" for which the X value is calculated. And the thermosetting agent (B2) are both applicable.

The epoxy-based thermosetting resin contained in the composition (III-1) and the thermosetting resin film may be of only one type, may be of two or more types, and may be of two or more types. The combination and ratio thereof can be arbitrarily selected.

-Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, and the like. Examples thereof include biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins having no unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the work piece with the first protective film obtained by using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) group. Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 from the viewpoint of the curability of the thermosetting resin film and the strength and heat resistance of the resin film after curing. It is more preferably 10000, and particularly preferably 300-3000.

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

As the epoxy resin (B1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resin, biphenol, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin. ..
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
The thermosetting agent (B2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, and is not suitable for the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) has a softening point or a glass transition temperature from the viewpoint of improving the peelability of the first protective film from the first support sheet. Is preferable.

Among the thermosetting agents (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 30,000. , 400 to 10000 is more preferable, and 500 to 3000 is particularly preferable.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.

As the thermosetting agent (B2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting agent (B2) is, for example, 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). , 1 to 250 parts by mass, 1 to 150 parts by mass, 1 to 100 parts by mass, 1 to 75 parts by mass, and 1 to 50 parts by mass. When the content of the thermosetting agent (B2) is at least the lower limit value, the curing of the thermosetting resin film is more likely to proceed. When the content of the thermosetting agent (B2) is not more than the upper limit value, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained by using the first protective film forming sheet is used. Is 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)) is a polymer component. The content of (A) is 100 parts by mass, for example, 300 to 1400 parts by mass, 400 to 1300 parts by mass, 500 to 1100 parts by mass, 600 to 1000 parts by mass, or 700 to 900 parts by mass. You may. When the content of the thermosetting component (B) is in such a 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. do.

[Curing accelerator (C)]
The composition (III-1) and the thermosetting resin film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles (one or more hydrogen atoms other than hydrogen atom) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine. Examples thereof include tetraphenylboron salts such as tetraphenylborate.

The curing accelerator (C) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, when it is two or more kinds. The combination and ratio thereof can be arbitrarily selected.

When the curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (III-1) and the thermosetting resin film is 100 parts by mass of the content of the thermosetting component (B). On the other hand, for example, it may be any one of 0.01 to 10 parts by mass and 0.1 to 7 parts by mass. When the content of the curing accelerator (C) is at least the lower limit value, the effect of using the curing accelerator (C) is more remarkable. When the content of the curing accelerator (C) is not more than the above upper limit value, for example, the highly polar curing accelerator (C) can be used as an adherend in the thermosetting resin film under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesive interface side of the film is enhanced. As a result, the reliability of the workpiece with the first protective film obtained by using the sheet for forming the first protective film is further improved.

[Filler (D)]
The composition (III-1) and the thermosetting resin film may contain a filler (D). Since the thermosetting resin film contains the filler (D), the first protective film obtained by curing the thermosetting resin film can easily adjust the thermal expansion coefficient. By optimizing this coefficient of thermal expansion for the object to be formed of the first protective film, the reliability of the workpiece with the first protective film obtained by using the sheet for forming the first protective film becomes higher. improves. Further, when the thermosetting resin film contains the filler (D), the hygroscopicity of the first protective film can be reduced and the heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina, and more preferably silica.

The average particle size of the filler (D) may be appropriately selected depending on the intended purpose, and is not particularly limited, and may be, for example, 0.02 to 2 μm.
In the present specification, the "average particle size" means the value _{of the particle size (D 50} ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction / scattering method, unless otherwise specified. ..

The filler (D) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, if they are two or more kinds. The combination and ratio of can be arbitrarily selected.

In the composition (III-1), the ratio of the content of the filler (D) to the total content of all the components other than the solvent (that is, the total mass of the thermosetting resin film in the thermosetting resin film). , Percentage of content of filler (D)) is, for example, 3 to 60% by mass, 4 to 40% by mass, 5 to 30% by mass, 5 to 20% by mass, and 5 to 15% by mass. There may be. When the ratio is in such a range, the above-mentioned adjustment of the coefficient of thermal expansion of the first protective film becomes easier.

[Coupling agent (E)]
The composition (III-1) and the thermosetting resin film may contain a coupling agent (E). By using a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesion of the thermosetting resin film to the adherend can be improved. Further, by using the coupling agent (E), the cured product of the thermosetting resin film has improved water resistance without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (A), the thermosetting component (B) and the like, and is preferably a silane coupling agent. More preferred.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

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

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the thermosetting resin film is the polymer component (A) and the thermosetting component (B). It may be any of 0.03 to 20 parts by mass, 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the total content of. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin is improved and the adhesiveness of the thermosetting resin film to the adherend is improved. The effect of using the coupling agent (E) is more remarkable. When the content of the coupling agent (E) is not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), a polymer having a functional group such as a vinyl group capable of binding to another compound, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group, such as the above-mentioned acrylic resin, is used. In this case, the composition (III-1) and the thermosetting resin film may contain a cross-linking agent (F). The cross-linking agent (F) is a component for bonding the functional group in the polymer component (A) to another compound for cross-linking, and by cross-linking in this way, the initial adhesion of the thermosetting resin film is achieved. The force and cohesive force can be adjusted.

Examples of the cross-linking agent (F) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”. (May be abbreviated); Trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compounds and the like with a polyol compound. And so on. The "adduct" includes the aromatic polyhydric isocyanate compound, the aliphatic polyhydric isocyanate compound or the alicyclic polyvalent isocyanate compound, and low ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like. It means a reaction product of a molecularly active hydrogen-containing compound. Examples of the adduct body include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at the terminal portion of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; tri Examples thereof include compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of a polyol such as methylolpropane; lysine diisocyanate and the like.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic multivalent isocyanate compound is used as the cross-linking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the cross-linking agent (F) and the polymer component (A) causes the thermosetting resin film to have a cross-linked structure. Can be easily introduced.

The cross-linking agent (F) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, if they are two or more kinds. The combination and ratio of can be arbitrarily selected.

When the cross-linking agent (F) is used, in the composition (III-1), the content of the cross-linking agent (F) is, for example, 0.01 to 100 parts by mass with respect to the content of the polymer component (A). It may be any of 20 parts by mass, 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) is more remarkable. When the content of the cross-linking agent (F) is not more than the upper limit value, the 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 an energy ray-curable resin (G). Since the thermosetting resin film contains the energy ray curable resin (G), its characteristics can be changed by irradiation with energy rays.

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

Examples of the acrylate-based compound include trimethylolpropanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (dipentaerythritol monohydroxypenta). Chain aliphatic skeleton-containing (meth) acrylates such as meta) acrylates, dipentaerythritol hexa (meth) acrylates, 1,4-butylene glycol di (meth) acrylates, and 1,6-hexanediol di (meth) acrylates; Cyclic aliphatic skeleton-containing (meth) acrylate such as cyclopentanyldi (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Oligoester (meth) acrylate; Urethane (meth) acrylate oligomer An epoxy-modified (meth) acrylate; a polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; an itaconic acid oligomer and the like can be mentioned.

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

The energy ray-curable compound used for the polymerization may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof 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 kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the energy ray-curable resin (G) is used, the ratio of the content of the energy ray-curable resin (G) to the total mass of the composition (III-1) in the composition (III-1) is, for example, It may be 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 the energy ray-curable resin (G), a photopolymerization initiator is used to efficiently proceed with the polymerization reaction of the energy ray-curable resin (G). (H) may be contained.

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, methyl benzoin benzoate and benzoin dimethyl ketal. Benzoin compounds such as acetophenone; acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2, 4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; 1-hydroxycyclohexyl Α-Ketol compounds such as phenylketone; azo compounds such as azobisisobutyronitrile; titanosen compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2, Examples thereof include 4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanol; 2-chloroanthraquinone and the like.
Further, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amines.

The photopolymerization initiator (H) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.

When the photopolymerization initiator (H) is used, in the composition (III-1), the content of the photopolymerization initiator (H) is based on 100 parts by mass of the energy ray-curable resin (G). For example, it may be any one 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 colorant (I).
Examples of the colorant (I) include known ones such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindrinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indolphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazoles Examples thereof include lone dyes, pyranthron dyes and slene dyes.

Examples of the inorganic pigment include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, and ITO ( Examples thereof include indium tin oxide) dyes and ATO (antimons tin oxide) dyes.

The colorant (I) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, if they are two or more kinds. The combination and ratio of can be arbitrarily selected.

When the colorant (I) is used, the content of the colorant (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 the components other than the solvent (that is, the total amount of the thermosetting resin film in the thermosetting resin film). The ratio of the content of the colorant (I) to the mass) may be 0.1 to 5% by mass. When the ratio is at least the lower limit, the effect of using the colorant (I) is more remarkable. When the ratio is not more than the upper limit value, an excessive decrease in the light transmittance of the thermosetting resin film is suppressed.

[General-purpose additive (J)]
The composition (III-1) and the thermosetting resin film may contain the general-purpose additive (J) as long as the effects of the present invention are not impaired.
The general-purpose additive (J) may be a known one and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, plasticizers, antistatic agents, antioxidants, gettering agents and the like. Can be mentioned.

The general-purpose additive (J) contained in the composition (III-1) and the thermosetting resin film may be only one kind, two or more kinds, or two or more kinds, when it is two or more kinds. The combination and ratio thereof can be arbitrarily selected.
The contents of the composition (III-1) and the general-purpose additive (J) of the thermosetting resin film are not particularly limited and may be appropriately selected depending on the intended purpose.

[solvent]
The composition (III-1) preferably further contains a solvent. The composition containing the solvent (III-1) has good handleability.
The solvent is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the composition (III-1) may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly.

The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on the type of the component other than the solvent, for example.

As an example of a preferable thermosetting resin film of the present embodiment, a thermosetting resin film for forming a first protective film on the surface of the work by affixing it to a surface having a protruding electrode and heat-curing the film. And
The thermosetting resin film contains two or more kinds of thermosetting components other than the acrylic resin having an epoxy group.
The ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film in the thermosetting resin film is 40% by mass or more.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 was obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film was obtained, the total value was 400 g / eq or less.
The total thickness is 200 μm, which is composed of one layer of the thermosetting resin film having a thickness of 200 μm or two or more layers of the thermosetting resin film having a thickness of less than 200 μm laminated. Examples thereof include a thermosetting resin film having a light transmittance of a laminated film having a wavelength of 1342 nm of 50% or more.

As another example of the preferable thermosetting resin film of the present embodiment, the thermosetting resin film has a thermosetting property for forming a first protective film on the surface by attaching the film to a surface having a protruding electrode and heat-curing the film. It ’s a resin film,
The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D).
The thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2).
In the thermosetting resin film, the total content of all kinds of the thermosetting components with respect to the total mass of the thermosetting resin film (in other words, the total of the epoxy resin (B1) and the thermosetting agent (B2)). Content) is 40% by mass or more,
The ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 30% by mass.
The ratio of the content of the filler (D) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 20% by mass.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 is obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film is obtained, the total value is 400 g / eq or less. Examples thereof include a curable resin film.

As another example of the preferable thermosetting resin film of the present embodiment, the thermosetting resin film is heat-curable for forming a first protective film on the surface by attaching the film to a surface having a protruding electrode and heat-curing the film. It ’s a resin film,
The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D).
The thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2).
In the thermosetting resin film, the total content of all kinds of the thermosetting components with respect to the total mass of the thermosetting resin film (in other words, the total of the epoxy resin (B1) and the thermosetting agent (B2)). Content) is 40% by mass or more,
The ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 30% by mass.
The ratio of the content of the filler (D) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 20% by mass.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 was obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film was obtained, the total value was 400 g / eq or less.
The total thickness is 200 μm, which is composed of one layer of the thermosetting resin film having a thickness of 200 μm or two or more layers of the thermosetting resin film having a thickness of less than 200 μm laminated. Examples thereof include a thermosetting resin film having a light transmittance of a laminated film having a wavelength of 1342 nm of 50% or more.

As another example of the preferable thermosetting resin film of the present embodiment, the thermosetting resin film has a thermosetting property for forming a first protective film on the surface by attaching the film to a surface having a protruding electrode and heat-curing the film. It ’s a resin film,
The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D).
The thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2).
In the thermosetting resin film, the total content of all kinds of the thermosetting components with respect to the total mass of the thermosetting resin film (in other words, the total of the epoxy resin (B1) and the thermosetting agent (B2)). Content) is 40% by mass or more,
The ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 30% by mass.
The ratio of the content of the filler (D) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 20% by mass.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 was obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film was obtained, the total value was 400 g / eq or less.
A first protective film having a size of 20 mm × 130 mm and a thickness of 40 μm obtained by thermosetting the thermosetting resin film at 130 ° C. for 2 hours was used between gripping devices. When the distance is 80 mm, the tensile speed is 200 mm / min, and the first protective film is pulled in a direction parallel to the surface by the grasping instrument, the breaking strength of the first protective film is 55 MPa or less. There is a thermosetting resin film.

As another example of the preferable thermosetting resin film of the present embodiment, the thermosetting resin film has a thermosetting property for forming a first protective film on the surface by attaching the film to a surface having a protruding electrode and heat-curing the film. It ’s a resin film,
The thermosetting resin film contains a polymer component (A), two or more thermosetting components other than an acrylic resin having an epoxy group, and a filler (D).
The thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2).
In the thermosetting resin film, the total content of all kinds of the thermosetting components with respect to the total mass of the thermosetting resin film (in other words, the total of the epoxy resin (B1) and the thermosetting agent (B2)). Content) is 40% by mass or more,
The ratio of the content of the polymer component (A) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 30% by mass.
The ratio of the content of the filler (D) to the total mass of the thermosetting resin film in the thermosetting resin film is 5 to 20% by mass.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 was obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film was obtained, the total value was 400 g / eq or less.
The total thickness is 200 μm, which is composed of one layer of the thermosetting resin film having a thickness of 200 μm or two or more layers of the thermosetting resin film having a thickness of less than 200 μm laminated. The light transmittance of the laminated film having a wavelength of 1342 nm is 50% or more.
A first protective film having a size of 20 mm × 130 mm and a thickness of 40 μm obtained by thermosetting the thermosetting resin film at 130 ° C. for 2 hours was used between gripping devices. When the distance is 80 mm, the tensile speed is 200 mm / min, and the first protective film is pulled in a direction parallel to the surface by the grasping instrument, the breaking strength of the first protective film is 55 MPa or less. There is a thermosetting resin film.

<< Manufacturing method of composition for forming a thermosetting resin layer >>
A composition for forming a thermosetting resin layer such as the composition (III-1) can be obtained by blending each component for forming the composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving it.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

-Method for manufacturing the first protective film forming sheet The first protective film forming sheet can be manufactured by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The method of forming each layer is as described above.
For example, when the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material when the first support sheet is manufactured, the above-mentioned first pressure-sensitive adhesive composition or the above-mentioned first pressure-sensitive adhesive composition or the above-mentioned first base material is used on the first base material. The first pressure-sensitive adhesive layer or the first intermediate layer can be laminated by applying the composition for forming the first intermediate layer and drying it as necessary, or by irradiating it with energy rays.

On the other hand, for example, in the case of further laminating a thermosetting resin layer (thermosetting resin film) on the first pressure-sensitive adhesive layer already laminated on the first base material, the thermosetting resin layer is placed on the first pressure-sensitive adhesive layer. It is possible to directly form the thermosetting resin layer by applying the composition for forming the thermosetting resin layer. Similarly, when the first pressure-sensitive adhesive layer is further laminated on the first intermediate layer already laminated on the first base material, the first pressure-sensitive adhesive composition is coated on the first intermediate layer. , It is possible to directly form the first pressure-sensitive adhesive layer. As described above, when a continuous two-layer laminated structure is formed by using any of the compositions, another composition is newly applied on the layer formed from the composition. It is possible to form a layer in. However, of these two layers, the layer to be laminated afterwards is formed in advance on another release film using the composition, and the side of the formed layer in contact with the release film is the same. It is preferable to form a laminated structure of two continuous layers by laminating the exposed surface on the opposite side with the exposed surface of the remaining layers that have already been formed. At this time, it is preferable that the composition is applied to the peeled surface of the peeling film. The release film may be removed as necessary after the laminated structure is formed.

For example, a first protective film forming sheet (the first support sheet is the first) in which the first pressure-sensitive adhesive layer is laminated on the first base material and the thermosetting resin layer is laminated on the first pressure-sensitive adhesive layer. In the case of producing a first protective film forming sheet) which is a laminate of a base material and a first pressure-sensitive adhesive layer, the first pressure-sensitive adhesive composition is applied onto the first base material and dried as necessary. By allowing the first substrate to be laminated, the first pressure-sensitive adhesive layer is separately applied on the release film, and the composition for forming a thermosetting resin layer is separately applied and dried as necessary. A thermosetting resin layer is formed on the release film, and the exposed surface of the thermosetting resin layer is bonded to the exposed surface of the first pressure-sensitive adhesive layer laminated on the first base material to be thermosetting. By laminating the sex resin layer on the first pressure-sensitive adhesive layer, a first protective film forming sheet can be obtained.
Further, for example, in the case of manufacturing a first support sheet in which the first intermediate layer is laminated on the first base material and the first pressure-sensitive adhesive layer is laminated on the first intermediate layer, the first base material is manufactured. The first intermediate layer is laminated on the first base material by applying the composition for forming the first intermediate layer on the first substrate and drying it as necessary, or by irradiating it with energy rays. The first pressure-sensitive adhesive composition is applied onto the release film and dried as necessary to form the first pressure-sensitive adhesive layer on the release film, and the exposed surface of the first pressure-sensitive adhesive layer is formed on the release film. The first support sheet is obtained by laminating the first pressure-sensitive adhesive layer on the first intermediate layer by laminating it with the exposed surface of the first intermediate layer already laminated on the first base material. In this case, for example, a composition for forming a thermosetting resin layer is separately applied on the release film and dried as necessary to form a curable resin layer on the release film. The exposed surface of the curable resin layer is bonded to the exposed surface of the first pressure-sensitive adhesive layer already laminated on the first intermediate layer, and the thermosetting resin layer is laminated on the first pressure-sensitive adhesive layer. 1 A sheet for forming a protective film is obtained.

When the first pressure-sensitive adhesive layer or the first intermediate layer is laminated on the first base material, as described above, the first pressure-sensitive adhesive composition or the composition for forming the first intermediate layer is formed on the first base material. Instead of the method of coating an object, a first pressure-sensitive adhesive composition or a composition for forming a first intermediate layer is applied on a release film, and if necessary, dried or irradiated with energy rays. By forming a first pressure-sensitive adhesive layer or a first intermediate layer on the release film and bonding the exposed surface of these layers to one surface of the first base material, the first pressure-sensitive adhesive layer or the first The intermediate layer may be laminated on the first base material.
In either method, the release film may be removed at an arbitrary timing after the desired laminated structure is formed.

As described above, all the layers other than the first base material constituting the first protective film forming sheet can be formed in advance on the release film and laminated on the surface of the target layer. If necessary, a layer that employs such a process may be appropriately selected to produce the first protective film forming sheet.

The first protective film forming sheet 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 side opposite to the first support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting resin layer, is applied onto the release film (preferably the release-treated surface thereof), and if necessary. By drying, a layer constituting the outermost layer is formed on the release film, and the remaining layers are placed on the exposed surface on the side opposite to the side in contact with the release film of this layer. The first protective film forming sheet can also be obtained by laminating by the method and leaving the release film in a bonded state without removing it.

A commercially available product may be used as the first support sheet.

-Method for manufacturing a workpiece with a first protective film A method for manufacturing a workpiece with a first protective film when the thermosetting resin film or the sheet for forming the first protective film according to the embodiment of the present invention is used. Is a step of attaching a thermosetting resin film to a surface of the work having a protruding electrode (that is, a surface on which the protruding electrode is formed) (in this specification, it may be abbreviated as "pasting step") and affixing. The subsequent step of thermally curing the thermosetting resin film to form a first protective film (in this specification, it may be abbreviated as "first protective film forming step") and the work. Then, a step of forming a modified layer inside the work by irradiating a laser beam from the side provided with the first protective film through the first protective film (in the present specification, By expanding the work after forming the modified layer together with the first protective film in a direction parallel to the circuit plane thereof). The work is divided at the site of the modified layer, and the first protective film is cut to form a work piece and a surface of the work piece having the projecting electrode (that is, a surface on which the projecting electrode is formed). It has a step of obtaining a work piece with a first protective film provided with the first protective film (in this specification, it may be abbreviated as "division / cutting step").
Hereinafter, the manufacturing method will be described in detail with reference to the drawings.

5A to 5C and FIGS. 6A to 6B are enlarged cross-sectional views for schematically explaining the method for manufacturing the work workpiece with the first protective film. Here, a manufacturing method when the first protective film forming sheet 1 shown in FIG. 2 is used will be described.

<< Pasting process >>
In the pasting step, as shown in FIG. 5A, the thermosetting resin film 12 is pasted on the projecting electrode forming surface of the work 90 (that is, the surface 91a of the projecting electrode 91 and the circuit surface 90a of the work 90). .. By performing this step, the thermosetting resin film 12 spreads between a large number of protruding electrodes 91 and adheres to the surface on which the protruding electrodes are formed, and at the same time, the surface 91a of the protruding electrodes 91, particularly the work 90. It is possible to cover the surface 91a in the vicinity of the circuit surface 90a and embed the projecting electrode 91 to cover these regions. Further, by performing this step, the upper portion of the protruding electrode 91 including the crown 910 penetrates the thermosetting resin film 12 and protrudes from the thermosetting resin film 12.

In the sticking step, for example, the thermosetting resin film 12 may be used alone, but as shown here, the first support sheet 101 and the thermosetting resin film provided on the first support sheet 101 are used. It is preferable to use the first protective film forming sheet 1 configured with the above twelve. As will be described later, when the back surface 90b of the work 90 is ground, a back grind surface protective tape can be used as the first support sheet 101.

When the first protective film forming sheet 1 as shown here is used in the attaching step, the thermosetting resin film 12 in the first protective film forming sheet 1 is attached to the projecting electrode forming surface of the work 90. By doing so, the first protective film forming sheet 1 itself may be attached to the projecting electrode forming surface of the work 90.

In this specification, a structure in which a first protective film forming sheet is attached to a projecting electrode forming surface of a work as shown here is referred to as a "first laminated structure". There is. FIG. 5A shows the first laminated structure 201 configured by attaching the first protective film forming sheet 1 to the projecting electrode forming surface of the work 90.

In the sticking step, the exposed surface (sometimes referred to as “first surface” in the present specification) 12a of the thermosetting resin film 12 on the side facing the work 90 is a protrusion of the work 90. The thermosetting resin film 12 can be attached to the projecting electrode forming surface by crimping it to the projecting electrode forming surface (that is, the surface 91a of the projecting electrode 91 and the circuit surface 90a of the work 90).

In the sticking step, it is preferable to stick the thermosetting resin film 12 to the projecting electrode forming surface while heating it. By doing so, between the thermosetting resin film 12 and the projecting electrode forming surface, that is, between the thermosetting resin film 12 and the circuit surface 90a of the work 90, and the thermosetting resin. The generation of voids can be further suppressed in any of between the film 12 and the surface 91a of the projecting electrode 91. Further, the residual thermosetting resin film 12 can be further suppressed in the upper portion including the crown portion 910 of the projecting electrode 91, and finally the residual of the first protective film can be further suppressed in the upper portion.

The heating temperature of the thermosetting resin film 12 at the time of application may not be an excessively high temperature, and is preferably 60 to 100 ° C., for example. Here, the "excessive high temperature" means a temperature at which an unintended effect is exhibited on the thermosetting resin film 12, for example, the thermosetting resin film 12 is thermally cured.

When the thermosetting resin film 12 is attached to the projecting electrode forming surface, the pressure applied to the thermosetting resin film 12 (in the present specification, it may be referred to as “attachment pressure”) is 0.3 to. It is preferably 1 MPa.

After the first laminated structure 201 is formed by the pasting step, the first laminated structure 201 may be used as it is in the next step, but if necessary, the back surface 90b of the work 90 may be ground. The thickness of the work 90 may be adjusted. The first laminated structure 201 after grinding the back surface 90b of the work 90 is also in the state shown in FIG. 5A except that the thickness of the work 90 is different.

Grinding of the back surface 90b of the work 90 can be performed by a known method such as a method using a grinder.

The thickness of the portion of the work 90 excluding the protruding electrode 91 before and after grinding the back surface 90b of the work 90 is as described above.

After forming the first laminated structure 201 by the sticking step, the first support sheet 101 is removed from the thermosetting resin film 12 in the first laminated structure 201. When the back surface 90b of the work 90 is ground, it is preferable to remove the first support sheet 101 after this grinding.
By performing such a step, as shown in FIG. 5B, the thermosetting resin film 12 is provided on the projecting electrode forming surface of the work 90, and the first support sheet 101 is not provided. A second laminated structure (in other words, a work with a thermosetting resin film) 202 is obtained.
In the second laminated structure 202, the upper portion of the protruding electrode 91 including the crown 910 penetrates the thermosetting resin film 12 and protrudes and is exposed.

When the first pressure-sensitive adhesive layer 13 is energy ray-curable, the first pressure-sensitive adhesive layer 13 is cured by irradiation with energy rays to reduce the adhesiveness of the first pressure-sensitive adhesive layer 13, and then heat is applied. It is preferable to remove the first support sheet 101 from the curable resin film 12.

<< First protective film forming step >>
In the first protective film forming step, the thermosetting resin film 12 after being attached is thermally cured to form the first protective film 12'as shown in FIG. 5C.
When the first laminated structure 201 is formed, the first protective film forming step can be performed after removing the first support sheet 101.
Further, when the back surface 90b of the work 90 is ground, the first protective film forming step can be performed after the back surface 90b is ground.
By performing this step, a third laminated structure (in other words, a work with a first protective film) 203 having a first protective film 12'on the protruding electrode forming surface of the work 90 can be obtained. .. In FIG. 5C, reference numeral 12a'indicates the contact surface of the first protective film 12'with the work 90 (sometimes referred to as the "first surface" in the present specification).

The curing conditions of the thermosetting resin film 12 are not particularly limited as long as the degree of curing is such that the first protective film 12'sufficiently exerts its function, and is appropriately appropriate depending on the type of the thermosetting resin film 12. You can select it.
For example, the heating temperature and the heating time at the time of heat curing of the thermosetting resin film 12 are as described above.
At the time of thermosetting the thermosetting resin film 12, the curable resin film 12 may be pressurized, and the pressurizing pressure in that case is preferably 0.3 to 1 MPa.

In the second laminated structure (work with thermosetting resin film) 202 shown in FIG. 5B, the residual thermosetting resin film 12 is suppressed in the upper portion including the crown 910 of the projecting electrode 91. Therefore, after the completion of this step, the residual of the first protective film 12'is also suppressed in the upper portion of the protruding electrode 91.

<< Modified layer formation process >>
In the modified layer forming step, as shown in FIG. 6A, the work 90 is irradiated with laser light R from the side provided with the first protective film 12'through the first protective film 12'. By doing so, the modified layer 900 is formed inside the work 90.
After the modified layer forming step, the work 90 is divided (that is, dicing) described later. Therefore, the modified layer forming step is performed on the work 90 in the third laminated structure (work with the first protective film) 203. It is preferable to attach a dicing sheet or a second protective film forming sheet to the back surface 90b.

In addition, in this specification, the structure is configured such that the projecting electrode forming surface of the work is provided with the first protective film and the back surface of the work is provided with the dicing sheet or the second protective film forming sheet. It may be referred to as a "fourth laminated structure".
Further, a structure having a modified layer formed inside the work in the fourth laminated structure may be referred to as a "fifth laminated structure".
In FIG. 6A, as the fifth laminated structure 205, the work 90 is provided with the first protective film 12'on the protruding electrode forming surface, and the back surface 90b of the work 90 is provided with the second protective film forming sheet 8. The modified layer 900 is formed inside the structure of the above.

The second protective film forming sheet 8 shown here includes a second base material 81, a second pressure-sensitive adhesive layer 83 provided on the second base material 81, and a resin provided on the second pressure-sensitive adhesive layer 83. It is configured to include a layer (resin film) 82.
The laminate of the second base material 81 and the second pressure-sensitive adhesive layer 83 is the second support sheet 801.
Therefore, the second protective film forming sheet 8 is provided on the second support sheet 801 and one surface 801a of the second support sheet 801 in other words, on one surface 83a of the second pressure-sensitive adhesive layer 83. It can be said that the resin layer (resin film) 82 is provided.

The resin layer (resin film) 82 is for forming a second protective film on the back surface 90b of the work 90. The second protective film covers and protects the back surface 90b of the work 90. More specifically, the second protective film is used in the workpiece during the division of the workpiece and before the workpiece obtained by the division of the workpiece is packaged to manufacture the target substrate apparatus. Prevent cracks from occurring.

The resin layer 82 may have only one of the properties of thermosetting and energy ray curability, may have both properties, or may not have both properties. May be good. When the resin layer 82 is curable (that is, has at least one of thermosetting and energy ray curable properties), the cured product is the second protective film. When the resin layer 82 is non-curable (that is, it does not have both thermosetting and energy ray curable properties), the second step is when the resin layer 82 is attached to the back surface 90b of the work 90. It is considered that a protective film has been provided.

The second pressure-sensitive adhesive layer 83 may be either energy ray-curable or non-energy ray-curable, like the first pressure-sensitive adhesive layer 13. The energy ray-curable second pressure-sensitive adhesive layer 83 can easily adjust its physical properties before and after curing.

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

In the above-mentioned manufacturing method, as the second protective film forming sheet, a sheet other than the second protective film forming sheet 8 may be used.
In the above-mentioned manufacturing method, not only the second protective film forming sheet 8 but also known ones can be used as the second protective film forming sheet.
Similarly, in the above-mentioned production method, a known dicing sheet can be used.

In the modified layer forming step, a focus is set on a specific region of the inside of the work 90, which is a division portion of the work 90, and laser light R is irradiated so as to focus on this focal point. By the irradiation of the laser beam R, the modified layer 900 is formed in the irradiation region.

The thermosetting resin film 12 and the first protective film 12'have a light transmittance with a wavelength of 1342 nm, and preferably, the thermocurable resin film 12 and the first protective film 12' have a light transmittance with a wavelength of 1342 nm. When the rate is high as described above, the laser light having a wavelength of 1342 nm is satisfactorily transmitted through the first protective film 12'. Therefore, even if the work 90 is irradiated with the laser beam R from the side provided with the first protective film 12'through the first protective film 12', the modified layer 900 is provided inside the work 90. Can be formed well.

<< Splitting / cutting process >>
In the dividing / cutting step, the work 90 after forming the modified layer 900 is placed together with the first protective film 12', in other words, the fifth laminated structure 205 is placed in a direction parallel to the circuit surface 90a (FIG. 6A). By expanding in the direction of arrow E in the middle, the work 90 is divided at the site of the modified layer 900, and the first protective film 12'is cut. As a result, as shown in FIG. 6B, the workpiece 9 is formed on the projecting electrode forming surface of the workpiece 9 (that is, the surface 91a of the projecting electrode 91 and the circuit surface 9a of the workpiece 9). A workpiece 990 with a first protective film provided with a first protective film (first protective film 120'after cutting) is obtained.
By performing this step, the work workpiece 9 having the first protective film 120'after cutting on the projecting electrode forming surface (that is, the workpiece workpiece 990 with the first protective film) is placed on the second support sheet 801. The sixth laminated structure 206 is obtained in a state where a plurality (many) are aligned. In FIG. 6B, reference numeral 120a'indicates the contact surface of the first protective film 120'after cutting with the workpiece 9 (in the present specification, it may be referred to as "first surface"), and reference numeral 9b. Indicates the back surface of the workpiece 9.

Since the first protective film 12'is formed of the thermosetting resin film 12 satisfying the condition of the total value of the X values, the first protective film 12'can be easily cut in the dividing / cutting step. As a result, the workpiece 9 having the first protective film 120'after cutting on the projecting electrode forming surface can be manufactured with high efficiency. In this step, the first protective film 12'is cut along the divided portion of the work 90, and finally is in a state of being cut along the outer periphery of the work workpiece 9.

In the dividing / cutting step, the expansion is preferably carried out under a temperature condition of -15 to 5 ° C. When the temperature at the time of expansion is not more than the upper limit value, the first protective film 12'can be easily cut. When the temperature at the time of expansion is equal to or higher than the lower limit, overcooling can be avoided.

Here, the case where the resin layer 82 in the second protective film forming sheet 8 is also cut by performing the splitting / cutting step is shown, but the cutting of the resin layer 82 is known after the splitting / cutting step. It may be done separately by the method of. In FIG. 6B, the resin layer 82 after cutting is designated by reference numeral 820. Further, although the case where the resin layer 82 is cut is shown here, the second protective film obtained by curing the resin layer 82 may be cut without cutting at the stage of the resin layer 82.

In the manufacturing method, the resin layer 82 or the second protective film is cut along the divided portion of the work 90 as in the case of the first protective film 12'.
In the present specification, the laminated structure of the second support sheet and the resin layer (in other words, the second support sheet and the resin layer after cutting) is maintained even after the resin layer is cut. As long as it is, this laminated structure is referred to as a "second protective film forming sheet".

◇ Manufacturing method of substrate device After obtaining the work 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 manufactured by a known method. After flip-chip connection to the circuit surface of the substrate, it is made into a package, and by using this package, the target substrate device can be manufactured (not shown). When the semiconductor chip with the first protective film is used, the target semiconductor device can be manufactured by using the semiconductor package after manufacturing the semiconductor package. Further, when a semiconductor chip provided with the first protective film and the second protective film is used, the semiconductor chips with the protective film can be flip-chip connected to manufacture a target semiconductor device.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.
For convenience, each object manufactured in the comparative examples shown below is given the same name as each object manufactured in the examples.

The components used in the production of the composition for forming a thermosetting resin layer are shown below.
[Polymer component (A)]
(A) -1: Polyvinyl butyral ("Eslek SV-10" manufactured by Sekisui Chemical Co., Ltd., weight average molecular weight 65000, glass transition temperature 66 ° C.)
(A) -2: Polyvinyl butyral ("Eslek BL-10" manufactured by Sekisui Chemical Co., Ltd., weight average molecular weight 25000, glass transition temperature 59 ° C.)
(A) -3: Copolymerization of n-butyl acrylate (55 parts by mass), methyl acrylate (10 parts by mass), glycidyl methacrylate (20 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). Acrylic resin (weight average molecular weight 800,000, glass transition temperature −28 ° C.).
[Thermosetting component (B)]
-Epoxy resin (B1)
(B1) -1: Bisphenol A type epoxy resin ("EXA-4810-1000" manufactured by DIC Corporation, epoxy equivalent 404 to 412 g / eq)
(B1) -2: Dicyclopentadiene type epoxy resin ("EPICLON HP-7200" manufactured by DIC Corporation, epoxy equivalent 265 g / eq)
(B1) -3: Liquid-modified epoxy resin ("YX7110" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 962 g / eq)
(B1) -4: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235 g / eq)
(B1) -5: Solid bisphenol A type epoxy resin ("Epicoat 1055" manufactured by Mitsubishi Chemical Corporation, molecular weight 1600, softening point 93 ° C., epoxy equivalent 800-900 g / eq)
(B1) -6: Dicyclopentadiene type epoxy resin ("XD-1000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 248 g / eq)
・ Thermosetting agent (B2)
(B2) -1: Novolac type phenol resin (Showa Denko's "Shonol BRG-556", hydroxyl group equivalent 104 g / eq)
(B2) -2: Dicyandiamide ("ADEKA HANDNER EH-3636AS" manufactured by ADEKA, solid dispersion type latent curing agent, active hydrogen amount 21 g / eq)
[Curing accelerator (C)]
(C) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ" manufactured by Shikoku Chemicals Corporation)
[Filler (D)]
(D) -1: Silica filler ("YA050C-MKK" manufactured by Admatex, average particle diameter 0.05 μm)
(D) -2: Silica filler ("SC2050MA" manufactured by Admatex Co., Ltd., silica filler surface-modified with an epoxy compound, average particle diameter 500 nm)
(D) -3: Silica filler (“SV-10” manufactured by Tatsumori Co., Ltd., average particle diameter 8 μm)
[Coupling agent (E)]
(E) -1: Silane coupling agent ("MKC silicate MSEP2" manufactured by Mitsubishi Chemical Corporation, a silicate compound to which γ-glycidoxypropyltrimethoxysilane is added)
[Colorant (I)]
(I) -1: Carbon black ("MA-600B" manufactured by Mitsubishi Chemical Corporation)

[Example 1]
<< Manufacture of thermosetting resin film and first protective film forming sheet >>
<Manufacturing of composition for forming a thermosetting resin layer>
Polymer component (A) -1 (9.9 parts by mass), epoxy resin (B1) -1 (37.8 parts by mass), epoxy resin (B1) -2 (25.0 parts by mass), thermosetting agent (25.0 parts by mass) B2) -1 (18.1 parts by mass), curing accelerator (C) -1 (0.2 parts by mass) and filler (D) -1 (9.0 parts by mass) are mixed, and further with methyl ethyl ketone. The composition (III-1) for forming a thermosetting resin layer having a total concentration of 55% by mass of the six components other than the above-mentioned methyl ethyl ketone was prepared by diluting and stirring at 23 ° C. Table 1 shows these components and their contents. In addition, the description of "-" in the column of the contained component in Table 1 means that the composition for forming a thermosetting resin layer does not contain the component. In addition, "ratio (% by mass) of the total content of all types of thermosetting components" in Table 1 means "all types of heat with respect to the total mass of the thermosetting resin film in the thermosetting resin film". It means "percentage of the total content of curable components".

<Manufacturing of thermosetting resin film>
A release film (“SP-PET38131” manufactured by Lintec Corporation, thickness 38 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment was used, and the thermosetting resin layer obtained above was used on the peeled surface. The forming composition (III-1) was applied and dried at 100 ° C. for 2 minutes to prepare a thermosetting resin film having a thickness of 30 μm.

<Manufacturing of first protective film forming sheet>
Next, on the exposed surface of the obtained thermosetting resin film (in other words, the surface opposite to the side on which the release film is provided), a surface protective tape for backgrinding (“Adwill E-8180HR” manufactured by Lintec Corporation). ), To prepare a first protective film forming sheet. The surface protective tape corresponds to the first support sheet.

<< Manufacturing of semiconductor chip 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 surface protective tape is provided. The first protective film forming sheet was attached to the bump forming surface of the semiconductor wafer by crimping the surface on the opposite side to the bump forming surface of the semiconductor wafer. At this time, the first protective film forming sheet is attached using a pasting device (roller type laminator, "RAD-3510 F / 12" manufactured by Lintec Corporation), a table temperature of 90 ° C., a sticking speed of 2 mm / sec, and a sticking pressure. This was performed while heating the thermosetting resin film under the condition of 0.5 MPa. As the semiconductor wafer, a wafer having a bump height of 210 μm, a bump width of 250 μm, a distance between adjacent bumps of 400 μm, and a thickness of a portion excluding the bump of 750 μm was used.
As described above, a first laminated structure was obtained in which a first protective film forming sheet was attached to the bump forming surface of the semiconductor wafer.

Next, using a grinder (“DGP8760” manufactured by Disco Corporation), the surface (back surface) of the semiconductor wafer in the obtained first laminated structure opposite to the bump forming surface was ground. At this time, the back surface was ground until the thickness of the portion of the semiconductor wafer excluding the bumps became 250 μm.

Next, the surface protective tape (in other words, the first support sheet) was removed from the thermosetting resin film in the first laminated structure.
As described above, a second laminated structure (semiconductor wafer with a thermosetting resin film) configured by providing a thermosetting resin film on the bump forming surface of the semiconductor wafer was obtained.

Next, using a thermosetting device (“RAD-9100 m / 12” manufactured by Lintec Corporation), the thermosetting resin film in the second laminated structure obtained above was subjected to a treatment temperature of 130 ° C. and a treatment pressure of 0. The first protective film was formed by thermosetting by heat and pressure treatment under the conditions of 5 MPa and a treatment time of 2 hours.
As described above, a third laminated structure (in other words, a semiconductor wafer with a first protective film) having a first protective film provided on the bump forming surface of the semiconductor wafer was obtained.

Next, a dicing tape (“Adwill D-841” manufactured by Lintec Corporation) is attached to the back surface (in other words, the ground surface) of the semiconductor wafer in the obtained third laminated structure to form bumps on the semiconductor wafer. A fourth laminated structure having a first protective film on the surface and a dicing tape on the back surface was obtained. The dicing tape corresponds to a second support sheet.

Next, using a dicing device (“DFL7361” manufactured by DISCO Corporation), the semiconductor wafer in the fourth laminated structure is provided with the first protective film so as to focus on the focal point set inside the semiconductor wafer. A modified layer was formed inside the semiconductor wafer by irradiating the semiconductor wafer with a laser beam from the side of the wafer through the first protective film. At this time, the wavelength of the laser beam was 1342 nm, the output was 0.7 W, and the frequency was 90 kHz.
As described above, a fifth laminated structure having a structure in which a modified layer was formed inside the semiconductor wafer in the fourth laminated structure was obtained.

Then, in an environment of 0 ° C., the semiconductor wafer (in other words, the fifth laminated structure) after forming this modified layer is expanded in a direction parallel to the circuit plane together with the first protective film. At the site of the modified layer, the semiconductor wafer was divided and the first protective film was cut along the divided portion of the semiconductor wafer. At this time, using a die separator (“DDS2300” manufactured by DISCO Corporation), the second support sheet in the fifth laminated structure is placed on the table in the die separator, and the peripheral edge portion of the fifth laminated structure is fixed. Then, in this state, the semiconductor wafer and the first protective film were expanded by pushing up the table under the conditions of a push-up speed of 50 mm / sec and a push-up amount of 20 mm. The size of the obtained semiconductor chip was 2 mm × 2 mm.
As described above, a plurality (many) of semiconductor chips (that is, semiconductor chips with the first protective film) having the first protective film after cutting on the bump forming surface are formed on the second support sheet (in other words, the dicing tape). A sixth laminated structure in an aligned state was obtained.

<< Evaluation of thermosetting resin film >>
<Confirmation of residual inhibitory property of thermosetting resin film on the upper part of bump>
At the time of manufacturing the above-mentioned semiconductor chip with the first protective film, a scanning electron microscope (“VE-9800” manufactured by KEYENCE CORPORATION) was used from the bump forming surface side of the semiconductor wafer, the acceleration voltage was 5 keV, and the first laminated structure was formed. Was observed. Then, the residual inhibitory property of the thermosetting resin film on the upper part of the bump in the first laminated structure was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The boundary between the bump and the thermosetting resin film can be confirmed, and it can be confirmed that the thermosetting resin film does not remain on the upper part of the bump.
B: The boundary between the bump and the thermosetting resin film cannot be confirmed, and it can be confirmed that the thermosetting resin film remains on the upper part of the bump.

<Measurement of light transmittance of thermosetting resin film>
The thermosetting resin film for testing (thickness) is the same as that used in the production of the thermosetting resin film described above, except that the coating amount of the thermosetting resin layer forming composition (III-1) is changed. 5 sheets (40 μm) were manufactured.
Next, these five test thermosetting resin films were laminated in these thickness directions to obtain a laminated film (thickness 200 μm).
Then, using a spectrophotometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by SHIMADZU), the transmittance of light having a wavelength of 1342 nm was measured for this laminated film. The results are shown in Table 1.

<< Evaluation of the first protective film >>
<Evaluation of splitability of semiconductor wafers>
Using a digital microscope (“VH-Z100” manufactured by KEYENCE CORPORATION), the sixth laminated structure obtained above was observed from the first protective film side thereof. At this time, as the observation region, the first region corresponding to the central portion of the alignment surface of the semiconductor chip with the first protective film of the second support sheet and the peripheral portion side having point symmetry with respect to the first region. A total of 5 regions were selected, that is, the second region, the third region, the fourth region, and the fifth region, which are located at the position of and have the same distance from the first region. Each of these five regions was defined as a region containing 25 semiconductor chips with a first protective film in 5 rows and 5 columns, assuming that the semiconductor wafer was normally divided. Further, the first region exists in the substantially central portion of the first line segment connecting the second region and the third region, and the first region exists in the substantially central portion of the second line segment connecting the fourth region and the fifth region. Then, these five regions were selected so that the second region, the fourth region, the third region, and the fifth region were located in this order in the clockwise direction. The first line segment and the second line segment are orthogonal to each other. Then, these five regions were observed, and the splittability of the semiconductor wafer was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The semiconductor wafer is normally divided in all five regions (all regions from the first region to the fifth region).
B: In at least one region (at least one of the first region to the fifth region), there is a portion where the semiconductor wafer is not normally divided.

<Evaluation of cutability of the first protective film>
At the same time as the evaluation of the separability of the semiconductor wafer described above, the cutability of the first protective film was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: In all 5 regions (all regions from the 1st region to the 5th region), the first protective film is normally cut.
B: In at least one region (at least one of the first region to the fifth region), there is a portion where the first protective film is not normally cut.

<Measurement of breaking strength of the first protective film>
The thermosetting resin film for testing (thickness) is the same as that used in the production of the thermosetting resin film described above, except that the coating amount of the thermosetting resin layer forming composition (III-1) is changed. 40 μm) was manufactured.
Next, the thermosetting resin film for this test was heat-cured by heating at 130 ° C. for 2 hours.
Next, a section having a size of 20 mm × 130 mm was cut out from this cured product (that is, the first protective film), and this was used as a test piece.
Using a universal tensile tester ("Autograph AG-IS" manufactured by Shimadzu Corporation), the distance between the gripping instruments is 80 mm, the tensile speed is 200 mm / min, and the test piece is placed in a direction parallel to the surface thereof. It was pulled by a grasping instrument, the maximum stress of the test piece at this time was measured, and this was adopted as the breaking strength of the first protective film. The results are shown in Table 1.

[Comparative Example 1]
<< Manufacture of thermosetting resin film and first protective film forming sheet >>
<Manufacturing of composition for forming a thermosetting resin layer>
Polymer component (A) -2 (10.0 parts by mass), epoxy resin (B1) -2 (30.0 parts by mass), epoxy resin (B1) -3 (33.0 parts by mass), heat curing agent ( B2) -1 (16.0 parts by mass), curing accelerator (C) -1 (0.2 parts by mass) and filler (D) -1 (11.0 parts by mass) are mixed, and further with methyl ethyl ketone. By diluting and stirring at 23 ° C., a composition for forming a resin layer having a total concentration of 55% by mass of the six components other than the above-mentioned methyl ethyl ketone was prepared. Table 1 shows these components and their contents.

<Manufacturing of thermosetting resin film and first protective film forming sheet>
A thermosetting resin film and a first protective film forming sheet were produced by the same method as in Example 1 except that the composition obtained above was used as the resin layer forming composition.

<< Manufacturing of semiconductor chip with first protective film >>
Manufacture of a semiconductor chip with a first protective film (in other words, a sixth laminated structure) by the same method as in Example 1 except that the sheet for forming the first protective film is used. I tried.

<< Evaluation of thermosetting resin film and first protective film >>
The thermosetting resin film and the first protective film produced in this comparative example were evaluated by the same method as in the case of Example 1. The results are shown in Table 1.

[Comparative Example 2]
<< Manufacture of thermosetting resin film and first protective film forming sheet >>
<Manufacturing of composition for forming a thermosetting resin layer>
Polymer component (A) -3 (21.0 parts by mass), epoxy resin (B1) -4 (10.0 parts by mass), epoxy resin (B1) -5 (2.0 parts by mass), epoxy resin (B1) ) -6 (5.6 parts by mass), thermal curing agent (B2) -2 (0.5 parts by mass), curing accelerator (C) -1 (0.5 parts by mass), filler (D) -2 (6.0 parts by mass), filler (D) -3 (54.0 parts by mass), coupling agent (E) -1 (0.4 parts by mass) and colorant (I) -1 (1.9 parts by mass) By mixing parts by mass), further diluting with methyl ethyl ketone, and stirring at 23 ° C., a composition for forming a resin layer having a total concentration of 10 components other than the above-mentioned methyl ethyl ketone of 55% by mass was prepared. Table 1 shows these components and their contents.

<Manufacturing of thermosetting resin film and first protective film forming sheet>
A thermosetting resin film and a first protective film forming sheet were produced by the same method as in Example 1 except that the composition obtained above was used as the resin layer forming composition.

<< Manufacturing of semiconductor chip with first protective film >>
Manufacture of a semiconductor chip with a first protective film (in other words, a sixth laminated structure) by the same method as in Example 1 except that the sheet for forming the first protective film is used. I tried.

<< Evaluation of thermosetting resin film and first protective film >>
The thermosetting resin film and the first protective film produced in this comparative example were evaluated by the same method as in the case of Example 1. The results are shown in Table 1.

As is clear from the above results, the thermosetting resin film of Example 1 was able to suppress the residue on the upper part of the bump when the semiconductor wafer was attached to the bump forming surface, and had preferable characteristics.
In the thermosetting resin film of Example 1, the ratio of the total content of all kinds of thermosetting components to the total mass of the thermosetting resin film was 80.9% by mass.

Further, in Example 1, the splittability of the semiconductor wafer was good.
The heat-curable resin film of Example 1 has a high light transmittance at a wavelength of 1342 nm, and as a result, the light transmittance of the first protective film formed from this film is also high, and the light transmittance is also high through the first protective film. When the semiconductor wafer was irradiated with laser light, the modified layer could be satisfactorily formed inside the semiconductor wafer.

Further, in Example 1, the cutability of the first protective film was good.
In Example 1, the total value of the X values is 296 (= {408 × 37.8 / (37.8 + 25.0 + 18.1)} + {265 × 25.0 / (37.8 + 25.0 + 18.1)} +. It was {104 × 18.1 / (37.8 + 25.0 + 18.1)}) g / eq, and the breaking strength of the first protective film was 45 MPa.

On the other hand, in Comparative Example 1, the cutting property of the first protective film was inferior.
In Comparative Example 1, the total value of the X values is 524 (= {265 × 30.0 / (30.0 + 33.0 + 16.0)} + {962 × 33.0 / (30.0 + 33.0 + 16.0)} +. It was {104 × 16.0 / (30.0 + 33.0 + 16.0)}) g / eq, and the breaking strength of the first protective film was 60 MPa.

The thermosetting resin film of Comparative Example 2 was inferior in characteristics because it could not suppress the residue on the upper part of the bump when the semiconductor wafer was attached to the bump forming surface.
In the thermosetting resin film of Comparative Example 2, the ratio of the total content of all kinds of thermosetting components to the total mass of the thermosetting resin film was 17.8% by mass.

Further, in Comparative Example 2, the splittability of the semiconductor wafer was inferior.
The heat-curable resin film of Comparative Example 2 has a low light transmittance at a wavelength of 1342 nm, and as a result, the light transmittance of the first protective film formed from this film is also low, via the first protective film. When the semiconductor wafer was irradiated with laser light, the modified layer could not be properly formed inside the semiconductor wafer. As a result, the semiconductor wafer could not be divided normally.
In Comparative Example 2, the first protective film could not be cut, but it was not possible to determine how much the characteristics of the first protective film itself had an effect on this result, and the cutability of the first protective film was evaluated. It was impossible. However, since the breaking strength of the first protective film was as small as 25 MPa, it was presumed that the reason why the first protective film could not be cut was mainly due to the inferior splittability of the semiconductor wafer.

INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing a workpiece or the like having a projecting electrode on a connection pad portion, which is used in a flip chip mounting method.

1, 2, 3 ... 1st protective film forming sheet, 11 ... 1st base material, 11a ... One surface of the 1st base material, 12 ... Thermosetting resin layer (thermosetting) (Resin resin film), 12'... first protective film, 120' ... first protective film after cutting, 13 ... first adhesive layer, 13a ... one of the first adhesive layers Surface, 14 ... 1st intermediate layer, 101, 102, 103 ... 1st support sheet, 101a, 102a, 103a ... surface of 1st support sheet, 206 ... 6th laminated structure, 90 ... Work, 90a ... Circuit surface of the work, 91 ... Projective electrode, 91a ... Surface of the projectile electrode, 900 ... Modified layer, 990 ... Work with first protective film Workpiece, R ... Laser light

Claims (2)

A thermosetting resin film for forming a first protective film on the surface of the work by affixing it to a surface having a protruding electrode and heat-curing the work.
The thermosetting resin film contains two or more kinds of thermosetting components other than the acrylic resin having an epoxy group.
The ratio of the total content of all kinds of the thermosetting components to the total mass of the thermosetting resin film in the thermosetting resin film is 40% by mass or more.
Regarding the thermosetting component contained in the thermosetting resin film, the following formula:
X = [equivalent of functional groups involved in the thermosetting reaction of the thermosetting component (g / eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)] / [thermosetting resin film] Total content of all types of thermosetting components (parts by mass)]
When the X value calculated in 1 is obtained and the total value of the X values in all kinds of the thermosetting components contained in the thermosetting resin film is obtained, the total value is 400 g / eq or less. Curable resin film. A sheet for forming a first protective film, comprising a first support sheet and having the thermosetting resin film according to claim 1 on one surface of the first support sheet.

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