TWI833912B - Thermosetting resin film and first protective film forming sheet - Google Patents

Abstract

The thermosetting resin film of this embodiment is attached to the surface of the workpiece with the protruding electrode and thermally cured to form a first protective film on the surface; one layer of the thermosetting resin film with a thickness of 200 μm The transmittance of the resin film or the laminated film with a total thickness of 200 μm by laminating two or more layers of the aforementioned thermosetting resin film less than 200 μm for light with a wavelength of 1342 nm is 50% or more.

Description

Thermosetting resin film and first protective film forming sheet

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. 2019-032829 filed in Japan on February 26, 2019, and the contents of this application are incorporated herein by reference.

Previously, when a multi-pin LSI (Large Scale Integration) package used in an MPU (Micro Processor Unit) or a gate array was mounted on a printed wiring board, The following flip-chip mounting method is adopted: using a workpiece (for example, a semiconductor wafer, etc.) equipped with protruding electrodes (for example, bumps, pillars, etc.), through the so-called face down method, the workpiece processing object (for example, , the protruding electrodes in the semiconductor wafer, etc., which are divided parts of the semiconductor wafer, are in opposing contact with the corresponding terminal portions on the substrate, thereby performing melting/diffusion bonding.

When this mounting method is used, in order to protect the circuit surface of the workpiece and the protruding electrode, a curable resin film is sometimes attached to the surface of the protruding electrode and the circuit surface of the workpiece to harden the film. Form a protective film on the surface. In addition, in this specification, the surface of the protruding electrode and the circuit surface of the workpiece or workpiece may be collectively referred to as the "protruding electrode forming surface".

The curable resin film is usually attached to the protruding electrode forming surface of the workpiece in a state softened by heating. Thereby, the upper part of the protruding electrode including the top of the head penetrates the curable resin film and protrudes from the curable resin film. On the other hand, the curable resin film covers the protruding electrodes of the workpiece, spreads between the protruding electrodes, is in close contact with the circuit surface, and covers the surface of the protruding electrodes, especially the surface of the vicinity of the circuit surface, thereby Bury the protruding electrode. Then, the curable resin film is further cured to cover the surface of the circuit surface of the workpiece and the vicinity of the circuit surface of the protruding electrode, thereby becoming a protective film that protects these areas.

When a semiconductor wafer is used, the semiconductor wafer used in the mounting method is obtained, for example, by: forming a protruding electrode on a circuit surface on a surface opposite to the circuit surface. Divide by grinding or cutting. In the process of obtaining such a semiconductor wafer, usually for the purpose of protecting the circuit surface and protruding electrodes of the semiconductor wafer, a curable resin film is attached to the protruding electrode formation surface, and the film is hardened to form the protruding electrode. Form a protective film on the surface. Furthermore, the semiconductor wafer is divided into semiconductor wafers, and finally becomes a semiconductor wafer having a protective film on the protruding electrode formation surface (sometimes referred to as "semiconductor wafer with protective film" in this specification) (see Patent Document 1).

Such a workpiece having a protective film on the protruding electrode formation surface (sometimes referred to as a "protective film-attached workpiece" in this specification) is mounted on a substrate to form a package, and the package is used. Make up the target device. When a semiconductor chip with a protective film is mounted on a substrate, the semiconductor package thus obtained is used to construct a target semiconductor device. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5515811.

[Problem to be solved by the invention]

When a conventional curable resin film is used, as represented by the protective film disclosed in Patent Document 1, division of the workpiece (for example, division of a semiconductor wafer into semiconductor wafers) is usually performed by blade cutting using a dicing blade. . However, although this method is the most widely used, it is not suitable for manufacturing small-sized workpieces or thin-thick workpieces, for example. The reason is that such workpieces are prone to cracks or defects.

Therefore, an object of the present invention is to provide a resin film capable of forming a protective film for protecting a protruding electrode forming surface of a workpiece or a workpiece to be processed, and by using the resin film, a novel method for dividing the workpiece can be applied. . [Means used to solve problems]

The present invention provides a thermosetting resin film that is attached to a surface with a protruding electrode in a workpiece and thermally hardened to form a first protective film on the surface; a layer of 200 μm in thickness is thermally cured. The transmittance of the thermosetting resin film or the laminated film with a total thickness of 200 μm by laminating two or more layers of the aforementioned thermosetting resin film less than 200 μm for light with a wavelength of 1342 nm is 50% or more. The thermosetting resin film of the present invention may also contain a thermosetting component other than an acrylic resin having an epoxy group, and the content of the thermosetting component in the thermosetting resin film is relative to the content of the thermosetting resin film. The proportion of the total mass is 40% by mass or more. Moreover, this invention provides the sheet for 1st protective film formation which is provided with the 1st support sheet, and is provided with the said thermosetting resin film on one surface of the said 1st support sheet. [Invention effect]

According to the present invention, a resin film is provided that can form a protective film for protecting a workpiece or a protruding electrode forming surface of a workpiece to be processed, and by using the resin film, a novel method for dividing the workpiece can be applied.

◇Thermosetting resin film, first protective film forming sheet The thermosetting resin film according to one embodiment of the present invention is used to form the first protective film by attaching the thermosetting resin film to the surface of the workpiece having the protruding electrode ( In this specification, (sometimes referred to as "protruding electrode formation surface")) and thermally hardened, thereby forming a first protective film on the aforementioned surface; a layer of the aforementioned thermosetting resin film with a thickness of 200 μm or a thickness of less than 200 μm. A laminated film having a total thickness of 200 μm, in which two or more layers of the aforementioned thermosetting resin film are laminated, has a transmittance of 50% or more for light with a wavelength of 1342 nm.

In addition, a first protective film forming sheet according to an embodiment of the present invention includes a first support sheet, and the thermosetting resin film is provided on one side of the first support sheet. In the first protective film-forming sheet, the “thermosetting resin film” may also be called a “thermosetting resin layer”.

In this embodiment, examples of the workpiece include a semiconductor wafer and the like. Examples of the workpiece include semiconductor wafers that are divided parts of a semiconductor wafer. The processing of workpieces includes, for example, segmentation. Examples of protruding electrodes include bumps, pillars, and the like. The protruding electrode is arranged on the connection pad of the workpiece and is composed of eutectic solder, high-temperature solder, gold or copper.

The first protective film forming sheet is attached to the protruding electrode forming surface of the workpiece (that is, the surface of the protruding electrode and the circuit surface of the workpiece) via the thermosetting resin film (thermosetting resin layer) of the sheet. ) and use. Furthermore, the fluidity of the adhered thermosetting resin film increases by heating, spreads between the protruding electrodes to cover the protruding electrodes, is in close contact with the circuit surface, and covers the surface of the protruding electrodes, especially the surface of the protruding electrodes. The protruding electrodes are embedded in the surface of the area near the circuit surface. The thermosetting resin film in this state is further cured by heating, and finally a first protective film is formed, and the first protective film is protected in a state of being in close contact with the circuit surface and the protruding electrode.

Furthermore, when the thermosetting resin film is attached to the protruding electrode formation surface of the workpiece, the protruding electrode including the upper portion of the head can penetrate the thermosetting resin film and protrude from the thermosetting resin film. In this case, the workpiece immediately becomes ready for flip-chip connection to the circuit surface of the substrate. As will be described later, the upper part of the protruding electrode must be finally exposed at the stage of processing the workpiece. On the other hand, when the thermosetting resin film is attached to the protruding electrode formation surface of the workpiece, if the upper part of the protruding electrode including the top of the head does not protrude from the thermosetting resin film, there will remain The thermosetting resin film on the upper part of the protruding electrode or the first protective film formed by curing the thermosetting resin film is separately removed, thereby exposing the upper part of the protruding electrode. Thereby, the workpiece becomes a state that can be flip-chip connected to the circuit surface of the substrate.

In this way, by using the thermosetting resin film of this embodiment, the circuit surface of the workpiece and the base portion of the protruding electrode near the circuit surface are fully protected by the first protective film.

For the workpiece with the first protective film forming sheet attached, for example, if necessary, grind the surface opposite to the circuit surface, remove the first supporting sheet, and then heat the thermosetting resin film. This results in the embedding of the protruding electrodes and the formation of the first protective film. Furthermore, the workpiece is divided (that is, divided into individual pieces into workpieces) and the first protective film is cut, and the workpiece thus obtained having the cut first protective film on the protruding electrode formation surface is used. (In this specification, it may be referred to as "the workpiece with a first protective film") to manufacture target substrate devices such as semiconductor devices. These steps will be explained in detail later.

In addition, in this specification, unless otherwise specified, when it is simply described as "curable resin film", it means "the curable resin film before curing", and when it is simply described as "curable resin layer", it means "hardened resin film". The hardening resin layer in front of it." For example, the term "thermosetting resin film" means "the thermosetting resin film before curing", and the term "first protective film" means the cured product of the thermosetting resin film.

The thermosetting resin film of this embodiment is suitable for applying a method different from the conventional method as a method of dividing (in other words, singulating) a workpiece into a workpiece to be processed. Here, as a "method different from the previous method", for example, the following method can be mentioned. That is, a workpiece having a first protective film formed of the thermosetting resin film on the protruding electrode formation surface is irradiated with laser light to form a modified layer inside the workpiece. Then, force is applied to the workpiece after the modified layer is formed. More specifically, in this embodiment, the workpiece is expanded in a direction parallel to the circuit surface of the workpiece. Thereby, the aforementioned workpiece is divided at the portion of the aforementioned modified layer. At this time, there is a case where force is also applied to the first protective film, and more specifically, the first protective film is expanded in a direction parallel to the surface of the first protective film attached to the workpiece, and at the same time The first protective film can also be cut off. At this time, the first protective film is cut along the divided parts of the workpiece. In this case, the workpiece processed with the first protective film can be immediately obtained by including the workpiece processed and the cut first protective film formed on the protruding electrode formation surface of the workpiece processed. On the other hand, when the first protective film cannot be cut simultaneously when the workpiece is divided, the first protective film is cut after the workpiece is divided. Thereby, the same workpiece processed product with the first protective film as described above can be obtained.

This method of dividing a workpiece with the formation of a modified layer is called stealth cutting (registered trademark). The workpiece is irradiated with laser light and the workpiece is cut away from the irradiated area while gradually cutting the workpiece from the surface of the workpiece. Laser cutting is completely different in nature.

[Light transmittance of thermosetting resin film] The transmittance of one layer of the thermosetting resin film having a thickness of 200 μm for light with a wavelength of 1342 nm is 50% or more as mentioned above. In addition, the transmittance of the laminated film with a total thickness of 200 μm, which is composed of two or more layers of the thermosetting resin film having a thickness of less than 200 μm, for light with a wavelength of 1342 nm is 50% or more as described above.

When the above-described method of forming a modified layer inside the workpiece is applied as a method of dividing the workpiece to produce a workpiece, the modified layer can be formed by irradiating the workpiece with laser light having a wavelength of 1342 nm. At this time, the laser light can be irradiated to the workpiece from the circuit surface side of the workpiece, or from the inner surface side of the workpiece. However, when the workpiece is irradiated with laser light from the circuit surface side of the workpiece, the laser light is irradiated through the first protective film formed on the circuit surface. On the other hand, the transmittances of the thermosetting resin film and the cured product of the thermosetting resin film (for example, the first protective film) for light of the same wavelength are substantially the same or exactly the same. Therefore, when the transmittance of one layer of thermosetting resin film with a thickness of 200 μm to light of wavelength 1342 nm is 50% or more, the transmittance of the cured product of the thermosetting resin film to light of wavelength 1342 nm also becomes above 50. Similarly, when the transmittance of the aforementioned laminated film to light with a wavelength of 1342 nm is 50% or more, the cured product of the thermosetting resin film also has a transmittance of 50% or more with respect to light with a wavelength of 1342 nm. That is, the first protective film formed using a thermosetting resin film having the same composition as the thermosetting resin film that satisfies the condition of such light transmittance allows the laser light with a wavelength of 1342 nm to pass through well. Therefore, a workpiece having such a first protective film on the circuit surface is suitable as a workpiece for irradiating laser light from the circuit surface side of the workpiece to form a modified layer inside the workpiece.

In order to make the above effect more remarkable, the transmittance of a thermosetting resin film with a thickness of 200 μm as one layer or a laminated film with a total thickness of 200 μm for light with a wavelength of 1342 nm can be, for example, 60% or more or 70% or more. , any of above 80% and above 85%.

There is no particular limit on the upper limit of the transmittance of light with a wavelength of 1342 nm for a thermosetting resin film with a thickness of 200 μm as one layer or a laminated film with a total thickness of 200 μm. The higher the value, the better. For example, in order to make the production of the thermosetting resin film relatively easy, the light transmittance is preferably 95% or less.

The aforementioned light transmittance can be appropriately adjusted within a range set by any combination of the aforementioned lower limit value and upper limit value. In one embodiment, the light transmittance may be any one of 50% to 95%, 60% to 95%, 70% to 95%, 80% to 95%, and 85% to 95%.

In a thermosetting resin film of one layer with a thickness of 200 μm and the laminated film with a total thickness of 200 μm, if the components contained in these films are the same, the light of these films (the thermosetting resin film of one layer and the laminated film) The transmittances will be the same as each other and are not limited to the case where the wavelength of light is 1342nm.

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

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

In this embodiment, the reason why the thickness of one layer of the thermosetting resin film or laminated film that is the specific target of the light transmittance is set to 200 μm is that by using the thermosetting resin with such a thickness film or laminated film, the transmittance of the light can be measured more accurately and easily. In this embodiment, the thickness of both the thermosetting resin film of one layer 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 can be adjusted, for example, by adjusting the types and contents 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. .

[Proportion of thermosetting component content] The thermosetting resin film preferably contains a thermosetting component other than an acrylic resin having an epoxy group, and the content of the thermosetting component in the thermosetting resin film is preferably greater than the total content of the thermosetting resin film. The mass ratio ([content of the thermosetting component of the thermosetting resin film (parts by mass)]/[total mass of the thermosetting resin film (parts by mass)] × 100) is 40 mass % or more. When the thermosetting resin film contains two or more types of thermosetting components, the content (parts by mass) of the above-mentioned thermosetting components means the total content (parts by mass) of all types of these two or more thermosetting components. share).

By satisfying the above-mentioned content ratio conditions, the thermosetting resin film can be prevented from remaining on the upper portion of the protruding electrode including the top portion of the protruding electrode when it is attached to the protruding electrode formation surface of the workpiece. In this way, the upper part of the protruding electrode protrudes through the attached thermosetting resin film, so that the workpiece finally obtained can be fully electrically connected to the substrate through the protruding electrode during flip-chip mounting. If there is no thermosetting resin film remaining on the upper part of the protruding electrode when it is attached to the protruding electrode formation surface of the workpiece, there is no need to remove such remaining thermosetting resin film or use the thermosetting resin film. The first protective film formed by hardening is removed separately, thereby simplifying the steps.

In the thermosetting resin film, the "thermosetting component" whose content ratio is specified above is a component that exhibits a curing reaction by heating. However, acrylic resin having an epoxy group is not included in this thermosetting component. Examples of the thermosetting component include the thermosetting component (B) described below. Examples of the thermosetting component (B) include epoxy thermosetting resin, polyimide resin, unsaturated polyester resin, 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 regulation of the above-mentioned content ratio. On the other hand, examples of the acrylic resin having an epoxy group that is not included in the thermosetting component include compounds having an epoxy group in the acrylic resin in the polymer component (A) described below. For example, acrylic resin having a glycidyl group is included in acrylic resin having an epoxy group.

The thermosetting resin film may contain only one type of the aforementioned thermosetting component, or may contain two or more types. In the case of two or more types, the combination and ratio of these components may be arbitrarily selected.

In order to obtain the above advantageous effects more significantly, the proportion of the content of the thermosetting component in the thermosetting resin film to the total mass of the thermosetting resin film may be, for example, 50% by mass or more, 60% by mass or more. Any of mass % or more, 70 mass % or more, or 80 mass % or more.

The upper limit of the aforementioned content ratio is not particularly limited. For example, in order to achieve better film-forming properties of the thermosetting resin film, the ratio of the total content is preferably 90 mass % or less.

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

[Total value of X values] When the thermosetting resin film contains two or more kinds of the thermosetting components other than the acrylic resin having an epoxy group, in the thermosetting resin film, the thermosetting component contained in the thermosetting resin film , for each type, the value of The value may be, for example, 400 g/eq or less. X = [equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)]/[of the thermosetting resin film Total content (parts by mass) of all types of thermosetting ingredients].

When the thermosetting resin film satisfies these conditions, when the workpiece with the first protective film is manufactured as described above, the first protective film can be cut simultaneously when the workpiece is divided at the modified layer. Protective film. Therefore, there is no need to provide a separate step for cutting the first protective film, and the workpiece processed with the first protective film can be manufactured with high efficiency.

The aforementioned X value is calculated from the aforementioned formula for one thermosetting component contained in the aforementioned thermosetting resin film. The "thermosetting component" to be calculated as the value of X is the same as the "thermosetting component" whose content ratio is specified in the thermosetting resin film.

The so-called "functional group related to the thermosetting reaction of the thermosetting component" used to calculate the value of In this case, it is a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, an acid group formed by anhydride, etc. However, these are examples of the aforementioned functional groups.

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

[Number 1]

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

[Number 2]

Furthermore, the total value of the above-mentioned X value (X ₁ , ..., _Xp ) among all types of thermosetting components (M ₁ , ... .

[Number 3]

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

In order to obtain the above advantageous effects more significantly, in the thermosetting resin film, the total value of the X values may be, for example, any one of 375 g/eq or less, 350 g/eq or less, and 325 g/eq or less.

The lower limit of the total value of the aforementioned X values is not particularly limited. For example, in the thermosetting resin film, in order to suppress reduction in flexibility due to excessive cross-linking reaction, the total value of the X values is preferably 100 g/eq or more.

The total value of the aforementioned X value can be appropriately adjusted to fall within a range set by any combination of the aforementioned lower limit value and upper limit value. For example, in one embodiment, the total value of the aforementioned .

Preferable examples of the thermosetting resin film include a thermosetting resin film that satisfies all the conditions of the above-mentioned light transmittance, the content ratio of the thermosetting component, and the total value of the X value. For example, the thermosetting resin film preferably contains two or more thermosetting components other than an acrylic resin having an epoxy group, and the total of all types of thermosetting components in the thermosetting resin film is preferably The proportion of the content relative to the total mass of the thermosetting resin film is 40% by mass or more, and one layer of the thermosetting resin film with a thickness of 200 μm or two layers of the aforementioned thermosetting resin film with a thickness less than 200 μm are laminated The transmittance of the above-mentioned laminated film with a total thickness of 200 μm for light with a wavelength of 1342 nm is 50% or more, and the thermosetting component contained in the thermosetting resin film is calculated as follows for each type: When the X value calculated by the above formula is the total value of the X value in all types of the thermosetting components contained in the thermosetting resin film, the total value is 400 g/eq or less. X = [equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)]/[of the thermosetting resin film Total content of all types of thermosetting ingredients (parts by mass)]

[Breaking strength of the first protective film] The breaking strength measured by the following method of the first protective film having a size of 20 mm×130 mm and a thickness of 40 μm may be, for example, 55 MPa or less. A first protective film having the same composition as the first protective film whose breaking strength is equal to or less than the upper limit value will be easier to cut by expansion as described later. As the breaking strength of the first protective film, the following maximum stress can be used. That is, the distance between the clamps in the first protective film is 80 mm, and the stretching speed of the first protective film is 200 mm/min. By The maximum stress measured when the clamp stretches the first protective film in a direction parallel to the surface of the first protective film. As the first protective film to be measured for the maximum stress, a film obtained by heating and thermosetting a thermosetting resin film at 130° C. for 2 hours can be used.

In order to make the above effect more remarkable, the breaking strength of the first protective film may be, for example, any one of 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 order to increase the protective ability of the first protective film, the breaking strength of the first protective film is preferably 0.1 MPa or more.

The aforementioned breaking strength of the first protective film can be appropriately adjusted to be within a range set by any combination of the aforementioned lower limit value and upper limit value. In one embodiment, the breaking strength of the first protective film may be, for example, any one of 0.1MPa to 55MPa, 0.1MPa to 52.5MPa, 0.1MPa to 50MPa, and 0.1MPa to 47.5MPa.

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

In workpieces and workpieces with protruding electrodes on the circuit surface, the surface (inner surface) opposite to the circuit surface may be exposed. Therefore, a protective film containing an organic material may be formed on the inner surface (in this specification, it may be called a "second protective film" to distinguish it from the first protective film). The second protective film is used to prevent cracks in the workpiece after the workpiece is divided or packaged. Such a workpiece with a second protective film on its inner surface and a second protective film will eventually be incorporated into a target substrate device such as a semiconductor device. On the other hand, the second protective film may be required to have the function of marking information about the workpiece using a laser or concealing the inner surface of the workpiece. As a second protective film that satisfies such a requirement, a curable resin film in which a second protective film can be formed by curing and whose light transmission characteristics are adjusted is known. However, since the second protective film for protecting the inner surface of the workpiece and the first protective film for protecting the protruding electrode forming surface of the workpiece are formed at different positions on the workpiece, the required characteristics are also different. different from each other. Therefore, it is generally difficult to directly use a thermosetting resin film capable of forming a second protective film for forming a first protective film.

FIG. 1 is a cross-sectional view schematically showing an example of a state in which a first protective film is formed on a protruding electrode formation surface using the thermosetting resin film of this embodiment. In order to make it easy to understand the features of the present invention and for convenience, the drawings used in the following description may show enlarged parts of the main components, and the dimensional ratios of each component may not be the same as the actual ones.

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

The first protective film 12' is formed using the thermosetting resin film of this embodiment, and covers the circuit surface 90a of the workpiece 90, and further covers the surface 91a of the protruding electrode 91 except for the top portion 910 of the protruding electrode 91 and its vicinity. outside areas. In this way, the first protective film 12' is in close contact with the surface 91a except the top portion 910 of the protruding electrode 91 and its vicinity, and is also in close contact with the circuit surface 90a of the workpiece 90, thereby burying the protruding electrode 91. The substantially spherical shape of the protruding 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 protruding electrode 91 is not particularly limited, but is preferably 50 μm to 500 μm. When the height H ₉₁ of the protruding electrode 91 is equal to or higher than the aforementioned lower limit, the function of the protruding electrode 91 can be further improved. When the height H ₉₁ of the protruding electrode 91 is equal to or less than the aforementioned upper limit, the thermosetting resin film is attached to the protruding electrode formation surface of the workpiece 90 (that is, the surface 91 a of the protruding electrode 91 and the surface of the workpiece 90 When the circuit surface 90a) is used, the effect of suppressing the residual thermosetting resin film on the upper part of the protruding electrode 91 including the top part 910 becomes higher, resulting in the effect of inhibiting the formation of the first protective film 12' on the upper part of the protruding electrode 91. get taller. In addition, in this specification, the "height of the protruding electrode" means the height of the protruding electrode at the highest position from the circuit surface of the workpiece or the workpiece to be processed (that is, the top of the head).

The width W ₉₁ of the protruding electrode 91 is not particularly limited, but is preferably 50 μm to 600 μm. When the width W ₉₁ of the protruding electrode 91 is equal to or greater than the aforementioned lower limit, the function of the protruding electrode 91 can be further improved. When the width W ₉₁ of the protruding electrode 91 is equal to or less than the aforementioned upper limit, the thermosetting resin film is attached to the protruding electrode formation surface of the workpiece 90 (that is, the surface 91 a of the protruding electrode 91 and the surface of the workpiece 90 When the circuit surface 90a) is used, the effect of suppressing the residual thermosetting resin film on the upper part of the protruding electrode 91 including the top part 910 becomes higher, resulting in the effect of inhibiting the formation of the first protective film 12' on the upper part of the protruding electrode 91. get taller. In addition, in this specification, the "width of the protruding electrode" means the difference in the surface of the protruding electrode when the protruding electrode is viewed from a direction perpendicular to the circuit surface of the workpiece or workpiece processing object. The maximum value of the line segment obtained by connecting two points with a straight line.

The distance D ₉₁ between adjacent protruding electrodes 91 is not particularly limited, but is preferably 100 μm to 800 μm. When the distance D ₉₁ between the protruding electrodes 91 is equal to or greater than the aforementioned lower limit, the thermosetting resin film is attached to the protruding electrode formation surface of the workpiece 90 (that is, the surface 91 a of the protruding electrode 91 and the workpiece 90 When the circuit surface 90a) is formed, the effect of inhibiting the thermosetting resin film from remaining on the upper portion of the protruding electrode 91 including the top portion 910 becomes higher, and as a result, the first protective film 12' is inhibited from being formed on the upper portion of the protruding electrode 91. The effect becomes higher. When the distance D ₉₁ between the protruding electrodes 91 is equal to or less than the upper limit, the degree of freedom in the arrangement of the protruding electrodes 91 becomes higher. In addition, in this specification, the "distance between adjacent protruding electrodes" means the minimum value of the distance between the surfaces of adjacent protruding electrodes.

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

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

For example, FIG. 1 shows a protruding electrode having a substantially spherical shape (a shape in which a part of a ball is cut off in a plane) as described above, but this substantially spherical shape is arranged along the height direction ( In FIG. 1 , the shape is elongated in a direction orthogonal to the circuit surface 90 a of the workpiece 90 ), that is, the shape of an ellipsoid that is a substantially prolate sphere (in other words, the shape including the long axis direction of the ellipsoid that is a prolate sphere). A protruding electrode in the shape of one end of which is cut off in a plane), or a shape in which the above-mentioned roughly spherical shape is flattened in the height direction, that is, in the shape of an ellipsoid that is a roughly oblate sphere (in other words, including A preferred shape of the protruding electrode is a protruding electrode in which one end of an oblate ellipsoid in the minor axis direction is cut off in a plane). This kind of substantially ellipsoid-shaped protruding electrode is particularly advantageous for forming the first protective film using the thermosetting resin film of the present embodiment, similarly to the above-mentioned substantially spherical protruding electrode. Examples of the protruding electrodes other than these include: protruding electrodes having a cylindrical shape, an elliptical columnar shape, a rectangular prism shape, an elliptical cone shape, a pyramid shape, a truncated cone shape, an elliptical truncated cone shape or a truncated cone shape; and A protruding electrode in a shape formed by combining a cylinder, an elliptical cylinder, a corner prism, a truncated cone, an elliptical frustum or a pyramidal cone with the above-mentioned approximate sphere or approximate ellipsoid. In addition, the shape of the protruding electrode described above is only an example of a preferred shape when applying the thermosetting resin film of this embodiment. In the present invention, the shape of the protruding electrode is not limited to these. Hereinafter, the structure of this invention is demonstrated in detail.

◎1st support piece The first supporting sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other. As long as the effects of the present invention are not impaired, the combination of these multiple layers is not particularly limited. In addition, in this specification, it is not limited to the case of the first support sheet. The term "multiple layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only some of the layers may be the same." Furthermore, "multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

As a preferred first support sheet, for example, a sheet including a first base material and a first adhesive layer provided on the first base material (in other words, the first base material and the first adhesive layer are A sheet in which these layers are laminated in the thickness direction); a sheet including a first base material, a first intermediate layer provided on the first base material, and a first adhesive layer provided on the first intermediate layer ( In other words, a sheet in which the first base material, the first intermediate layer and the first adhesive layer are laminated in this order in the thickness direction of these layers); a sheet consisting only of the first base material, etc.

Hereinafter, examples of the first protective film forming sheet of this embodiment will be described for each type of such first supporting sheet with reference to the drawings.

FIG. 2 is a cross-sectional view schematically showing an example of the first protective film forming sheet according to this embodiment. The first protective film forming sheet 1 shown here is a sheet in which a first base material and a first adhesive layer are laminated in the thickness direction of these layers as a first supporting sheet. That is, the first protective film forming sheet 1 is provided with the first base material 11, the first adhesive layer 13 provided on one side of the first base material 11, and the first adhesive layer 13 provided in the first adhesive layer 13. 1 The base material 11 side is composed of a thermosetting resin layer (thermosetting resin film) 12 on the opposite surface 13a. The first support sheet 101 is a laminate of the first base material 11 and the first adhesive layer 13 . Furthermore, the first protective film forming sheet 1 can be said to include the first support sheet 101 and the thermosetting resin layer 12 provided on one surface 101 a of the first support sheet 101 , in other words, one surface 13 a of the first adhesive layer 13 .

The first protective film forming sheet 1 includes one thermosetting resin layer 12 with a thickness of 200 μm or a laminated film with a total thickness of 200 μm formed by laminating two or more thermosetting resin layers 12 with a thickness of less than 200 μm. The transmittance of light with a wavelength of 1342nm is more than 50%. In addition, in the thermosetting resin layer 12 in the first protective film forming sheet 1, the content ratio of the above-mentioned thermosetting component may be 40 mass% or more.

FIG. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet according to this embodiment. In addition, in the drawings after FIG. 3 , the same constituent elements as those shown in the previously described drawings are assigned the same reference numerals as in the already described drawings, and detailed descriptions of the constituent elements are omitted.

The first protective film forming sheet 2 shown here uses a first base material, a first intermediate layer, and a first adhesive layer laminated in this order in the thickness direction of these layers as a first supporting sheet. That is, the first protective film forming sheet 2 is provided with the first base material 11, the first intermediate layer 14 provided on one side of the first base material 11, and the first base material provided in the first intermediate layer 14. The first adhesive layer 13 on the side opposite to the first intermediate layer 14, and the thermosetting resin layer (thermosetting resin layer) provided on the surface 13a of the first adhesive layer 13 opposite to the first intermediate layer 14 side. It is composed of a flexible resin film) 12. The first support sheet 102 is a laminate of the first base material 11, the first intermediate layer 14, and the first adhesive layer 13. Furthermore, it can be said that the first protective film forming sheet 2 includes the first support sheet 102, and the thermosetting resin layer 12 is provided on one side 102a of the first support sheet 102, in other words, one side 13a of the first adhesive layer 13.

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

The first protective film forming sheet 2 includes one thermosetting resin layer 12 with a thickness of 200 μm or a laminated film with a total thickness of 200 μm formed by laminating two or more thermosetting resin layers 12 with a thickness of less than 200 μm. The transmittance of light with a wavelength of 1342nm is more than 50%. In addition, in the thermosetting resin layer 12 in the first protective film forming sheet 2, the content ratio of the above-mentioned thermosetting component may be 40 mass% or more.

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

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

The first protective film forming sheet 3 includes one thermosetting resin layer 12 with a thickness of 200 μm or a laminated film with a total thickness of 200 μm formed by laminating two or more thermosetting resin layers 12 with a thickness of less than 200 μm. The transmittance of light with a wavelength of 1342nm is more than 50%. In addition, the content ratio of the above-mentioned thermosetting component in the thermosetting resin layer 12 in the first protective film forming sheet 3 may be 40% by mass or more.

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

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

The resin constituting the first base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

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

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

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

The first base material may be transparent or opaque, may be colored according to the purpose, and may be vapor-deposited with other layers. When the first adhesive layer or thermosetting resin layer described below has energy ray curability, it is preferable that the first base material transmits energy rays.

The first base material may be, for example, a release film in which one side of a resin film is subjected to a release treatment such as polysiloxane treatment as described in the Examples below.

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

○1st adhesive layer The aforementioned first adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the adhesive include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate and other adhesive resins, and acrylic resin is preferred. .

In addition, in the present invention, the concept of "adhesive resin" includes both adhesive resins and adhesive resins. For example, it includes not only resins that have adhesive properties by themselves, but also resins that are used in combination with other ingredients such as additives. Resin that exhibits adhesiveness, or resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.

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

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

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

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

The first adhesive composition may be coated by a known method. For example, the following methods may be used: air knife coater, blade coater, rod coater, gravure coater, roller coater, etc. Type coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.

The drying conditions of the first adhesive composition are not particularly limited. When the first adhesive composition contains a solvent, it is preferable to perform heat drying. The first adhesive composition containing a solvent can be dried, for example, at 70°C to 130°C for 10 seconds to 5 minutes.

When the first adhesive layer is energy ray curable, examples of the first adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable first adhesive composition include the following. The first adhesive composition, etc.: The first adhesive composition (I-1) contains a non-energy ray curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-1a)"). )") and an energy ray curable compound; the first adhesive composition (I-2), which contains an energy ray curable adhesive resin in which an unsaturated group is introduced into the side chain of the aforementioned adhesive resin (I-1a) (I-2a) (hereinafter, sometimes referred to as "adhesive resin (I-2a)"); the first adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and energy ray curing Sexual low molecular compounds.

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

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

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

○1st middle layer The first intermediate layer is in the form of a sheet or a film, and the material constituting the first intermediate layer is not particularly limited as long as it is appropriately selected according to the purpose. For example, when the purpose is to prevent the shape of the protruding electrode existing on the circuit surface from being reflected on the first protective film provided on the protruding electrode formation surface, causing the first protective film to be deformed, as the first Preferred constituent materials of the intermediate layer include (meth)acrylic urethane and the like, in terms of further improving the adhesion of the first intermediate layer.

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

The thickness of the first intermediate layer can be appropriately adjusted according to the height of the protruding electrode present on the surface of the workpiece to be protected or the workpiece processed object. For example, the thickness of the first intermediate layer is preferably 50 μm to 600 μm in order to easily absorb the influence of a relatively high-height protruding electrode. Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer. For example, the thickness of the first intermediate layer composed of multiple layers means the total thickness of all the layers constituting the first intermediate layer. .

[First intermediate layer forming composition] The first intermediate layer can be formed using a first intermediate layer-forming composition containing a constituent material of the first intermediate layer. For example, the first intermediate layer can be formed at the target site by applying the first intermediate layer forming composition on the surface to be formed of the first intermediate layer, drying it or hardening it by irradiating energy rays if necessary. A more specific method of forming the first intermediate layer will be described in detail later along with methods of forming other layers.

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

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

[Method for manufacturing the first intermediate layer forming composition] The first intermediate layer forming composition can be produced by the same method as the above-mentioned first adhesive composition, except that the ingredients are different.

◎Thermosetting resin film (thermosetting resin layer) The thermosetting resin film (thermosetting resin layer) is a film (layer) used to protect the circuit surface of the workpiece and the workpiece processed object, and the protruding electrodes provided on the circuit surface. The thermosetting resin film is thermally cured to form a first protective film.

In addition, in this specification, even after the thermosetting resin film is cured (in other words, after the first protective film is formed), as long as the first supporting sheet and the cured product of the thermosetting resin film are maintained (in other words, the first supporting sheet and the cured product of the thermosetting resin film are maintained). first protective film), the laminated structure is also called a "first protective film forming sheet".

In addition to thermosetting properties, the thermosetting resin film may or may not have energy ray curing properties. However, when the thermosetting resin film has the property of energy ray curability, in forming the first protective film from the thermosetting resin film, the contribution of the thermosetting of the thermosetting resin film is greater than that of the energy ray curing. contribution.

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

The thickness of the thermosetting resin film, regardless of whether it has energy ray curability or not, is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and particularly preferably 5 μm to 60 μm. When the thickness of the thermosetting resin film is equal to or greater than the aforementioned lower limit, a first protective film with higher protective capability can be formed. By keeping the thickness of the thermosetting resin film below the aforementioned upper limit, when the thermosetting resin film is attached to the protruding electrode forming surface of the workpiece, the residual thermosetting resin film on the upper portion of the protruding electrode is suppressed. The effect becomes higher. Furthermore, when the thickness of the thermosetting resin film is equal to or less than the aforementioned upper limit, the first protective film can be cut more favorably when the workpiece is divided. Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film. For example, the thickness of the thermosetting resin film composed of multiple layers means the entire thickness of the thermosetting resin film. The total thickness of the layers.

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

The thermosetting resin layer-forming composition may be coated by a known method. For example, methods using the following various coaters: air knife coater, blade coater, rod coater, gravure coater Machine, roller coater, roller knife coater, curtain coater, mold coater, knife coater, screen coater, Meyer rod coater, light touch coating Machine etc.

The drying conditions of the thermosetting resin layer-forming composition are not particularly limited regardless of whether the thermosetting resin film has energy ray curability or not. However, when the composition for forming a thermosetting resin layer contains a solvent described below, it is preferable to perform heating and drying. The composition for forming a thermosetting resin layer containing a solvent may be dried, for example, at 70°C to 130°C for 10 seconds to 5 minutes. However, the composition for forming a thermosetting resin layer is preferably heated and dried so that the composition itself and the thermosetting resin film formed from the composition are not thermally cured.

The curing conditions when thermally curing the thermosetting resin film to form the first protective film are not particularly limited as long as the first protective film has a degree of curing that fully exhibits the function of the first protective film. The type of curable resin film may be appropriately selected. For example, the heating temperature during thermal curing of the thermosetting resin film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. Furthermore, the heating time during the thermal hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, even more preferably 1 to 3 hours.

Preferable thermosetting resin films include, for example, films containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component formed by polymerization reaction as a polymerizable compound. In addition, the thermosetting component (B) is a component that can perform a curing (polymerization) reaction using heat as a trigger for the reaction. In addition, in this specification, the polymerization reaction also includes the polycondensation reaction.

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

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the 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 type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be Take your pick.

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 acrylic resin.

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

[Chemical 1] (In the formula, l, m and n are each independently an integer above 1)

The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5,000 to 200,000, more preferably 8,000 to 100,000. When the weight average molecular weight of the polyvinyl acetal is in this range, when the thermosetting resin film is attached to the protruding electrode formation surface, the effect of suppressing the residual thermosetting resin film on the upper part of the protruding electrode is achieved. get taller.

The glass transition temperature (Tg) of polyvinyl acetal is preferably 40°C to 80°C, more preferably 50°C to 70°C. Since the Tg of the polyvinyl acetal is in this range, when the thermosetting resin film is attached to the protruding electrode formation surface, the effect of suppressing the residual thermosetting resin film on the upper part of the protruding electrode becomes higher.

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

The acrylic resin in the polymer component (A) means a resin having a structural unit derived from (meth)acrylic acid or a derivative thereof. In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, the concept of "(meth)acrylyl" includes both "acrylyl" and "methacrylyl", and "(meth)acrylate" The concept includes both "acrylate" and "methacrylate". In addition, in this specification, a "derivative" of a specific compound means a compound having a structure in which one or more hydrogen atoms of the compound are substituted with groups (substituents) other than hydrogen atoms. For example, (meth)acrylates are derivatives 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 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or higher than the aforementioned lower limit, the shape stability of the thermosetting resin film (stability over time during storage) is improved. When the weight average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit, the thermosetting resin film becomes easier to follow the uneven surface of the adherend, thereby further suppressing the generation of gaps between the adherend and the thermosetting resin film. wait. In addition, in this specification, the so-called "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) unless otherwise specified.

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

Examples of the acrylic resin include polymers of one or more (meth)acrylic acid esters selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxy. Copolymers of two or more monomers such as methacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester , n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate )Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate Ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), Tridecyl (meth)acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate Alkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute one of the alkyl esters The alkyl group is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid cycloalkyl groups such as (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, etc. Esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenoxy (meth)acrylate (meth)acrylic acid cycloalkenyloxyalkyl esters such as ethyl ester; (meth)acrylimide; (meth)acrylic acid glycidyl ester and other glycidyl-containing (meth)acrylates; (meth)acrylates )Hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth)acrylates containing hydroxyl groups, such as 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; N-methylaminoethyl (meth)acrylate, etc. containing substituted amine groups (meth)acrylate, etc. 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 hydrogen atoms.

For example, in addition to the aforementioned (meth)acrylate, the acrylic resin may also be one selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. It is formed by copolymerizing two or more monomers.

The monomer constituting the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be selected arbitrarily.

Acrylic resin may also have functional groups such as vinyl group, (meth)acryl group, amine group, hydroxyl group, carboxyl group, isocyanate group, etc. that can be bonded with other compounds. The aforementioned functional group of the acrylic resin may be bonded to other compounds via the cross-linking agent (F) described below, or may be directly bonded to other compounds without the cross-linking agent (F). Since the acrylic resin is bonded to other compounds via the functional groups, the reliability of the package obtained using the first protective film forming sheet tends to be improved.

In the present invention, for example, as the polymer component (A), instead of using polyvinyl acetal and acrylic resin, a thermoplastic resin other than polyvinyl acetal and acrylic resin (hereinafter, sometimes simply referred to as "thermoplastic resin") may be used alone. ”), can also be used together with polyvinyl acetal or acrylic resin. By using the aforementioned thermoplastic resin, the releasability of the first protective film from the first support sheet may be improved, or the thermosetting resin film may become easier to follow the uneven surface of the adherend, thereby further suppressing the interference between the adherend and the adherend. Gaps etc. are generated between thermosetting resin films.

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

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

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

The aforementioned thermoplastic resin contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these can be selected arbitrarily.

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

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

[Thermosetting ingredient (B)] The thermosetting component (B) has thermosetting properties and is a component for thermosetting the thermosetting resin film to form a hard first protective film. In addition, in the thermosetting resin film, the thermosetting component (B) conforms to both the "thermosetting component" that stipulates the above-mentioned content ratio and the "thermosetting component" that is the object of calculation of the aforementioned X value.

The thermosetting component (B) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these You can choose whatever you want.

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

[Epoxy thermosetting resin] The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2). In the thermosetting resin film, both the epoxy resin (B1) and the thermosetting agent (B2) meet the "thermosetting component" that stipulates the above-mentioned content ratio, and the "thermosetting component" that is the calculation target of the aforementioned X value. ingredients" both.

The epoxy thermosetting resin contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these You can choose whatever you want.

・Epoxy resin (B1) Examples of the epoxy resin (B1) include known epoxy resins. Examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolak epoxy. Resin, dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenylene skeleton type epoxy resin and other 2-functional or higher epoxy resins compound.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the workpiece processed product with the first protective film obtained using the first protective film forming sheet is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by addition reaction of (meth)acrylic acid or a derivative thereof and an epoxy group. Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include: ethylidene (vinyl), 2-propenyl (allyl), (meth)acrylyl, (Meth)acrylamide group and the like, preferably acrylyl group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of the curability of the thermosetting resin film and the strength and heat resistance of the cured resin film, it is preferably 300 to 30,000, more preferably The range is 300 to 10,000, preferably 300 to 3,000.

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

One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio of these may be selected arbitrarily.

・Thermal hardener (B2) The thermosetting agent (B2) functions as a hardening 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 carboxyl group, an acidic group and the like, and preferably a phenolic hydroxyl group, an alcoholic hydroxyl group, an acidic group and an anhydride group. The group is preferably a phenolic hydroxyl group or an amine group.

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

The thermal hardener (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include: a compound in which a part of the hydroxyl groups of the phenol resin is substituted with a group having an unsaturated hydrocarbon group; and a compound having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Based compounds, etc. The aforementioned unsaturated hydrocarbon group in the thermal hardener (B2) is the same as the aforementioned unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

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

In the thermal hardener (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300 to 30,000, more preferably 300 to 30,000. The best value is 400 to 10,000, especially the best value is 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

One type of thermosetting agent (B2) can be used alone, or two or more types can be used in combination. When two or more types are used in combination, the combination and ratio of these can be selected arbitrarily.

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

In the composition (III-1) and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer component ( The content of A) is 100 parts by mass, for example, it can be 300 to 1400 parts by mass, 400 to 1300 parts by mass, 500 to 1100 parts by mass, 600 to 1000 parts by mass, and 700 to 900 parts by mass Any kind of portion. When the aforementioned 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.

[Harding accelerator (C)] The composition (III-1) and the thermosetting resin film may contain a hardening accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). Preferred hardening 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- Imidazoles such as hydroxymethylimidazole (imidazole in which more than one hydrogen atom is replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (more than one hydrogen atom is substituted by a group other than a hydrogen atom); Phosphines in which hydrogen atoms are substituted by organic groups); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

The hardening accelerator (C) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be Take your pick.

When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III-1) and the thermosetting resin film is 100 parts by mass relative to the content of the thermosetting component (B). For example, it may be any one of 0.01 to 10 parts by mass and 0.1 to 7 parts by mass. By setting the aforementioned content of the hardening accelerator (C) to be equal to or more than the aforementioned lower limit, the effect obtained by using the hardening accelerator (C) can be more significantly obtained. When the content of the hardening accelerator (C) is below the above-mentioned upper limit, for example, the highly polar hardening accelerator (C) is adhered to the thermosetting resin film in the thermosetting resin film under high temperature and high humidity conditions. As the body moves to the interface side, the segregation suppression effect becomes higher. As a result, the reliability of the workpiece processed product with the first protective film obtained using the first protective film forming sheet is further improved.

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

The filler material (D) can be either an organic filler material or an inorganic filler material, and an inorganic filler material is preferred. Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, titanium dioxide, silicon carbide, boron nitride, etc.; these inorganic fillers are formed into spherical shapes. Beads; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, and more preferably silica.

The average particle diameter of the filler (D) may be appropriately selected depending on the purpose and is not particularly limited. For example, it may be 0.02 μm to 2 μm. In addition, in this specification, the "average particle diameter" means the particle diameter (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction and scattering method, unless otherwise specified. value.

The filler material (D) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.

In the composition (III-1), the ratio of the content of the filler (D) to the total content of all components except the solvent (that is, the ratio of the content of the filler (D) in the thermosetting resin film to the total content of the thermosetting resin film) The proportion of the total mass of the flexible resin film) may be, 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. Any of mass %. When the aforementioned ratio is within this range, it becomes easier to adjust the thermal expansion coefficient of the above-mentioned first protective film.

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

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A), the thermosetting component (B), etc., and is more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyltriethyloxysilane, imidazolesilane, etc.

The coupling agent (E) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.

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 relative to the polymer component (A) and the thermosetting component (B). The total content may be any one of 0.03 to 20 parts by mass, 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass per 100 parts by mass. By having the aforementioned content of the coupling agent (E) above the aforementioned lower limit, the following effects brought about by the use of the coupling agent (E) can be more significantly obtained: the dispersibility of the filler (D) in the resin is improved; Or the adhesion between the thermosetting resin film and the adherend can be improved, etc. When the content of the coupling agent (E) is equal to or less than the upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)] When the above-mentioned acrylic resin, etc., having functional groups such as vinyl, (meth)acrylyl, amine, hydroxyl, carboxyl, and isocyanate groups that can be bonded to other compounds is used as the polymer component (A), the composition The substance (III-1) and the thermosetting resin film may also contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the aforementioned functional group in the polymer component (A) by bonding it to other compounds. By cross-linking in this way, the initial adhesion of the thermosetting resin film can be adjusted. strength and cohesion.

Examples of the cross-linking agent (F) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate-based cross-linking agents (cross-linking agents having a metal chelate structure), and aziridine-based cross-linking agents. Agent (cross-linking agent with aziridine group), etc.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); Terpolymers, isocyanurates and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant of low molecular weight active hydrogen compounds. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. In addition, the term "terminated isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specific examples of the organic polyisocyanate compound include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylenedimethyldiisocyanate; 1,4-xylylenediisocyanate Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate added to all or part of the hydroxyl groups of polyols such as trimethylolpropane, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

Examples of the organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinemethane), trimethylolpropane-tris-β-nitrogen Propiridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene Based on melamine, etc.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (F), it is preferred to use a hydroxyl-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 cross-linked structure can be easily introduced through the reaction between the cross-linking agent (F) and the polymer component (A). In thermosetting resin film.

The cross-linking agent (F) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be Take your pick.

When a cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III-1) relative to 100 parts by mass of the content of the polymer component (A) can be, for example, 0.01 to 0.01 parts by mass. Any one of 20 parts by mass, 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass. By setting the aforementioned content of the cross-linking agent (F) to be equal to or more than the aforementioned lower limit, the effects brought about by the use of the cross-linking agent (F) can be more significantly obtained. When the content of the cross-linking agent (F) is equal to or less than the upper limit, excessive use of the cross-linking agent (F) is suppressed.

[Energy ray curable resin (G)] The composition (III-1) and the thermosetting resin film may contain energy ray curable resin (G). By containing energy ray curable resin (G), the thermosetting resin film can change its characteristics by irradiating energy rays.

Energy ray curable resin (G) is obtained by polymerizing (hardening) 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 preferably are acrylate compounds having a (meth)acrylyl group.

Examples of the acrylate compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. hydroxy) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylates and other (meth)acrylates containing a chain aliphatic skeleton; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyethylene glycol Polyalkylene glycol (meth)acrylate such as di(meth)acrylate; oligoester (meth)acrylate; (meth)acrylic urethane oligomer; epoxy modified (meth)acrylate (meth)acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

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 polymerization may be only one type or two or more types. In the case of two or more types, the combination and ratio of these compounds may be selected arbitrarily.

The energy ray curable resin (G) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

When an energy ray curable resin (G) is used, the ratio of the content of the energy ray curable resin (G) in the composition (III-1) to the total mass of the composition (III-1) can be, for example, Any one of 1 mass% to 95 mass%, 5 mass% to 90 mass%, and 10 mass% to 85 mass%.

[Photopolymerization initiator (H)] When the composition (III-1) and the thermosetting resin film contain the energy ray curable resin (G), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G), a photopolymerizable polymer may be included. Starter (H).

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, and benzoin benzoic acid methyl ether. Benzoin compounds such as ester, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethane-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide compounds such as phosphine oxide; thioether compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketool compounds such as 1-hydroxycyclohexylphenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diethyl; benzoyl; diphenyl chloride; benzophenone ;2,4-diethylthioxanthone;1,2-diphenylmethane;2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone;2- Chloranthraquinone, etc. 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 type, or may be two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

When a photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is 100 parts by mass relative to the content 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.

[Color(I)] The composition (III-1) and the thermosetting resin film may contain the colorant (I). Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, and azulium pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo-based pigments, metal complex-based pigments (metal complex dyes), dithiol metal complex-based pigments, indoxyl-based pigments, triallylmethane-based pigments, anthraquinone-based pigments, naphthols pigments, methine azo pigments, benzimidazolone pigments, picanthrone pigments and threne pigments, etc.

Examples of the inorganic pigment include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO (Indium Tin Oxide; indium tin oxide) pigments, ATO (Antimony Tin Oxide; antimony tin oxide) pigments, etc.

The colorant (I) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select.

When using the colorant (I), the content of the colorant (I) in the thermosetting resin film may be appropriately adjusted depending on the purpose. For example, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components except the solvent (that is, the ratio of the content of the colorant (I) in the thermosetting resin film to the total content of all components except the solvent) The proportion of the total mass of the thermosetting resin film) may be 0.1% by mass to 5% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the colorant (I) can be more significantly obtained. When the ratio is equal to or less than the upper limit, excessive decrease in the light transmittance of the thermosetting resin film is suppressed.

[General Additive(J)] The composition (III-1) and the thermosetting resin film may contain a general-purpose additive (J) within a range that does not impair the effects of the present invention. The general-purpose additive (J) can be a well-known compound, and can be selected arbitrarily according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives (J) include plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) etc.

The general additive (J) contained in the composition (III-1) and the thermosetting resin film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary. select. The content of the general-purpose additive (J) in the composition (III-1) and the thermosetting resin film is not particularly limited and may be appropriately selected depending on the purpose.

[solvent] The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good operability. The solvent is not particularly limited. Examples of preferred solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amide such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds )wait. The solvent contained in the composition (III-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio of these solvents may be selected arbitrarily.

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

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

As an example of a preferred thermosetting resin film of the present embodiment, a thermosetting resin film used to form the first protective film in the following manner, that is, the thermosetting resin is The film is attached to the surface of the workpiece with the protruding electrode and is thermally hardened, thereby forming a first protective film on the aforementioned surface; a layer of the aforementioned thermosetting resin film with a thickness of 200 μm or a layer of the aforementioned thermosetting resin film with a thickness less than 200 μm is formed. The transmittance of the laminated film with a total thickness of 200 μm, which is composed of two or more layers of the thermosetting resin film, for light with a wavelength of 1342 nm is more than 50%; the aforementioned thermosetting resin film contains a polymer component (A) and has an epoxy Epoxy resin (B1), thermosetting agent (B2), and filler material (D) other than the base acrylic resin; the aforementioned epoxy resin (B1) and thermosetting agent (B2) in the aforementioned thermosetting resin film The ratio of the total content to the total mass of the thermosetting resin film is 40% by mass or more; the content of the polymer component (A) in the thermosetting resin film to the total mass of the thermosetting resin film is The proportion is 5 mass % to 30 mass %; the content of the filler material (D) in the thermosetting resin film is 5 mass % to 20 mass % relative to the total mass of the thermosetting resin film.

Another example of a preferred thermosetting resin film of this embodiment is a thermosetting resin film used to form a first protective film in the following manner: that is, the thermosetting resin film is The resin film is attached to the surface of the workpiece with the protruding electrode and is thermally hardened, thereby forming a first protective film on the aforementioned surface; a layer of the aforementioned thermosetting resin film with a thickness of 200 μm may be less than 200 μm thick. The transmittance of the laminated film with a total thickness of 200 μm, which is composed of two or more layers of the aforementioned thermosetting resin film, for light with a wavelength of 1342 nm is more than 50%; the aforementioned thermosetting resin film contains a polymer component (A), has a ring Two or more thermosetting components other than oxygen-based acrylic resin, and filler material (D); the aforementioned thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2); the aforementioned thermosetting resin The ratio of the total content of all types of the thermosetting components in the film (in other words, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) to the total mass of the thermosetting resin film is 40 Mass% or more; the content of the polymer component (A) in the thermosetting resin film is 5 to 30 mass% relative to the total mass of the thermosetting resin film; in the thermosetting resin film The content of the filler (D) is 5% to 20% by mass relative to the total mass of the thermosetting resin film; for the thermosetting component contained in the thermosetting resin film, type, the X value calculated from the following formula is calculated, and when the total value of the aforementioned eq below. X = [equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)]/[of the thermosetting resin film Total content (parts by mass) of all types of thermosetting ingredients].

As another example of the preferred thermosetting resin film of this embodiment, the following thermosetting resin film can be cited, which is used to form the first protective film in the following manner. That is, the aforementioned thermosetting resin film is The resin film is attached to the surface of the workpiece with the protruding electrode and is thermally hardened, thereby forming a first protective film on the aforementioned surface; a layer of the aforementioned thermosetting resin film with a thickness of 200 μm may be less than 200 μm thick. The transmittance of the laminated film with a total thickness of 200 μm, which is composed of two or more layers of the aforementioned thermosetting resin film, for light with a wavelength of 1342 nm is more than 50%; the aforementioned thermosetting resin film contains a polymer component (A), has a ring Two or more thermosetting components other than oxygen-based acrylic resin, and filler material (D); the aforementioned thermosetting component is composed of an epoxy resin (B1) and a thermosetting agent (B2); the aforementioned thermosetting resin The ratio of the total content of all types of the thermosetting components in the film (in other words, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) to the total mass of the thermosetting resin film is 40 Mass% or more; the content of the polymer component (A) in the thermosetting resin film is 5 to 30 mass% relative to the total mass of the thermosetting resin film; in the thermosetting resin film The content of the filler (D) is 5% to 20% by mass relative to the total mass of the thermosetting resin film; for the thermosetting component contained in the thermosetting resin film, type, the X value calculated from the following formula is calculated, and when the total value of the aforementioned eq or less; by heating the aforementioned thermosetting resin film at 130°C for 2 hours to thermoset, a first protective film with a size of 20 mm × 130 mm and a thickness of 40 μm was obtained. Using the obtained first protective film, the jig was The distance is set to 80 mm, the stretching speed is set to 200 mm/min, and the first protective film is stretched by the clamp in a direction parallel to the surface of the first protective film. The breaking strength is 55MPa or less. X = [equivalent of functional groups related to the thermosetting reaction of the thermosetting component (g/eq)] × [content of the thermosetting component of the thermosetting resin film (parts by mass)]/[of the thermosetting resin film Total content (parts by mass) of all types of thermosetting ingredients].

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

◇Method for manufacturing the first protective film forming sheet The said 1st protective film formation sheet can be manufactured by laminating|stacking each said layer sequentially so that it may become a corresponding positional relationship. The formation method of each layer is as described above. For example, when the first adhesive layer or the first intermediate layer is laminated on the first base material when manufacturing the first support sheet, the above-mentioned first adhesive composition or first intermediate layer is coated on the first base material. The layer-forming composition can be laminated by drying or irradiating energy rays as necessary, thereby laminating the first adhesive layer or the first intermediate layer.

On the other hand, for example, when a thermosetting resin layer (thermosetting resin film) is laminated on the first adhesive layer that has been laminated on the first base material, the first adhesive layer may be coated with heat The composition for forming a curable resin layer directly forms a thermosetting resin layer. Similarly, when the first adhesive layer is further laminated on the first intermediate layer that has been laminated on the first base material, the first adhesive composition can be applied on the first intermediate layer to directly form the first adhesive layer. agent layer. In this way, when any one composition is used to form a continuous two-layer laminated structure, another composition can be applied on the layer formed of the aforementioned composition to form a new layer. However, it is preferable that the layer to be laminated later among these two layers is formed in advance on another release film using the composition described above, so that the exposed surface of the formed layer is opposite to the side in contact with the release film. The exposed surfaces of the remaining layers that have been formed are bonded together to form a continuous two-layer laminate structure. At this time, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film can be removed if necessary.

For example, a first protective film forming sheet (the first support sheet is the first base material) is manufactured by laminating a first adhesive layer on a first base material and laminating a thermosetting resin layer on the first adhesive layer. When the first protective film forming sheet is a laminate of a material and a first adhesive layer), apply the first adhesive composition on the first base material and dry it if necessary, thereby coating the first base material The first adhesive layer is preliminarily laminated on the release film, and a thermosetting resin layer-forming composition is separately applied to the release film and dried if necessary, thereby forming a thermosetting resin layer on the release film in advance to make the thermosetting resin layer The exposed surface of the resin layer is bonded to the exposed surface of the first adhesive layer laminated on the first base material, and the thermosetting resin layer is laminated on the first adhesive layer to obtain the first protective film. piece. In addition, for example, when manufacturing a first support sheet in which a first intermediate layer is laminated on a first base material and a first adhesive layer is laminated on the first intermediate layer, the first support sheet is coated on the first base material. The composition for forming the intermediate layer is preliminarily laminated on the first base material by drying or irradiating energy rays as necessary, and the first adhesive composition is separately applied to the release film and dried as necessary. , whereby a first adhesive layer is formed in advance on the release film, and the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer laminated on the first base material, and the first adhesive layer is The first intermediate layer is laminated to obtain a first support sheet. In this case, for example, a thermosetting resin layer-forming composition is further separately applied to the release film and dried if necessary, thereby forming a curable resin layer on the release film in advance so that the exposed surface of the curable resin layer The exposed surface of the first adhesive layer laminated on the first intermediate layer is bonded together, and a thermosetting resin layer is laminated on the first adhesive layer, thereby obtaining a first protective film forming sheet.

In addition, when the first adhesive layer or the first intermediate layer is laminated on the first base material, as mentioned above, the first adhesive composition or the first intermediate layer forming agent may be applied instead of the first base material. The method of forming a composition is to apply the first adhesive composition or the first intermediate layer forming composition on the release film, dry it or irradiate it with energy rays if necessary, thereby preforming the first adhesive on the release film. layer or the first intermediate layer, and the exposed surfaces of these layers are bonded to a surface of the first base material, thereby laminating the first adhesive layer or the first intermediate layer on the first base material. In either method, the release film can be removed at any time point after the target multilayer structure is formed.

In this way, since the layers other than the first base material constituting the first protective film forming sheet can be laminated by a method of being formed in advance on the release film and then bonded to the surface of the target layer, this method can be appropriately selected as needed. In the next step, the first protective film forming sheet may be produced.

In addition, the first protective film forming sheet is usually stored in a state where a release film is bonded to the surface of the outermost layer (for example, the thermosetting resin layer) of the sheet that is opposite to the first support sheet. Therefore, the first protective film-forming sheet can also be obtained by applying a thermosetting resin layer-forming composition or the like on the release film (preferably the release-treated surface of the release film) to form the first protective film-forming sheet. The composition constituting the layer constituting the outermost layer is dried if necessary, thereby forming the layer constituting the outermost layer on the release film in advance, and using the above-described method on the exposed surface of the layer opposite to the side in contact with the release film. Either method can be used to stack the remaining layers without removing the release film and maintaining the bonded state.

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

◇Method for manufacturing workpiece with first protective film When using the thermosetting resin film or the first protective film forming sheet according to one embodiment of the present invention, a method for manufacturing a workpiece with a first protective film has the following steps: having a protruding electrode in the workpiece The step of attaching the thermosetting resin film to the surface (that is, the protruding electrode formation surface) (in this specification, sometimes referred to as the "attachment step"); thermally curing the attached thermosetting resin film The step of forming the first protective film (sometimes referred to as the "first protective film forming step" in this specification); for the aforementioned workpiece, from the side of the aforementioned workpiece having the aforementioned first protective film, through the aforementioned first protective film The step of irradiating laser light to form a modified layer inside the workpiece (sometimes referred to as the "modified layer forming step" in this specification); and positioning the edge of the workpiece after the modified layer is formed relative to the The circuit surface of the workpiece is expanded in a parallel direction together with the first protective film, thereby dividing the workpiece at the location of the modified layer to obtain a workpiece processed product (in this specification, it may be simply referred to as the "dividing step" ). Hereinafter, the aforementioned manufacturing method will be described in detail with reference to the drawings.

5A to 5C and 6A to 6C are enlarged cross-sectional views for schematically explaining the manufacturing method of the aforementioned workpiece. Here, the manufacturing method in the case of using the 1st protective film formation sheet 1 shown in FIG. 2 is demonstrated.

[Attach steps] In the aforementioned attaching step, as shown in FIG. 5A , the thermosetting resin film 12 is attached to the protruding electrode forming surface of the workpiece 90 (that is, the surface 91 a of the protruding electrode 91 and the circuit surface 90 a of the workpiece 90 ). By performing this step, the thermosetting resin film 12 spreads between the plurality of existing protruding electrodes 91, is in close contact with the protruding electrode formation surface, and covers the surface 91a of the protruding electrode 91, especially the circuit surface of the workpiece 90. The protruding electrode 91 is embedded in the surface 91a of the vicinity of the surface 90a, so that these areas can be covered. Furthermore, when the proportion of the content of the thermosetting component in the thermosetting resin film 12 is adjusted, by performing this step, the upper part of the protruding electrode 91 including the top portion 910 will penetrate the thermosetting resin film 12 , protruding from the thermosetting resin film 12 .

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

In the attaching step, when using the first protective film forming sheet 1 as shown here, the thermosetting resin film 12 in the first protective film forming sheet 1 is attached to the protruding electrode of the workpiece 90 It is sufficient to attach the first protective film forming sheet 1 itself to the protruding electrode forming surface of the workpiece 90 by forming the surface.

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

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

In the attaching step, it is preferable to attach the thermosetting resin film 12 to the protruding electrode formation surface while heating. Thereby, between the thermosetting resin film 12 and the protruding electrode formation surface, that is, between the thermosetting resin film 12 and the circuit surface 90 a of the workpiece 90 , and between the thermosetting resin film 12 and the protruding electrode 91 Anywhere between the surfaces 91a can further suppress the occurrence of voids. In addition, it is possible to further suppress the thermosetting resin film 12 from remaining on the upper portion of the protruding electrode 91 including the top portion 910 , and ultimately it is possible to further suppress the first protective film from remaining on the upper portion.

The heating temperature of the thermosetting resin film 12 during attachment only needs to be not excessively high, and is preferably 60°C to 100°C, for example. Here, "excessive high temperature" means a temperature at which, for example, the thermosetting resin film 12 undergoes thermal curing and the thermosetting resin film 12 exhibits unintended effects.

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

After the first laminated structure 201 is formed through the attachment step, the first laminated structure 201 can also be directly used in subsequent steps. If necessary, the workpiece 90 can also be adjusted by grinding the inner surface 90b of the workpiece 90 . thickness of. The first laminated structure 201 after grinding the inner surface 90b of the workpiece 90 is in the state shown in FIG. 5A except that the thickness of the workpiece 90 is different.

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

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

After the first laminated structure 201 is formed through the attachment step, the first supporting sheet 101 is removed from the thermosetting resin film 12 in the first laminated structure 201 . When the inner surface 90b of the workpiece 90 is ground, it is preferable to remove the first support piece 101 after the grinding. By performing such steps, as shown in FIG. 5B , a second laminated structure is obtained in which the protruding electrode formation surface of the workpiece 90 is provided with the thermosetting resin film 12 and does not include the first supporting sheet 101 (in other words, Workpiece with thermosetting resin film attached) 202. In the second laminated structure 202 , the upper portion of the protruding electrode 91 including the top portion 910 penetrates the thermosetting resin film 12 and protrudes, thereby being exposed.

When the first adhesive layer 13 has energy ray curability, it is preferable to harden the first adhesive layer 13 by irradiating energy rays so that the adhesiveness of the first adhesive layer 13 is reduced. The first support sheet 101 is removed from the resin film 12 .

[First protective film formation step] In the aforementioned first protective film forming step, the attached thermosetting resin film 12 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 may be performed after removing the first supporting sheet 101 . In addition, when the inner surface 90b of the workpiece 90 is ground, the first protective film forming step may be performed after the inner surface 90b is ground. By performing this step, a third laminated structure (in other words, a workpiece with a first protective film) 203 in which the first protective film 12' is provided on the protruding electrode formation surface of the workpiece 90 is obtained. In FIG. 5C , symbol 12 a ′ represents the surface of the first protective film 12 ′ that contacts the workpiece 90 (sometimes referred to as the “first surface” in this specification).

The curing conditions of the thermosetting resin film 12 are not particularly limited as long as the first protective film 12' has a degree of curing that can fully exert the function of the first protective film 12'. There are 12 types, just choose appropriately. For example, the heating temperature and heating time during thermal curing of the thermosetting resin film 12 are as described above. When the thermosetting resin film 12 is thermally cured, the curable resin film 12 may also be pressurized. In this case, the pressurizing pressure is preferably 0.3 MPa to 1 MPa.

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

[Modification layer formation step] In the aforementioned modified layer forming step, as shown in FIG. 6A , the workpiece 90 is irradiated with the laser light R from the side of the workpiece 90 having the first protective film 12 ′ through the first protective film 12 ′, whereby the workpiece 90 is A modified layer 900 is formed inside. After the modified layer forming step, the workpiece 90 described below is divided (i.e., cut). Therefore, the modified layer forming step is preferably performed on the workpiece in the third laminated structure (the workpiece with the first protective film) 203 The cutting sheet or the second protective film forming sheet is attached to the inner surface 90b of 90.

In addition, in this specification, the structure in which the first protective film is provided on the protruding electrode formation surface of the workpiece, and the cutting sheet or the second protective film forming sheet is provided on the inner surface of the workpiece is sometimes referred to as "the fourth "Laminated structure". Furthermore, a structure having a structure in which a modified layer is formed inside the workpiece in the fourth laminated structure may be called a "fifth laminated structure". In FIG. 6A , as the fifth laminated structure 205 , the first protective film 12 ′ is provided on the protruding electrode formation surface of the workpiece 90 , and the second protective film forming sheet 8 is provided on the inner surface 90 b of the workpiece 90 . A modified layer 900 is formed inside the structure 90 .

The second protective film forming sheet 8 shown here includes a second base material 81, a second adhesive layer 83 provided on the second base material 81, and a resin layer provided on the second adhesive layer 83. (resin film) 82. The second supporting sheet 801 of the lamination system of the second base material 81 and the second adhesive layer 83. Therefore, it can be said that the second protective film forming sheet 8 includes the second support sheet 801 and the resin layer (resin film) 82 provided on one side 801a of the second support sheet 801, in other words, one side 83a of the second adhesive layer 83. .

The resin layer (resin film) 82 is used to form a second protective film on the inner surface 90b of the workpiece 90. The second protective film covers and protects the inner surface 90b of the workpiece 90. More specifically, the second protective film prevents cracks from occurring in the workpiece when the workpiece is divided or before the workpiece obtained by dividing the workpiece is packaged to manufacture the target substrate device.

The resin layer 82 may have only one of thermosetting properties and energy ray curing properties, may have both properties, or may not have both properties. When the resin layer 82 is curable (that is, has at least one of thermosetting properties and energy ray curing properties), the cured product of the resin layer 82 is the second protective film. When the resin layer 82 is non-hardening (that is, does not have both the characteristics of thermosetting property and energy ray hardening property), it is considered that the third layer is provided at the stage when the resin layer 82 is attached to the inner surface 90b of the workpiece 90 . 2 protective film.

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

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

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

In the modified layer forming step, a focus is set on a specific region of the divided portion of the workpiece 90 inside the workpiece 90, and the laser light R is irradiated to focus on the focus. By irradiating the laser light R, a modified layer 900 is formed in the irradiated area.

The thermosetting resin film 12 and the first protective film 12' have transmittance to light with a wavelength of 1342 nm. Preferably, the transmittance of the thermosetting resin film 12 and the first protective film 12' to the light with a wavelength of 1342 nm is as described above. When the laser light is as high as described, the laser light with a wavelength of 1342 nm can pass through the first protective film 12' well. Therefore, even if the workpiece 90 is irradiated with the laser light R through the first protective film 12 ′ from the side of the workpiece 90 having the first protective film 12 ′, the modified layer 900 can be favorably formed inside the workpiece 90 .

[Segmentation steps] In the aforementioned dividing step, the workpiece 90 after the modified layer 900 is formed is separated together with the first protective film 12 ′ (in other words, the fifth laminated structure 205 ) in a direction parallel to the circuit surface 90 a of the workpiece 90 ( FIG. 6A , in the direction of arrow E), the workpiece 90 is divided into parts of the modified layer 900, and the workpiece 90 is obtained. By performing this step, for example, as shown in FIG. 6B , a plurality (a large number) of workpieces 9 having the uncut first protective film 12' on the protruding electrode formation surface are obtained and arranged on the second support sheet 801. The fifth intermediate laminated structure 205' in the state.

Alternatively, in the aforementioned dividing step, there may be a case where the workpiece 90 can be divided at the portion of the modified layer 900 and the first protective film 12' can be cut by expanding as described above. In this case, as shown in FIG. 6C instead of FIG. 6B , the workpiece 9 and the protruding electrode forming surface (that is, the surface 91 a of the protruding electrode 91 and the workpiece 9 ) formed on the workpiece 9 are immediately obtained. The workpiece 990 with the first protective film (the first protective film 120' after cutting) on the circuit surface 9a) of 9 (in this case, this step is sometimes called "dividing and cutting" Steps"). That is, the aforementioned manufacturing method may also divide the aforementioned workpiece at the portion of the aforementioned modified layer and cut the aforementioned first protective film in the aforementioned dividing step (in other words, the step of obtaining the workpiece processed product). In this case, by performing this step, the workpiece 9 having the cut first protective film 120' on the protruding electrode formation surface (that is, the workpiece 990 with the first protective film) is obtained. A plurality (a large number) of the sixth laminated structure 206 are arranged on the support sheet 801 . In FIG. 6C , the symbol 120 a ′ represents the contact surface (sometimes referred to as “the first surface” in this specification) with the workpiece 9 in the first protective film 120 ′ after cutting, and the symbol 9 b represents the workpiece 9 the inner surface.

In the aforementioned dividing and cutting steps, the first protective film 12' is cut along the divided portions of the workpiece 90, and finally is cut along the outer periphery of the workpiece 90.

In this step, whether the first protective film 12' is also cut when the workpiece 90 is divided is determined by the composition or expansion conditions of the first protective film 12', in other words, the thermosetting resin film 12.

For example, when the first protective film 12' is formed of the thermosetting resin film 12 that satisfies the condition of the total value of the aforementioned X value, the first protective film 12' can be easily cut in the dividing step ( Segmentation and cutting steps). As a result, the workpiece 9 having the cut first protective film 120' on the protruding electrode formation surface can be manufactured with high efficiency. In this step, the first protective film 12' is cut along the outer periphery of the workpiece 9.

On the other hand, when the first protective film 12' is formed of the thermosetting resin film 12 that does not satisfy the above-mentioned condition of the total value of X, it is difficult to cut the first protective film 12' in the dividing step. In this case, after the workpiece 90 is divided (that is, after the aforementioned dividing step), the first protective film 12' is cut (in this specification, this step is sometimes referred to as a "cutting step"). Thereby, the same workpiece 990 with the first protective film as described above is obtained. The aforementioned cutting step may be performed simultaneously with the step of picking up the workpiece 9 (more specifically, the workpiece having the uncut first protective film) by pulling it away from the second support piece 801 . In this way, when the cutting step of the first protective film 12' is separately performed after the workpiece 9 is divided, the workpiece 9 does not necessarily have the second protective film in its original state as shown in FIG. 6C during the aforementioned cutting step. Sheet 8 is formed.

In the dividing step (or dividing and cutting step), the aforementioned expansion is preferably carried out under a temperature condition of -15°C to 5°C. When the temperature during expansion is below the upper limit, cutting of the first protective film 12' becomes easier. By keeping the temperature during expansion above the aforementioned lower limit, excessive cooling 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 aforementioned dividing step (or dividing and cutting step) is shown, but the resin layer 82 may also be cut. After the dividing step (or dividing and cutting step), it is performed separately by a known method. In FIGS. 6B to 6C , the resin layer 82 after cutting is marked with a symbol 820 . In addition, although the resin layer 82 is shown to be cut here, it is also possible to cut the second protective film obtained by hardening the resin layer 82 without cutting it at the stage of the resin layer 82 .

In the aforementioned manufacturing method, the resin layer 82 or the second protective film is cut along the divided portions of the workpiece 90 in the same manner as the first protective film 12'. In addition, in this specification, even after the aforementioned resin layer is cut, as long as the laminated structure of the second support sheet and the aforementioned resin layer (in other words, the second support sheet and the aforementioned resin layer after cutting) is maintained, this term will also be used. The laminated structure is called "the second protective film forming sheet".

In the above-mentioned attaching step, when the upper part of the protruding electrode 91 including the top portion 910 does not penetrate the thermosetting resin film 12 and does not protrude from the thermosetting resin film 12, any step after the aforementioned attaching step will be performed. In another stage, the thermosetting resin film remaining on the upper part of the protruding electrode or the first protective film that is a cured product of the thermosetting resin film is removed to expose the thermosetting property of the upper part of the protruding electrode. Resin film removal step or first protective film removal step. The thermosetting resin film removal step is performed after the attaching step and before the first protective film forming step. The first protective film removing step is performed after the first protective film forming step. Thereby, the sixth laminated structure 206 shown in FIG. 6C is finally obtained. For example, the remaining thermosetting resin film or first protective film can be removed by irradiating the thermosetting resin film or first protective film with plasma.

◇Manufacturing method of substrate device After the workpiece processed with the first protective film (in other words, the sixth laminated structure) is obtained by the above-mentioned manufacturing method, the workpiece processed with the first protective film is flip-chip connected to the substrate by a known method. After the circuit surface is formed, a package is formed, and by using this package, a target substrate device (not shown) can be manufactured. When a semiconductor wafer with a first protective film is used, a target semiconductor device can be manufactured by using the semiconductor package after fabricating the semiconductor package. In addition, when a semiconductor wafer provided with a first protective film and a second protective film is used, these semiconductor wafers with protective films can be flip-chip connected to manufacture a target semiconductor device. [Example]

Hereinafter, the present invention will be described in more detail through specific examples. However, the present invention is not limited to the Examples shown below at all. In addition, for the sake of convenience, each object produced in the comparative example shown below is given the same name as each object produced in the example.

The components used for producing the composition for forming a thermosetting resin layer are shown below. [Polymer component (A)] (A)-1: Polyvinyl butyral ("S-LEC SV-10" manufactured by Sekisui Chemical Industry Co., Ltd., weight average molecular weight 65000, glass transition temperature 66°C) (A)-2: Polyvinyl butyral ("S-LEC BL-10" manufactured by Sekisui Chemical Industry Co., Ltd., weight average molecular weight 25000, glass transition temperature 59°C) (A)-3: 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) Copolymerized acrylic resin (weight average molecular weight 800,000, glass transition temperature -28°C). [Thermosetting ingredient (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A type epoxy resin ("EXA-4810-1000" manufactured by DIC Corporation, epoxy equivalent 404g/eq to 412g/eq) (B1)-2: Dicyclopentadiene-type epoxy resin ("EPICLON HP-7200" manufactured by DIC Corporation, epoxy equivalent 265g/eq) (B1)-3: Liquid modified epoxy resin ("YX7110" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 962g/eq) (B1)-4: A mixture of liquid bisphenol A-type epoxy resin and acrylic rubber particles ("BPA328" manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235g/eq) (B1)-5: Solid bisphenol A type epoxy resin ("Epikote 1055" manufactured by Mitsubishi Chemical Corporation, molecular weight 1600, softening point 93°C, epoxy equivalent 800g/eq to 900g/eq) (B1)-6: Dicyclopentadiene-type epoxy resin ("XD-1000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 248g/eq) ・Thermal hardener (B2) (B2)-1: Novolak type phenol resin ("Shonol BRG-556" manufactured by Showa Denko Co., Ltd., hydroxyl equivalent weight: 104 g/eq) (B2)-2: Dicyandiamide ("Adeka Hardener EH-3636AS" manufactured by ADEKA, solid dispersion latent hardener, active hydrogen content 21g/eq) [Harding accelerator (C)] (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("YA050C-MKK" manufactured by Admatechs, average particle size 0.05 μm) (D)-2: Silica filler ("SC2050MA" manufactured by Admatechs, a silica filler surface-modified with an epoxy compound, average particle size 500nm) (D)-3: Silica filler ("SV-10" manufactured by TATSUMORI Co., Ltd., average particle size 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) [Color(I)] (I)-1: Carbon black ("MA-600B" manufactured by Mitsubishi Chemical Corporation)

[Example 1] [Production of thermosetting resin film and first protective film forming sheet] [Production of composition for forming 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 (B2)- 1 (18.1 parts by mass), hardening accelerator (C)-1 (0.2 parts by mass) and filler (D)-1 (9.0 parts by mass) were mixed, diluted with methyl ethyl ketone, and carried out at 23°C By stirring, a thermosetting resin layer-forming composition (III-1) in which the total concentration of the above-mentioned six components other than methyl ethyl ketone was 55% by mass was prepared. These ingredients and their contents are shown in Table 1. In addition, when "-" is written in the column of contained components in Table 1, it means that the composition for forming a thermosetting resin layer does not contain this component. In addition, "the ratio of the content of the thermosetting component (mass %)" in Table 1 means "the ratio of the content of the thermosetting component in the thermosetting resin film to the total mass of the thermosetting resin film."

[Manufacture of thermosetting resin film] A release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) made of polyethylene terephthalate and subjected to release treatment by polysiloxane treatment on one side. The thermosetting resin layer-forming composition (III-1) obtained above was applied to the peeling-treated surface and dried at 100° C. for 2 minutes to prepare a thermosetting resin film with a thickness of 30 μm.

[Manufacturing of the first protective film forming sheet] Next, a surface protective tape for back grinding ("Adwill E-8180HR manufactured by Lintec Corporation") was bonded to the exposed surface of the obtained thermosetting resin film (in other words, the surface opposite to the side provided with the release film). ”) to prepare the first protective film forming sheet. The aforementioned surface protection tape corresponds to the first support piece.

[Manufacture of semiconductor wafer with first protective film] The peeling 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 thus produced (in other words, the side provided with the surface protective tape) is The opposite side) is pressed against the bump formation surface of the semiconductor wafer, whereby the first protective film forming sheet is attached to the bump formation surface of the semiconductor wafer. At this time, the first protective film forming sheet was attached using an attachment device (drum type laminating machine, "RAD-3510 F/12" manufactured by Lintec Co., Ltd.) at a workbench temperature of 90°C. The thermosetting resin film is heated at a speed of 2mm/sec and a bonding pressure of 0.5MPa. As a semiconductor wafer, a semiconductor 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 750 μm in parts other than the bumps was used. Through the above steps, a first laminated structure in which the first protective film forming sheet is attached to the bump formation surface of the semiconductor wafer is obtained.

Next, the surface (inner surface) of the semiconductor wafer in the obtained first laminated structure that is opposite to the bump formation surface was ground using a grinding machine ("DGP8760" manufactured by DISCO). At this time, the back surface of the semiconductor wafer was ground to a thickness of 250 μm except for the bumps.

Next, the surface protection tape (in other words, the first supporting sheet) is removed from the thermosetting resin film in the first laminated structure. Through the above steps, a second laminated structure (semiconductor wafer with thermosetting resin film) in which the bump formation surface of the semiconductor wafer is provided with a thermosetting resin film is obtained.

Next, using a thermosetting apparatus ("RAD-9100 m/12" manufactured by Lintec Corporation), the thermosetting resin film in the second laminated structure obtained above was cured at a processing temperature of 130° C. and a processing pressure of 0.5 MPa. , perform heat and pressure treatment under the conditions of a treatment time of 2 hours, thereby thermally hardening it to form a first protective film. Through the above steps, a third laminated structure (in other words, a semiconductor wafer with a first protective film) in which the bump formation surface of the semiconductor wafer is provided with a first protective film is obtained.

Next, a dicing tape ("Adwill D-841" manufactured by Lintec Corporation) was attached to the aforementioned inner surface (in other words, the grinding surface) of the semiconductor wafer in the obtained third multilayer structure, thereby obtaining a semiconductor wafer. The bump formation surface of the wafer is provided with a first protective film, and the fourth laminated structure is composed of a dicing tape on the inner surface. The aforementioned cutting tape corresponds to the second support piece.

Next, using a cutting device ("DFL7361" manufactured by DISCO Corporation), the semiconductor wafer in the fourth multilayer structure is focused toward a focal point set inside the semiconductor wafer, from which the semiconductor wafer has The side of the first protective film is irradiated with laser light through the first protective film, thereby forming a modified layer inside the semiconductor wafer. At this time, the wavelength of the laser light is set to 1342nm, the output is set to 0.7W, and the frequency is set to 90kHz. Through the above steps, a fifth laminated structure in which a modified layer is formed inside the semiconductor wafer in the fourth laminated structure is obtained.

Then, in an environment of 0° C., the semiconductor wafer after the modified layer was formed (in other words, the fifth laminated structure) was placed in contact with the first protective film in a direction parallel to the circuit surface of the semiconductor wafer. By expanding together, the semiconductor wafer is divided at the modified layer portion, and the first protective film is cut along the divided portion of the semiconductor wafer. At this time, using a Die Separator ("DDS2300" manufactured by DISCO Corporation), the second support piece in the fifth laminated structure is placed on the table in the die Separator, and the second support piece is placed on the table of the die Separator. 5. The peripheral portion of the laminated structure is fixed, and in this state, the worktable is lifted up at a lifting speed of 50 mm/sec and a lifting amount of 20 mm, thereby spreading the semiconductor wafer and the first protective film. The size of the obtained semiconductor wafer is 2mm×2mm. Through the above steps, a semiconductor wafer having a cut first protective film on the bump formation surface (that is, a semiconductor wafer with a first protective film) is obtained on the second support sheet (in other words, the aforementioned dicing tape). The sixth laminated structure in a (large) array state.

[Evaluation of thermosetting resin film] [Confirmation of the residual inhibitory properties of the thermosetting resin film on the upper part of the bump] During the production of the above-mentioned semiconductor wafer with the first protective film, a scanning electron microscope ("VE-9800" manufactured by KEYENCE Corporation) was used from the bump formation surface side of the semiconductor wafer, and the acceleration voltage was set to 5keV. Observe the first laminated structure. Furthermore, based on the following evaluation criteria, the residual suppressive property of the thermosetting resin film on the upper portion of the bump in the first laminated structure was evaluated. 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 no thermosetting resin film remains on the upper part of the bump. B: The boundary between the bump and the thermosetting resin film was not confirmed, and it was confirmed that the thermosetting resin film remained on the upper part of the bump.

[Measurement of light transmittance of thermosetting resin film] Except for changing the coating amount of the thermosetting resin layer-forming composition (III-1), the same method as in the production of the above-mentioned thermosetting resin film was used to produce 5 pieces of thermosetting test pieces. Resin film (thickness 40μm). Next, these five thermosetting resin films for testing were laminated in the thickness direction of these films to obtain a laminated film (thickness: 200 μm). Next, a spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by SHIMADZU Corporation) was used to measure the transmittance of light with a wavelength of 1342 nm for this laminated film. The results are shown in Table 1.

[Evaluation of the first protective film] [Evaluation of divisibility of semiconductor wafers] The sixth laminated structure obtained above was observed from the first protective film side of the sixth laminated structure using a digital microscope ("VH-Z100" manufactured by KEYENCE Corporation). At this time, as the observation area, the first area in the second support sheet corresponding to the central portion of the arrangement surface of the semiconductor wafers with the first protective film and the peripheral portion side that is point symmetrical with respect to the first area are selected. The location and distance from the first area are equal to the 2nd area, 3rd area, 4th area and 5th area, a total of 5 areas. These five regions are all regions including 25 semiconductor wafers with a first protective film in 5 columns and 5 rows, assuming that the semiconductor wafer is normally divided. In addition, the first region exists approximately at the center of the first line segment connecting the second region and the third region, and the first region exists approximately at the center of the second line segment connecting the fourth region and the fifth region. Select these 5 areas so that there are 2nd area, 4th area, 3rd area and 5th area in order in the clockwise direction. The first line segment and the second line segment are orthogonal to each other. Furthermore, these five regions were observed, and the divisibility of the semiconductor wafer was evaluated based on the following evaluation criteria. The results are shown in Table 1. [Evaluation criteria] A: The semiconductor wafer is normally divided in all 5 areas (all areas from the 1st area to the 5th area). B: In at least one region (at least any one of the first region to the fifth region), there is a portion where the semiconductor wafer is not normally divided.

[Evaluation of the cutability of the first protective film when dividing semiconductor wafers] During the above-mentioned evaluation of the separability of the semiconductor wafer, the cutting property of the first protective film was also evaluated based on the following evaluation criteria. The results are shown in Table 1. [Evaluation criteria] A: In all 5 areas (all areas from the 1st area to the 5th area), the first protective film is cut off normally. B: In at least one area (at least any one of the first to fifth areas), there is a portion where the first protective film is not cut normally.

[Measurement of breaking strength of the first protective film] Except for changing the coating amount of the thermosetting resin layer-forming composition (III-1), a thermosetting resin film for testing was produced using the same method as the above-mentioned production of the thermosetting resin film. (Thickness 40μm). Next, the thermosetting resin film for this test was heated at 130° C. for 2 hours, thereby thermally curing it. Next, a slice of 20 mm×130 mm was cut out from the hardened material (that is, the first protective film), and the slice was used as a test piece. A universal tensile testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation) was used, the distance between the clamps was set to 80 mm, the tensile speed was set to 200 mm/min, and the test piece was placed along the surface of the test piece. The test piece is stretched in a parallel direction by a clamp, and the maximum stress of the test piece at this time is measured, and the maximum stress is used as the breaking strength of the first protective film. The results are shown in Table 1.

[Example 2] [Production of thermosetting resin film and first protective film forming sheet] [Production of composition for forming 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), thermosetting agent (B2)- 1 (16.0 parts by mass), hardening accelerator (C)-1 (0.2 parts by mass) and filler (D)-1 (11.0 parts by mass) were mixed, diluted with methyl ethyl ketone, and carried out at 23°C The mixture was stirred to prepare a resin layer-forming composition in which the total concentration of the above-mentioned six components other than methyl ethyl ketone was 55% by mass. These ingredients and their contents are shown in Table 1.

[Production of thermosetting resin film and first protective film forming sheet] Using the resin layer-forming composition obtained above as the resin layer-forming composition, a thermosetting resin film and a first protective film-forming sheet were produced in the same manner as in Example 1 except for this point.

[Manufacture of semiconductor wafer with first protective film] The first protective film-forming sheet obtained above was used as the first protective film-forming sheet. Except for this point, an attempt was made to manufacture a semiconductor wafer with a first protective film (in other words, using the same method as in Example 1). 6th layered structure).

[Evaluation of thermosetting resin film and first protective film] The thermosetting resin film and the first protective film produced in this example were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative example 1] [Production of thermosetting resin film and first protective film forming sheet] [Production of composition for forming 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 hardener (B2)-2 (0.5 parts by mass), hardening accelerator (C)-1 (0.5 parts by mass), filling material (D)-2 (6.0 parts by mass), filling material (D)-3 (54.0 parts by mass), coupling agent (E)-1 (0.4 parts by mass) and coloring agent (I)-1 (1.9 parts by mass) were mixed, diluted with methyl ethyl ketone, and By stirring at 23° C., a resin layer-forming composition in which the total concentration of the 10 components other than the above-mentioned methyl ethyl ketone was 55% by mass was prepared. These ingredients and their contents are shown in Table 1.

[Production of thermosetting resin film and first protective film forming sheet] Using the resin layer-forming composition obtained above as the resin layer-forming composition, a thermosetting resin film and a first protective film-forming sheet were produced in the same manner as in Example 1 except for this point.

[Manufacture of semiconductor wafer with first protective film] The first protective film-forming sheet obtained above was used as the first protective film-forming sheet. Except for this point, an attempt was made to manufacture a semiconductor wafer with a first protective film (in other words, using the same method as in Example 1). 6th layered structure).

[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 in the same manner as in Example 1. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Comparative example 1 Components of the composition for forming the thermosetting resin layer (content (parts by mass)) Polymer component (A) (A)-1 9.9 - - (A)-2 - 10.0 - (A)-3 - - 21.0 Epoxy resin (B1) (B1)-1 37.8 - - (B1)-2 25.0 30.0 - (B1)-3 - 33.0 - (B1)-4 - - 10.0 (B1)-5 - - 2.0 (B1)-6 - - 5.6 Thermal hardener (B2) (B2)-1 18.1 16.0 - (B2)-2 - - 0.5 Hardening accelerator (C) (C)-1 0.2 0.2 0.5 Filling material(D) (D)-1 9.0 11.0 - (D)-2 - - 6.0 (D)-3 - - 54.0 Coupling agent(E) (E)-1 - - 0.4 Colorant(I) (I)-1 - - 1.9 Content ratio of thermosetting components (mass %) 80.9 78.8 17.8 Total value of X values (g/eq) 296 524 301 Evaluation results of thermosetting resin films Residual suppression of the thermosetting resin film on the upper part of the bump A A B Transmittance (%) of thermosetting resin film to light (wavelength 1342nm) 90 65 5 Evaluation results of the first protective film Semiconductor wafer divisibility A A B Cutability of the first protective film when dividing semiconductor wafers A B - Breaking strength of the first protective film (MPa) 45 60 25

From the above results, it is apparent that in Example 1, the semiconductor wafer has good separability. The thermosetting resin film of Example 1 has a high transmittance for light with a wavelength of 1342 nm. As a result, the light transmittance of the first protective film formed from the film is also high. When the semiconductor wafer is irradiated through the first protective film When irradiating laser light, the modified layer can be well formed inside the semiconductor wafer.

In addition, when the thermosetting resin film of Example 1 is attached to the bump formation surface of the semiconductor wafer, it can suppress residues on the upper portion of the bumps and has better characteristics. The ratio of the content of the thermosetting component in the thermosetting resin film of Example 1 to the total mass of the thermosetting resin film was 80.9% by mass.

In addition, in Example 1, the cutability of the first protective film during division of the semiconductor wafer was also good. In Example 1, the total value of 37.8＋25.0＋18.1)})g/eq, the breaking strength of the first protective film is 45MPa.

In Example 2, the divisibility of the semiconductor wafer was also good. The thermosetting resin film of Example 2 has a high transmittance for light with a wavelength of 1342 nm. As a result, the light transmittance of the first protective film formed from the film is also high. When the semiconductor wafer is irradiated through the first protective film When irradiating laser light, the modified layer can be well formed inside the semiconductor wafer.

In addition, when the thermosetting resin film of Example 2 is attached to the bump formation surface of the semiconductor wafer, it can also suppress residues on the upper portion of the bump, and has better characteristics. The ratio of the content of the thermosetting component in the thermosetting resin film of Example 2 to the total mass of the thermosetting resin film was 78.8% by mass.

Furthermore, in Example 2, the first protective film has poor cutability when dividing the semiconductor wafer. However, the first protective film can be cut in subsequent steps, and a semiconductor wafer with a first protective film can be manufactured. In Example 2, the total value of 30.0＋33.0＋16.0)})g/eq, the breaking strength of the first protective film is 60MPa.

On the other hand, in Comparative Example 1, the divisibility of the semiconductor wafer was poor. The thermosetting resin film of Comparative Example 1 has low transmittance for light with a wavelength of 1342 nm. As a result, the light transmittance of the first protective film formed from this film is also low. When the semiconductor wafer is irradiated through the first protective film When irradiating laser light, the modified layer cannot be properly formed inside the semiconductor wafer. As a result, the semiconductor wafer cannot be divided normally.

In addition, when the thermosetting resin film of Comparative Example 1 is attached to the bump formation surface of the semiconductor wafer, it cannot be prevented from remaining on the upper part of the bump. Compared with the thermosetting resin film of Examples 1 to 2, The membrane has poor properties. The ratio of the content of the thermosetting component in the thermosetting resin film of Comparative Example 1 to the total mass of the thermosetting resin film was 17.8% by mass.

In Comparative Example 1, the first protective film could not be cut when the semiconductor wafer was divided, but it was not possible to determine to what extent the characteristics of the first protective film itself affected the result. The cutability of the protective film cannot be evaluated. However, since the breaking strength of the first protective film is as low as 25 MPa, it is speculated that the reason why the first protective film cannot be cut is mainly due to poor separability of the semiconductor wafer. [Industrial Availability]

The present invention can be used to manufacture workpieces having protruding electrodes on connection pads used in flip-chip mounting methods.

1, 2, 3: First protective film forming sheet 8: Second protective film forming sheet 9: Workpiece processed object 9a: Circuit surface of the workpiece processed object 9b: Inner surface of the workpiece processed object 11: First base material 11a : One side of the first base material 12: Thermosetting resin layer (thermosetting resin film) 12a: First side of the thermosetting resin layer (thermosetting resin film) 12': First protective film 12a': 1 The first side of the protective film 13: The first adhesive layer 13a: One side of the first adhesive layer 14: The first intermediate layer 81: The second base material 82: Resin layer (resin film) 83: The second adhesive layer 83a: One side of the second adhesive layer 90: Workpiece 90a: Circuit surface of the workpiece 90b: Inner surface of the workpiece 91: Protruding electrode 91a: Surface of the protruding electrode 101, 102, 103: 1st support piece 101a, 102a, 103a: 1st Surface 120' of the support sheet: first protective film after cutting 120a': first surface of the first protective film after cutting 201: first laminated structure 202: second laminated structure 203: third laminated structure 205 : 5th laminated structure 205': 5th intermediate laminated structure 206: 6th laminated structure 801: 2nd supporting piece 801a: One side of the 2nd supporting piece 820: Cut resin layer 900: Modified layer 910: Top of head 990: Workpiece with first protective film D ₉₁ : Distance between protruding electrodes E: Arrow H ₉₁ : Height of protruding electrodes R: Laser light T ₉₀ : Thickness of workpiece W ₉₁ : Protruding electrode Width

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

1: First protective film forming sheet

11: 1st base material

12: Thermosetting resin layer (thermosetting resin film)

13: 1st adhesive layer

13a: One side of the first adhesive layer

101: 1st support piece

101a: Surface of the first support piece

Claims (3)

A thermosetting resin film that is attached to a surface with a protruding electrode in a workpiece and heat-hardened to form a first protective film on the surface; one layer of the thermosetting resin film with a thickness of 200 μm Or the transmittance of the laminated film with a total thickness of 200 μm is 50% or more for light with a wavelength of 1342 nm, which is formed by laminating two or more layers of the aforementioned thermosetting resin film with a thickness less than 200 μm; Heat it at 130°C for 2 hours to thermally harden it to obtain a first protective film with a size of 20 mm × 130 mm and a thickness of 40 μm. The distance between the clamps is set to 80 mm, and the stretching speed is set to 200 mm/min. When the first protective film is stretched in a direction parallel to the surface of the first protective film, the breaking strength of the first protective film is 55 MPa or less. The thermosetting resin film according to claim 1, wherein the thermosetting resin film contains a thermosetting component other than an acrylic resin having an epoxy group; the content of the thermosetting component in the thermosetting resin film The proportion relative to the total mass of the thermosetting resin film is 40% by mass or more. A first protective film forming sheet including a first support sheet, and a thermosetting resin film according to claim 1 or 2 on one side of the first support sheet.