JP2023043538A - Protective film forming film, composite sheet for forming protective film and method for manufacturing workpiece article with protective film - Google Patents

Abstract

To provide a protective film forming film for forming a protective film provided at any of a workpiece article in a workpiece article with a protective film comprising the workpiece article and the protective film which can form a film which can suppress light absorption as the protective film and is easily visible under normal conditions and to provide a composite sheet for forming a protective film provided with the protective film forming film.SOLUTION: There is provided a protective film forming film in which when the protective film forming film is curable, the reflectance of light in the entire wavelength range of 400 to 700 nm of a cured product of the protective film forming film is 20% or more and when the protective film forming film is noncurable, the reflectance of light in the entire wavelength range of 400 to 700 nm of the protective film forming film is 20% or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a protective film-forming film, a protective film-forming composite sheet, and a method for producing a protective film-attached workpiece.

2. Description of the Related Art A wafer such as a semiconductor wafer or an insulator wafer has a circuit formed on one surface (circuit surface) thereof, and further has projecting electrodes such as bumps on that surface (circuit surface). Such a wafer is divided into chips, which are mounted on a circuit board by connecting projecting electrodes to connection pads on the circuit board.
In such wafers and chips, the surface opposite to the circuit surface (back surface) is sometimes protected with a protective film in order to prevent damage such as cracks (see Patent Document 1).
Further, in the manufacturing process of a semiconductor device, a semiconductor device panel, which will be described later, is used as a work, and in order to suppress the generation of warpage and cracks in this panel, some part of the panel may be protected with a protective film.

In such a case, for example, a protective film-forming film for forming a protective film is attached to the desired location of the workpiece, such as the back surface of the wafer, and then the workpiece is processed to produce a workpiece, and the necessary The protective film-forming film is cured according to the above, and the protective film-forming film or the protective film is cut to form a workpiece and a protective film-attached workpiece having a protective film provided on any part of the workpiece. to manufacture. An example of a work piece with a protective film is a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip.

WO2014/148642

In a light-emitting device having a work piece with a protective film, the protective film in the work piece with a protective film may absorb light. In that case, the amount of light output from the light-emitting device is reduced, and the protective film appears dark like a shadow in the light-emitting device. On the other hand, the protective film disclosed in Patent Document 1 cannot solve such problems.

The present invention provides a protective film-forming film for forming the protective film in a work piece with a protective film, which includes a work piece and a protective film provided at any part of the work piece, As the protective film, a protective film-forming film capable of suppressing light absorption and capable of forming a film that is easily visible under normal conditions; and a protective film-forming composite sheet comprising the protective film-forming film. , is intended to provide

The present invention provides a protective film-forming film for forming a protective film on any part of a workpiece obtained by processing a workpiece, wherein the protective film-forming film is curable. When the cured product of the protective film-forming film has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm, and the protective film-forming film is non-curable, the protective film Provided is a protective film-forming film having a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm.

When the protective film-forming film of the present invention is curable, the arithmetic mean height Sa of one surface or both surfaces of the cured product of the protective film-forming film is 100 nm or less, and the protective film of the present invention is When the film-forming film is non-curing, the arithmetic mean height Sa of one surface or both surfaces of the protective film-forming film may be 100 nm or less.
The protective film-forming film of the present invention may contain a white pigment.
When the protective film-forming film of the present invention is curable, the x value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the cured product of the protective film-forming film is , 0.26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34, and when the protective film-forming film of the present invention is non-curable, The x value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the protective film-forming film is 0.26 to 0.34, and in the Yxy color system The y-value may be between 0.26 and 0.34.

When the protective film-forming film of the present invention is curable, the Y value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the cured product of the protective film-forming film is , 20 or more, and when the protective film-forming film of the present invention is non-curable, the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the protective film-forming film may be 20 or more.
When the protective film-forming film of the present invention is curable, the cured product of the protective film-forming film has a maximum reflectance of 25% or more for light in the wavelength range of 400 to 700 nm. When the protective film-forming film is non-curable, the protective film-forming film may have a maximum reflectance of 25% or more for light in a wavelength range of 400 to 700 nm.
In the protective film-forming film of the present invention, the workpiece may be a chip in a light-emitting device.

The present invention comprises a support sheet and a protective film-forming film provided on one surface of the support sheet, wherein the protective film-forming film is the protective film-forming film of the present invention. To provide a composite sheet for

The present invention is a method for manufacturing a work piece with a protective film, wherein the work piece with a protective film includes a work piece obtained by machining a work piece and a and a protective film provided, wherein the protective film is formed from the protective film-forming film in the protective film-forming composite sheet of the present invention, and the protective film-forming film is curable. In some cases, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, the protection after being attached to any part of the work The film-forming film is the protective film, and the manufacturing method includes attaching the protective film-forming film in the protective film-forming composite sheet to a target location of the work, thereby forming the protective film on the work. A pasting step of producing a first laminate provided with a forming composite sheet, a processing step of producing the workpiece by processing the workpiece after the pasting step, and after the pasting step, and a cutting step of cutting the protective film-forming film or the protective film, and when the protective film-forming film is curable, further curing the protective film-forming film after the attaching step. and a curing step of forming the protective film.

The present invention is a method for manufacturing a work piece with a protective film, wherein the work piece with a protective film includes a work piece obtained by machining a work piece and a and a protective film provided, wherein the protective film is formed from the protective film-forming film of the present invention, and when the protective film-forming film is curable, the protective film When the cured product of the forming film is the protective film, and the protective film-forming film is non-curable, the protective film-forming film after being attached to any part of the work is the protective film. wherein the manufacturing method includes attaching the protective film-forming film to a target location of the work to produce a second laminate in which the protective film-forming film or the protective film is provided on the work. a processing step of fabricating the workpiece by processing the workpiece after the attaching step; and a cutting step of cutting the protective film-forming film or the protective film after the attaching step. and, when the protective film-forming film is curable, further comprising a curing step of forming the protective film by curing the protective film-forming film after the attaching step. A method for manufacturing a membrane-coated work piece is provided.

According to the present invention, a protective film-forming film for forming the protective film in a work piece with a protective film, which includes a work piece and a protective film provided at any part of the work piece, As the protective film, a protective film-forming film capable of suppressing light absorption and capable of forming a film that is easily visible under normal conditions; and a protective film-forming composite sheet comprising the protective film-forming film. , is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the protective film formation film which concerns on one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the composite sheet for protective film formation which concerns on one Embodiment of this invention. FIG. 4 is a cross-sectional view schematically showing another example of the protective film-forming composite sheet according to one embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing still another example of the protective film-forming composite sheet according to one embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing still another example of the protective film-forming composite sheet according to one embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view for schematically explaining an example of a method for manufacturing a workpiece with a protective film according to one embodiment of the present invention; FIG. 4 is a cross-sectional view for schematically explaining another example of the method for manufacturing a workpiece with a protective film according to one embodiment of the present invention;

◇ Protective film-forming film The protective film-forming film according to one embodiment of the present invention is a protective film-forming film for forming a protective film on any part of a workpiece obtained by processing the workpiece. When the protective film-forming film is curable, the cured product of the protective film-forming film has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm, and the protective film When the forming film is non-curing, the protective film forming film has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm.
The protective film-forming film of the present embodiment can constitute a protective film-forming composite sheet, for example, by laminating it with a support sheet as described later.

The protective film-forming film of the present embodiment is a film used for protecting the workpiece by providing a protective film on any part of the workpiece.
The protective film-forming film is soft and can be attached to a workpiece before being processed into the workpiece.

In this embodiment, the work includes, for example, a semiconductor wafer, a semiconductor device panel, and the like. A semiconductor device panel is handled in the manufacturing process of a semiconductor device. These semiconductor devices are arranged planarly in a circular, rectangular, or other area.
In this specification, a machined workpiece is referred to as a "workpiece". For example, if the workpiece is a semiconductor wafer, the workpiece may be a semiconductor chip.

Hereinafter, the present embodiment will be described by taking a wafer as an example of a work and taking a chip as an example of a workpiece to be processed.

The protective film-forming film of the present embodiment may be curable or non-curable. That is, the protective film-forming film may function as a protective film when cured, or may function as a protective film in an uncured state.
The curable protective film-forming film may be either thermosetting or energy ray-curable, or may have both thermosetting and energy ray-curable properties.

As used herein, the term "energy ray" means an electromagnetic wave or charged particle beam that has energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be applied by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source. The electron beam can be generated by an electron beam accelerator or the like.
As used herein, "energy ray-curable" means the property of curing by irradiation with energy rays, and "non-energy ray-curable" means the property of not curing even when irradiated with energy rays. do.
As used herein, the term "non-curing" means the property of not being cured by any means such as heating or energy ray irradiation. A non-curing overcoat-forming film can be considered to be a overcoat after it is provided (formed) on the intended object.

As used herein, the term "wafer" refers to elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC. Semiconductor wafers; An insulator wafer made of an insulator can be mentioned.
A circuit is formed on one surface of these wafers, and in this specification, the surface of the wafer on which the circuit is formed is referred to as a "circuit surface". The surface of the wafer opposite to the circuit surface is called the "back surface".
The wafer is divided into chips by means of dicing or the like. In this specification, as in the case of a wafer, the side of the chip on which the circuit is formed is called the "circuit side", and the side opposite to the circuit side of the chip is called the "back side".
Both the circuit surface of the wafer and the circuit surface of the chip are provided with projecting electrodes such as bumps and pillars. The projecting electrodes are preferably made of solder.

By using the protective film-forming film of the present embodiment or the protective film-forming composite sheet including the same, a chip with a protective film having a chip and a protective film provided on the back surface of the chip can be manufactured. .
Then, prior to the production of the chip with a protective film, by using the protective film, a wafer with a protective film is produced, which includes a wafer and a protective film formed on the back surface of the wafer. can.

Furthermore, by using the chip with the protective film, a substrate device can be manufactured.
As used herein, the term "substrate device" means a chip with a protective film that is flip-chip connected to connection pads on a circuit board at protruding electrodes on the circuit surface of the chip. For example, if a semiconductor wafer is used as the wafer, the substrate device may be a semiconductor device.

When the protective film-forming film of the present embodiment is curable, the cured product of the protective film-forming film is measured for the reflectance of light in the entire wavelength range of 400 to 700 nm. is 20% or more. In other words, the minimum reflectance of the cured product of the protective film-forming film to light in the wavelength range of 400 to 700 nm is 20% or more.
When the protective film-forming film of the present embodiment is non-curing, when the reflectance of light in the entire wavelength range of 400 to 700 nm is measured for the protective film-forming film, the reflectance of these lights is 20 % or more. In other words, the protective film-forming film has a minimum reflectance of 20% or more for light in the wavelength range of 400 to 700 nm.
Visible light absorption is suppressed in the protective film obtained using the protective film-forming film having such properties. Therefore, for example, when the light-emitting device includes a work piece with a protective film obtained using the protective film-forming film, a decrease in the amount of light output from the light-emitting device is suppressed, and the It also prevents the protective film from appearing dark like a shadow in the light-emitting device. Furthermore, the protective film obtained using the protective film-forming film having such properties is easily visible under normal conditions.

That is, in this embodiment, the workpiece is preferably a chip in a light emitting device, and may be a semiconductor chip in the light emitting device.

The light-emitting device may be any device provided with a light-emitting element such as an LED (Light Emitting Diode), and its type is not particularly limited. Examples of the light emitting device include a substrate device having a surface-mounted LED package with a light emitting element, a substrate device having a mini LED element, a substrate device having a micro LED element, and the like.

In this specification, unless otherwise specified, the cured product of the protective film-forming film means a cured product with a sufficiently high degree of curing, and is synonymous with the protective film.

Hereinafter, in the present specification, when the protective film-forming film is curable, the cured product of the protective film-forming film, the reflectance of light in the entire wavelength range of 400 to 700 nm, and the protective film-forming film When is non-curable, the protective film-forming film is simply referred to as "light (400 to 700 nm) reflectance", including the reflectance of light in the entire wavelength range of 400 to 700 nm. There is

The reflectance of light (400-700 nm) can be measured by the following method.
That is, for each of the protective film-forming film or its cured product and the reference plate made of barium sulfate, the incident angle of incident light to these measurement objects is set to 8°, and an integrating sphere is used to measure 400 to 700 nm. In the wavelength range, the light quantity of the total reflected light including specular reflected light (regular reflected light) and diffuse reflected light is measured by the SCI (Specular Component Include) method. Then, the ratio of the measured value of the protective film-forming film or its cured product to the measured value of the reference plate ([measured value of the amount of light reflected by the cured product of the protective film-forming film] / [reference Measured amount of all reflected light on the plate] x 100, or [Measured amount of all reflected light on the protective film forming film] / [Measured amount of all reflected light on the reference plate ]×100), that is, the relative total light reflectance of the protective film-forming film or its cured product is obtained, and this can be used as the reflectance of light (400 to 700 nm). Then, the maximum and minimum values of them can be adopted as the maximum and minimum values of the reflectance of light (400 to 700 nm), respectively, which will be described later.

The reflectance of light (400 to 700 nm) may be 20% or higher, for example, 22% or higher, 24% or higher, or 26% or higher.
The upper limit of reflectance for light (400 to 700 nm) is not particularly limited. For example, a protective film-forming film having a reflectance of light (400 to 700 nm) of 55% or less can be produced more easily, and the reflectance of light (400 to 700 nm) may be, for example, 45% or less. .
The reflectance of light (400-700 nm) may be, for example, any of 20-55%, 22-55%, 24-55%, and 26-55%. It may be either 45%, 24-45%, and 26-45%.

When the protective film-forming film of the present embodiment is curable, the maximum reflectance of light in the wavelength range of 400 to 700 nm of the cured product of the protective film-forming film is 25% or more. preferable.
When the protective film-forming film of the present embodiment is non-curing, the maximum reflectance of the protective film-forming film for light in the wavelength range of 400 to 700 nm is preferably 25% or more.
Visible light absorption is further suppressed in the protective film obtained using the protective film-forming film having such properties. Therefore, for example, when the light-emitting device includes a workpiece with a protective film obtained using the protective film-forming film, a decrease in the amount of light output from the light-emitting device is further suppressed, and The shadowy appearance of the protective film in the light-emitting device is also reduced, and the protective film is more easily visible under normal conditions.

The maximum reflectance of light (400 to 700 nm) may be, for example, 28% or more, 32% or more, or 36% or more.
The upper limit of the maximum reflectance of light (400 to 700 nm) is not particularly limited. For example, a protective film-forming film having a maximum reflectance of light (400 to 700 nm) of 60% or less can be produced more easily, and the maximum value may be, for example, 50% or less.
The maximum reflectance of light (400-700 nm) may be, for example, 25-60%, 28-60%, 32-60%, and 36-60%, or 25-50%. , 28-50%, 32-50%, and 36-50%.

In the protective film-forming film, the reflectance of light (400 to 700 nm) and its maximum value are determined by, for example, the components contained in the protective film-forming composition described later, particularly the colorant (thermosetting protective film-forming composition ( Colorant (J) in III), colorant in energy ray-curable protective film-forming composition (IV) and non-curable protective film-forming composition (V)) and its content can be adjusted, When the colorant is a pigment, it can also be adjusted by its particle size. For example, the reflectance of light (400 to 700 nm) can be increased by using a colorant having a high degree of whiteness and increasing its content. For example, when the protective film-forming film contains a white pigment, such a protective film-forming film has a reflectance of light (400 to 700 nm), or a reflectance of light (400 to 700 nm) and its maximum is preferred as satisfying the above conditions.

When the protective film-forming film of the present embodiment is curable, the arithmetic mean height Sa of one surface or both surfaces of the cured product of the protective film-forming film is preferably 100 nm or less, In particular, it is preferable that the arithmetic mean height Sa of the surface opposite to the surface to be attached to the work (for example, the surface on which laser printing is performed) is 100 nm or less.
When the protective film-forming film of the present embodiment is non-curable, the arithmetic mean height Sa of one surface or both surfaces of the protective film-forming film is preferably 100 nm or less. It is preferable that the arithmetic mean height Sa of the surface opposite to the surface to be adhered to (for example, the surface on which laser marking is performed) is 100 nm or less.
The cured product of the curable protective film-forming film of the present embodiment or the exposed surface of the non-curable protective film-forming film has such roughness characteristics, so that the cured product or the non-curable protective film-forming film ( That is, when laser marking is performed on the exposed surface of the protective film), the marking can be visually recognized more easily. Said Sa generally does not affect the reflectance of light (400-700 nm).

In this specification, the arithmetic mean height Sa of the surface may be simply referred to as "Sa".
In this specification, the arithmetic mean height Sa of the surface means a measured value measured according to ISO 25178.

From the viewpoint of enhancing the above effects, the arithmetic mean height Sa of one or both surfaces of the cured product or non-curable protective film-forming film is preferably 85 nm or less, and is 70 nm or less. is more preferably 65 nm or less.
The lower limit of Sa is not particularly limited. For example, a protective film-forming film having Sa of 30 nm or more can be produced more easily.
Said Sa may be, for example, any one of 30 to 100 nm, 30 to 85 nm, 30 to 70 nm, and 30 to 65 nm.

The arithmetic mean height Sa of one side or both sides of the cured product can be adjusted by adjusting the arithmetic mean height Sa of the corresponding side of the curable protective film-forming film.
Then, regardless of whether it is curable or non-curable, the arithmetic mean height Sa of one surface or both surfaces of the protective film-forming film is the surface to be formed of the protective film-forming film. It can be adjusted by adjusting the surface condition of the surface to be formed of the protective film-forming film when forming the protective film-forming film by applying the film-forming composition and drying it as necessary. Further, when pressing the surface of means for transferring the surface state (hereinafter sometimes referred to as "transfer means") against one or both surfaces of the formed protective film-forming film, Sa can be adjusted by using, as the transfer means, means whose surface condition has been adjusted, or by adjusting the pressure with which the surface of the transfer means is pressed. Examples of the transfer means include a first release film, which will be described later. Sa can also be adjusted by adjusting the particle size of solid components such as fillers in the composition for forming a protective film, which will be described later.

When the protective film-forming film of the present embodiment is curable, the x value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the cured product of the protective film-forming film is preferably 0.26 to 0.34, more preferably 0.28 to 0.33.
When the protective film-forming film of the present embodiment is non-curing, the x value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the protective film-forming film is It is preferably 0.26 to 0.34, more preferably 0.28 to 0.33.
When the x value is within such a range, absorption of visible light is further suppressed in the protective film obtained using the protective film-forming film. Therefore, for example, when the light-emitting device includes a workpiece with a protective film obtained using the protective film-forming film, a decrease in the amount of light output from the light-emitting device is further suppressed, and It is also more suppressed that the protective film looks dark like a shadow in the light-emitting device.
In this embodiment, as the x value, a value calculated with C light source (2° field of view), which is a standard light source, can be used.

When the protective film-forming film of the present embodiment is curable, the cured product of the protective film-forming film is calculated from the reflectance of light in the wavelength range of 380 to 780 nm, y in the Yxy color system The value is preferably between 0.26 and 0.34, more preferably between 0.28 and 0.34.
When the protective film-forming film of the present embodiment is non-curable, the y value in the Yxy color system, which is calculated from the reflectance of light in the wavelength range of 380 to 780 nm, of the protective film-forming film is It is preferably 0.26 to 0.34, more preferably 0.28 to 0.34.
The protective film-forming film of the present embodiment exhibits the same effect as the case where the above-mentioned x value is limited due to the y value being within such a range.
In this embodiment, as the y value, a value calculated with C light source (2° field of view), which is a standard light source, can be used.

When the protective film-forming film of the present embodiment is curable, the cured product of the protective film-forming film preferably satisfies both the x-value and y-value conditions described above. When the film is non-curable, the protective film-forming film preferably satisfies both the x value and y value conditions described above. In such a case, in the protective film obtained using the protective film-forming film of the present embodiment, the absorption of visible light is suppressed. A more excellent effect is achieved in that a decrease in the amount of light output from the light-emitting device is suppressed, and that the protective film is suppressed from appearing dark like a shadow in the light-emitting device.
As a protective film-forming film that provides such a better effect, for example, when the protective film-forming film is curable, the cured product of the protective film-forming film has a wavelength range of 380 to 780 nm. The x value in the Yxy color system calculated from the light reflectance is 0.26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34. When the protective film-forming film is non-curing, the x value in the Yxy color system, calculated from the reflectance of light in the wavelength range of 380 to 780 nm, of the protective film-forming film is , 0.26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34. However, this is an example of a protective film-forming film that provides the above-mentioned superior effects.

When the protective film-forming film of the present embodiment is curable, the cured product of the protective film-forming film is calculated from the reflectance of light in the wavelength range of 380 to 780 nm, Y in the Yxy color system The value is preferably 20 or greater.
When the protective film-forming film of the present embodiment is non-curing, the Y value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the protective film-forming film is It is preferably 20 or more.
When the Y value is in such a range, absorption of visible light is further suppressed in the protective film obtained using the protective film-forming film. Therefore, for example, when the light-emitting device includes a workpiece with a protective film obtained using the protective film-forming film, a decrease in the amount of light output from the light-emitting device is further suppressed, and It is also more suppressed that the protective film looks dark like a shadow in the light-emitting device.
In this embodiment, as the Y value, a value calculated with a C light source (2° field of view), which is a standard light source, can be used.

The Y value may be, for example, 25 or more, 30 or more, or 35 or more, regardless of whether the protective film-forming film of the present embodiment is curable or non-curable.
The upper limit of the Y value is not particularly limited regardless of whether the protective film-forming film of the present embodiment is curable or non-curable. For example, a protective film-forming film having a Y value of 60 or less can be produced more easily, and the Y value may be, for example, 50 or less.
The Y value may be, for example, any one of 20 to 60, 25 to 60, 30 to 60, and 35 to 60; It can be either.

When the protective film-forming film of the present embodiment is curable, it is more preferable that the cured product of the protective film-forming film satisfies all the conditions of the above-mentioned x value, y value and Y value, and the present embodiment When the protective film-forming film of (1) is non-curing, it is more preferable that the protective film-forming film satisfies all of the above-mentioned x-value, y-value and Y-value conditions. In such a case, in the protective film obtained using the protective film-forming film, the absorption of visible light is suppressed, for example, when the light-emitting device includes a workpiece with a protective film, the light-emitting device A particularly excellent effect is obtained in that a decrease in the amount of light output from the light-emitting device is suppressed, and that the protective film is suppressed from appearing dark like a shadow in the light-emitting device.
Examples of the protective film-forming film that provides such a particularly excellent effect include, for example, when the protective film-forming film is curable, the cured product of the protective film-forming film has a wavelength range of 380 to 780 nm. The x value in the Yxy color system calculated from the light reflectance is 0.26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34, And the Y value in the Yxy color system is 20 or more, and when the protective film-forming film is non-curable, the protective film-forming film has a wavelength range of 380 to 780 nm. The x value in the Yxy color system calculated from the light reflectance is 0.26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34, Also, the Y value in the Yxy color system is 20 or more. However, this is an example of a protective film-forming film that provides the particularly excellent effects described above.

In the protective film-forming film, the x value, y value and Y value in the Yxy color system are, for example, the components of the protective film-forming composition described later, particularly the colorant (thermosetting protective film-forming composition ( The colorant (J) in III), the colorant in the energy ray-curable protective film-forming composition (IV) and the non-curable protective film-forming composition (V)) and the content thereof can be adjusted. If the colorant is a pigment, it can also be adjusted by its particle size. For example, the Y value can be increased by using a colorant having a high degree of whiteness and increasing its content.

At least both sides of the protective film-forming film of the present embodiment preferably have a single color tone, and the protective film-forming film as a whole may have a single color tone. Such a protective film-forming film is advantageous in that the printing can be clearly visually confirmed in the state of the protective film on which laser printing has been finally applied. In addition, such a protective film-forming film is advantageous in that it is easy to manufacture, and that the color tone of all chips with a protective film produced from one wafer with a protective film-forming film is uniform. be.
Both surfaces of the protective film-forming film are the same as the first surface and the second surface which will be described later, for example.

Note that both surfaces of the protective film-forming film have a single color tone means that both surfaces of the protective film-forming film have a single color tone (same color tone) over the entire area.
In addition, when the entire protective film-forming film has a single color tone, it means that not only the entire area of both sides of the protective film-forming film, but also the entire internal area has a single color tone (same color). means that

The color tone of the protective film-forming film is determined, for example, by the components contained in the protective film-forming composition described later, particularly the colorant (the colorant (J) in the thermosetting protective film-forming composition (III), the energy ray-curable protective It can be adjusted by the type and content of the colorant in the film-forming composition (IV) and the non-curable protective film-forming composition (V).

When the protective film-forming film is thermosetting, the protective film that defines the reflectance of the light (400 to 700 nm) and its maximum value, the Sa, the x value, the y value, and the Y value. The cured product of the forming film is a thermosetting product, which is the protective film and is a cured product obtained by heating the protective film forming film at 140° C. for 2 hours.
When the protective film-forming film is energy ray-curable, the protection that defines the reflectance of the light (400 to 700 nm) and its maximum value, the Sa, the x value, the y value, and the Y value The cured product of the film-forming film is an energy ray-cured product, and the protective film is cured under the conditions of an illuminance of 220 mW/cm ² and an energy ray light amount of 600 mJ/cm ² with respect to the protective film-forming film. It is a cured product obtained by irradiating energy rays.

In the case of forming a protective film by thermally curing the protective film-forming film, unlike the case of curing by irradiation with energy rays, the protective film-forming film is sufficiently cured by heating even if its thickness increases. Since it cures, a protective film with high protective ability can be formed. Moreover, by using a normal heating means such as a heating oven, a large number of protective film-forming films can be collectively heated and thermally cured.
When the protective film-forming film is cured by irradiation with energy rays to form a protective film, unlike the case of thermal curing, the protective film-forming composite sheet described later does not need to have heat resistance, and can be used in a wide range of applications. A composite sheet for forming a protective film within the range can be constructed. Moreover, it can be cured in a short time by irradiation with energy rays.
When the protective film-forming film is used as the protective film without being cured, the curing step can be omitted, so that a chip with a protective film can be manufactured in a simplified process.

The protective film-forming film is preferably thermosetting or energy ray-curable. A thermosetting or energy ray-curable protective film-forming film not only has good adhesion aptitude to a wafer, but can also be cured to form a protective film with higher protective ability.

The protective film-forming film may consist of one layer (single layer) or may consist of two or more layers. When the protective film-forming film consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

In this specification, not only in the case of the protective film-forming film, "multiple layers may be the same or different" means "all the layers may be the same or all the layers may be different. "A plurality of layers may be the same, or only some of the layers may be the same." means that

When the protective film-forming film is composed of multiple layers of two or more layers, the adhesion between each layer is poor, or the protective film warps due to the difference in the ease of expansion and contraction of each layer. There is a possibility that problems such as peeling from the back surface of the chip may occur, and from the point of view of suppressing such problems, the protective film-forming film preferably consists of a single layer.
In addition, a single-layer protective film-forming film is preferable because it can be easily manufactured with high uniformity in thickness and because it has a high degree of freedom in design.

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm. 38 μm, and 20-30 μm. When the thickness of the protective film-forming film is at least the lower limit, a protective film with higher protective ability can be formed. When the thickness of the protective film-forming film is equal to or less than the upper limit value, it is possible to avoid an excessive thickness of the chip with the protective film.
Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. means the total thickness of the layers of

<<Composition for Forming Protective Film>>
The protective film-forming film can be formed using a protective film-forming composition containing its constituent materials. For example, a protective film-forming film can be formed by applying a protective film-forming composition to the surface to be formed, and drying it as necessary. The content ratio of the components that do not vaporize at room temperature in the protective film-forming composition is generally the same as the content ratio of the components in the protective film-forming film. As used herein, the term "ordinary temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature.

In the protective film-forming film, the ratio of the total content of one or more components described later in the protective film-forming film to the total mass of the protective film-forming film is 100% by mass or less.
Similarly, in the protective film-forming composition, the ratio of the total content of one or more components described later in the protective film-forming composition to the total weight of the protective film-forming composition is 100 mass. % or less.

The thermosetting protective film-forming film can be formed using a thermosetting protective film-forming composition, and the energy ray-curable protective film-forming film can be formed using the energy ray-curable protective film-forming composition, A non-curable protective film-forming film can be formed using a non-curable protective film-forming composition. In the present specification, when the protective film-forming film has both thermosetting and energy ray-curing properties, the contribution of the thermosetting of the protective film-forming film to the formation of the protective film is the energy ray curing. is greater than the contribution of the protective film-forming film is treated as thermosetting. Conversely, when the contribution of energy ray curing of the protective film-forming film to the formation of the protective film is greater than the contribution of thermal curing, the protective film-forming film is treated as energy ray-curing.

The protective film-forming composition may be applied by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, A method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater can be used.

Drying conditions for the composition for forming a protective film are not particularly limited. However, when the composition for forming a protective film contains a solvent, which will be described later, it is preferable to heat and dry the composition. The protective film-forming composition containing a solvent is preferably dried by heating, for example, at 70 to 130° C. for 10 seconds to 5 minutes. However, the thermosetting protective film-forming composition is preferably dried by heating so that the composition itself and the thermosetting protective film-forming film formed from the composition are not thermally cured.

Hereinafter, the thermosetting protective film-forming film, the energy ray-curable protective film-forming film, and the non-curable protective film-forming film will be described in order.

◎ Thermosetting protective film-forming film The curing conditions when thermosetting a thermosetting protective film-forming film to form a protective film are as long as the degree of curing is such that the protective film can fully demonstrate its function. It is not particularly limited, and may be appropriately selected according to the type of the thermosetting protective film-forming film.
For example, the heating temperature during thermosetting of the thermosetting protective film-forming film is preferably 100 to 200°C, more preferably 110 to 170°C, and particularly preferably 120 to 150°C. The heating time during thermosetting is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
The protective film formed by thermosetting is preferably slowly cooled to room temperature. The slow cooling method is not particularly limited, and cooling may be performed.

The protective film-forming film at room temperature is heated to a temperature exceeding room temperature and then cooled to room temperature to obtain a protective film-forming film after heating and cooling, and the protective film-forming film after heating and cooling is hardened. and the hardness of the protective film-forming film before heating at the same temperature, if the protective film-forming film after heating and cooling is harder, the protective film-forming film is thermosetting. .

Preferred thermosetting protective film-forming films include, for example, those containing a polymer component (A), a thermosetting component (B) and a colorant (J).
The polymer component (A) is a component that can be regarded as being formed by a polymerization reaction of a polymerizable compound.
The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction with heat as a reaction trigger. In addition, in this specification, a polycondensation reaction is also included in the polymerization reaction.

<Composition (III) for forming a thermosetting protective film>
Preferred thermosetting protective film-forming compositions include, for example, the thermosetting protective film-forming composition (III ) (which may be simply abbreviated as “composition (III)” in this specification) and the like.

[Polymer component (A)]
The polymer component (A) imparts film-forming properties, flexibility, toughness, spreadability, etc. to the thermosetting protective film-forming film, and imparts flexibility, toughness, spreadability, etc. to the protective film. is an ingredient.
The composition (III) and the polymer component (A) contained in the thermosetting protective film-forming film may be of one type or may be of two or more types. Any combination and ratio thereof can be selected.

Examples of the polymer component (A) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, etc. Acrylic resins are preferred. In this specification, the acrylic resin as the polymer component (A) may be referred to as "acrylic resin (A1)".

The weight average molecular weight (Mw) of the acrylic resin (A1) is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight-average molecular weight of the acrylic resin (A1) is at least the lower limit, the shape stability (stability over time during storage) of the thermosetting protective film-forming film is improved. When the weight average molecular weight of the acrylic resin (A1) is equal to or less than the upper limit, the thermosetting protective film-forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film-forming film The generation of voids and the like is further suppressed between.

As used herein, "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin (A1) is preferably -60 to 70°C, more preferably -50 to 50°C, even more preferably -45 to 40°C, and - It is more preferably 40 to 30°C, more preferably -35 to 20°C, and particularly preferably -35 to 10°C. When the Tg of the acrylic resin (A1) is equal to or higher than the lower limit, the adhesive strength between the cured product of the protective film-forming film and the support sheet is suppressed, and the releasability is moderately improved. When the Tg of the acrylic resin (A1) is equal to or less than the upper limit, the adhesion of the thermosetting protective film-forming film to the adherend and the adhesion of the protective film to the adherend are improved.

The acrylic resin (A1) has m types (m is an integer of 2 or more) of structural units, and each of the m types of monomers that derive these structural units overlaps from 1 to m. When the numbers are sequentially assigned and named as "monomer m", the glass transition temperature (Tg) of the acrylic resin (A1) can be calculated using the following Fox formula.

（式中、Ｔｇはアクリル樹脂（Ａ１）のガラス転移温度であり；ｍは２以上の整数であり；Ｔｇ_ｋはモノマーｍのホモポリマーのガラス転移温度であり；Ｗ_ｋはアクリル樹脂（Ａ１）における、モノマーｍから誘導された構成単位ｍの質量分率であり、ただし、Ｗ_ｋは下記式を満たす。）

(Wherein, Tg is the glass transition temperature of the acrylic resin (A1); m is an integer of 2 or more; Tg _k is the glass transition temperature of the homopolymer of the monomer m; W _k is the acrylic resin (A1) is the mass fraction of the structural unit m derived from the monomer m in, provided that _Wk satisfies the following formula.)

（式中、ｍ及びＷ_ｋは、前記と同じである。）

(Wherein, m and _Wk are the same as above.)

As the Tg _k , values described in Polymer Data Handbook, Adhesive Handbook, Polymer Handbook, etc. can be used. For example, the Tg _k of a homopolymer of methyl acrylate is 10°C, the Tg _k of a homopolymer of methyl methacrylate is 105°C, and the Tg _k of a homopolymer of 2-hydroxyethyl acrylate is -15°C. , the Tg _k of the homopolymer of n-butyl acrylate is -54°C, and the Tg _k of the homopolymer of glycidyl methacrylate is 41°C.

Examples of the acrylic resin (A1) include polymers of one or more (meth)acrylic acid esters; one or more (meth)acrylic acid esters, (meth)acrylic acid, and itaconic acid. , vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like with one or two or more monomers selected from the group.

Examples of the (meth)acrylic acid ester constituting the acrylic resin (A1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) ) heptyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylic Decyl acid, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), (meth)acrylate Alkyl groups constituting alkyl esters such as pentadecyl acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate) is a chain structure having 1 to 18 carbon atoms, (meth)acrylic acid alkyl ester;
Cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;
(meth)acrylic acid aralkyl ester such as benzyl (meth)acrylate;
(meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;
(meth)acrylic acid cycloalkenyloxyalkyl ester such as (meth)acrylic acid dicyclopentenyloxyethyl ester;
(meth)acrylic acid imide;
glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) ) hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate;
Examples thereof include substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate. Here, "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms.

Monomers constituting the acrylic resin (A1) may be of one type or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic resin (A1) may have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acryloyl groups, amino groups, hydroxyl groups, carboxy groups, and isocyanate groups. The functional group of the acrylic resin (A1) may be bonded to another compound via a cross-linking agent (G), which will be described later, or directly bonded to another compound without the cross-linking agent (G). good too. The adhesion reliability of the protective film to the adherend tends to be improved by bonding the acrylic resin (A1) with the other compound through the functional group.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (A1) (hereinafter sometimes simply referred to as "thermoplastic resin") is used without using the acrylic resin (A1). It may be used alone or in combination with the acrylic resin (A1). By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, and the thermosetting protective film-forming film easily follows the uneven surface of the adherend, and the adherend and thermosetting Generation|occurrence|production of a void etc. may be suppressed more between protective film formation films.

The weight average molecular weight of the 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 to 150°C, more preferably -20 to 120°C.

Examples of the thermoplastic resin include urethane resin, phenoxy resin, silicone resin, and saturated polyester resin.

In composition (III), the ratio of the content of polymer component (A) to the total content of all components other than the solvent is 5 to 80% by mass, regardless of the type of polymer component (A). It is preferably 10 to 65% by mass, and may be, for example, 15 to 50% by mass or 15 to 35% by mass.
This content is that the ratio of the content of the polymer component (A) to the total mass of the thermosetting protective film-forming film in the thermosetting protective film-forming film is, regardless of the type of polymer component (A), It is preferably 5 to 80% by mass, more preferably 10 to 65% by mass, for example, it may be either 15 to 50% by mass or 15 to 35% by mass. be.
This is based on the fact that the amounts of components other than the solvent usually do not change in the process of removing the solvent from the resin composition containing the solvent and forming the resin film, and the resin composition and the resin film , the content ratios of the components other than the solvent are the same. Therefore, in the present specification, hereinafter, not only in the case of a thermosetting protective film-forming film, but with regard to the content of components other than the solvent, only the content in the resin film obtained by removing the solvent from the resin composition is described. .

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III) is the polymer component Considered to contain (A) and a thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component that has thermosetting properties and cures the thermosetting protective film-forming film.
The composition (III) and the thermosetting component (B) contained in the thermosetting protective film-forming film may be of one kind, or may be of two or more kinds, and in the case of two or more kinds of , their combination and ratio can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy resins, thermosetting polyimide resins, unsaturated polyester resins and the like, with epoxy resins being preferred.
In this specification, the epoxy resin as the thermosetting component (B) may be referred to as "epoxy resin (B1)".
Moreover, a thermosetting polyimide resin is a general term for a polyimide precursor and a thermosetting polyimide that form a polyimide resin by thermosetting.

・Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, ortho-cresol novolak epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenylene skeleton-type epoxy resins, and other epoxy compounds having a functionality of two or more can be used.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 from the viewpoint of the curability of the thermosetting protective film-forming film and the strength and heat resistance of the protective film that is the cured product thereof. is preferred, 300 to 10,000 is more preferred, and 300 to 3,000 is particularly preferred.
The epoxy equivalent of the epoxy resin (B1) is preferably 100-1000 g/eq, more preferably 150-950 g/eq.

The epoxy resin (B1) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

[Heat curing agent (C)]
When the thermosetting component (B) is the epoxy resin (B1), the composition (III) and the thermosetting protective film-forming film preferably contain the thermosetting agent (C).
Examples of the thermosetting agent (C) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an anhydrided group of an acid group. is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among thermosetting agents (C), phenol-based curing agents having phenolic hydroxyl groups include, for example, polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, aralkyl-type phenolic resins, and the like. .
Among the thermosetting agents (C), amine-based curing agents having an amino group include, for example, dicyandiamide.

The thermosetting agent (C) may have an unsaturated hydrocarbon group.

Of the thermosetting agent (C), the number average molecular weight of resin components such as polyfunctional phenolic resins, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins is preferably 300 to 30,000. , 400 to 10,000, and particularly preferably 500 to 3,000.
Among the thermosetting agent (C), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent (C) may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

The content of the thermosetting agent (C) in the thermosetting protective film-forming film is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the thermosetting component (B), More preferably 0.1 to 200 parts by mass, even more preferably 0.1 to 100 parts by mass, particularly preferably 0.5 to 50 parts by mass, for example, 0.5 to 25 parts by mass parts, 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass. When the content of the thermosetting agent (C) is at least the lower limit, curing of the thermosetting protective film-forming film proceeds more easily. When the content of the thermosetting agent (C) is equal to or less than the upper limit, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the adhesion reliability of the protective film to the adherend is further improved.

In the thermosetting protective film-forming film, the ratio of the total content of the thermosetting component (B) and the thermosetting agent (C) to the total weight of the thermosetting protective film-forming film is 3 to 50% by mass. 5 to 35% by mass is more preferable, 7 to 25% by mass is even more preferable, and 9 to 20% by mass is particularly preferable. When the ratio is within such a range, the performance of the protective film to protect chips and the like is further improved. Moreover, the adhesion reliability of the protective film to the adherend is further improved. In addition, the adhesive strength between the cured product of the protective film-forming film and the support sheet is suppressed, and the releasability is moderately improved.

[Colorant (J)]
The coloring agent (J) is a component for adjusting the light reflectance of the thermosetting protective film-forming film and the protective film. The protective film containing the coloring agent (J) is more easily visible under normal conditions, and the protective film provided anywhere on the workpiece is also visible under normal conditions. is easier.

Examples of the coloring agent (J) include organic dyes and inorganic pigments.

Examples of the organic dyes include diimmonium dyes, aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine dyes. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazolones dyes, spirone-based dyes, pyranthrone-based dyes, threne-based dyes, and the like.

Examples of the inorganic pigment include carbon materials such as carbon black; lanthanum-based materials; tin-based materials; antimony-based materials; tungsten-based materials; Here, the lanthanum-based materials, tin-based materials, antimony-based materials, tungsten-based materials, and titanium-based materials are respectively lanthanum-containing materials, tin-containing materials, antimony-containing materials, tungsten-containing materials, and titanium-containing materials. means material.

The composition (III) and the colorant (J) contained in the thermosetting protective film-forming film may be of only one type, or may be of two or more types. can be selected arbitrarily.
For example, the composition (III) and the thermosetting protective film-forming film may contain, as the colorant (J), only one or two or more organic pigments, or one or two inorganic pigments. It may contain more than one kind, or may contain one or more kinds of organic dyes and inorganic pigments.

The colorant (J) is preferably a white pigment, that is, the thermosetting protective film-forming film preferably contains a white pigment. In the protective film (protective film containing white pigment) obtained using such a thermosetting protective film-forming film, the reflectance of light (400 to 700 nm) is higher, and the value is 20% or more. , and it is also easy to adjust the maximum reflectance of light (400 to 700 nm) to 25% or more. Also, a protective film containing a white pigment has such a higher reflectance of light (400-700 nm) that the light output from the light emitting device when the light emitting device is provided with a work piece with the protective film. In addition to being highly effective in suppressing the decrease in the amount of light emitted from the light-emitting device, the effect of suppressing the appearance of dark shadows in the protective film in the light-emitting device is also high. The visible effect is also increased.
Preferred white pigments include, for example, titanium oxide-based pigments (pigments containing titanium oxide).

The content of the colorant (J) in the composition (III) can be appropriately adjusted according to the type of the colorant (J), for example.

For example, when the colorant (J) is a white pigment, the ratio of the content of the colorant (J) in the thermosetting protective film-forming film to the total mass of the thermosetting protective film-forming film is 0. .1 to 15% by mass, more preferably 0.3 to 12% by mass, even more preferably 0.4 to 9% by mass, for example, 0.5 to 6% by mass. There may be. When the ratio is equal to or higher than the lower limit, the effect of using the colorant (J), that is, the effect of suppressing light absorption in the protective film obtained using the protective film-forming film can be obtained. , higher. Excessive use of the colorant (J) is suppressed when the ratio is equal to or less than the upper limit.

For example, when the colorant (J) is a component other than a white pigment, the ratio of the content of the colorant (J) in the thermosetting protective film-forming film to the total mass of the thermosetting protective film-forming film may be, for example, 0.1 to 15% by weight. When the ratio is equal to or higher than the lower limit, the effect of using the colorant (J) can be obtained more remarkably. Excessive use of the colorant (J) is suppressed when the ratio is equal to or less than the upper limit.

[Curing accelerator (D)]
The composition (III) and the thermosetting protective film-forming film may contain a curing accelerator (D). The curing accelerator (D) is a component for adjusting the curing speed of composition (III).
Preferred curing accelerators (D) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms other than hydrogen atoms) imidazole substituted with a group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Tetraphenylboron salts such as tetraphenylborate and the like are included.

The composition (III) and the curing accelerator (D) contained in the thermosetting protective film-forming film may be of only one type, or may be of two or more types. Any combination and ratio thereof can be selected.

When using the curing accelerator (D), the content of the curing accelerator (D) in the thermosetting protective film-forming film is the total content of the thermosetting component (B) and the thermosetting agent (C) 100 mass It is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 7 parts by mass. When the content of the curing accelerator (D) is at least the lower limit, the effect of using the curing accelerator (D) can be obtained more remarkably. When the content of the curing accelerator (D) is equal to or less than the upper limit, for example, the highly polar curing accelerator (D) adheres in the thermosetting protective film-forming film under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesive interface side with the body is enhanced. As a result, the adhesion reliability of the protective film to the adherend is further improved.

[Filler (E)]
The composition (III) and the thermosetting protective film-forming film may contain a filler (E). By containing the filler (E) in the thermosetting protective film-forming film, the thermal expansion coefficient of the thermosetting protective film-forming film and its cured product (that is, the protective film) can be easily adjusted. is optimized for the object on which the protective film is to be formed, the adhesion reliability of the protective film to the adherend is further improved. In addition, by including the filler (E) in the thermosetting protective film-forming film, the moisture absorption rate of the protective film can be reduced and the heat dissipation can be improved.

The filler (E) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferable inorganic fillers include, for example, powders of silica, stainless steel, alumina, etc.; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; etc.
Among these, the inorganic filler is preferably silica or alumina, more preferably silica.

The average particle size of the filler (E) is not particularly limited, but is preferably 10 to 4000 nm, more preferably 30 to 3500 nm, even more preferably 40 to 1000 nm, and 50 to 600 nm. is particularly preferred. When the average particle size of the filler (E) is in such a range, the effect of using the filler (E) can be obtained more remarkably, and Sa can be adjusted within the above range. easier.
As used herein, the term "average particle size" means the value of the particle size ( _D50 ) at an integrated value of 50% in a particle size distribution curve determined by a laser diffraction scattering method, unless otherwise specified.

The composition (III) and the filler (E) contained in the thermosetting protective film-forming film may be of only one type, or may be of two or more types. can be selected arbitrarily.

When the filler (E) is used, the ratio of the content of the filler (E) to the total mass of the thermosetting protective film-forming film in the thermosetting protective film-forming film is 20 to 75% by mass. is preferred, and more preferably 30 to 70% by mass, for example, it may be either 40 to 67.5% by mass or 50 to 65% by mass. When the ratio is in such a range, it is easier to adjust the thermal expansion coefficient of the thermosetting protective film-forming film and the protective film, and Sa is more easily adjusted within the above range. easier.

[Coupling agent (F)]
The composition (III) and the thermosetting protective film-forming film may contain a coupling agent (F). By using a coupling agent (F) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion reliability of the protective film to the adherend can be improved.

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

Preferred silane coupling agents include, for example, oligomeric silane coupling agents having a plurality of alkoxysilyl groups in one molecule. The oligomeric silane coupling agent is less volatile and has a plurality of alkoxysilyl groups in one molecule, and thus is preferable in that it is effective in improving the durability of the protective film.
Examples of the oligomeric silane coupling agents include epoxy group-containing oligomeric silane coupling agents "X-41-1053", "X-41-1059A", "X-41-1056" and "X- 40-2651” (both manufactured by Shin-Etsu Chemical Co., Ltd.); mercapto group-containing oligomeric silane coupling agents “X-41-1818”, “X-41-1810” and “X-41-1805” (both manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The composition (III) and the coupling agent (F) contained in the thermosetting protective film-forming film may be of only one type, or may be of two or more types. Any combination and ratio thereof can be selected.

When the coupling agent (F) is used, the content of the coupling agent (F) in the thermosetting protective film-forming film is the polymer component (A), the thermosetting component (B) and the thermosetting agent (C ) is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and 0.1 to 2 parts by mass with respect to 100 parts by mass of the total content of More preferred. By setting the content of the coupling agent (F) to be at least the lower limit, it is possible to improve the dispersibility of the filler (E) in the resin and improve the adhesion reliability of the protective film to the adherend. The effect of using the ring agent (F) is more remarkably obtained. Moreover, generation|occurrence|production of outgassing is suppressed more because the said content of a coupling agent (F) is below the said upper limit.

[Crosslinking agent (G)]
The polymer component (A) has a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc., capable of bonding with other compounds such as the acrylic resin (A1) described above. is used, the composition (III) and the thermosetting protective film-forming film may contain a cross-linking agent (G). The cross-linking agent (G) is a component for linking the functional groups in the polymer component (A) with other compounds for cross-linking. Adhesiveness and cohesive force at the time of application to an adherend can be adjusted.

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

The cross-linking agent (G) contained in the composition (III) and the thermosetting protective film-forming film may be of only one type, or may be of two or more types. can be selected arbitrarily.

When the cross-linking agent (G) is used, the content of the cross-linking agent (G) in the composition (III) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer component (A). preferably 0.1 to 10 parts by mass, even more preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (G) is at least the lower limit, the effect of using the cross-linking agent (G) can be obtained more remarkably. Excessive use of the cross-linking agent (G) is suppressed because the content of the cross-linking agent (G) is equal to or less than the upper limit.

[Energy ray-curable resin (H)]
The composition (III) and the thermosetting protective film-forming film may contain an energy ray-curable resin (H). Since the thermosetting protective film-forming film contains the energy ray-curable resin (H), its properties can be changed by irradiation with energy rays.

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

Examples of the acrylate-based compound include compounds described in paragraph 0203 of Japanese Patent Application Laid-Open No. 2019-062107.

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

The energy ray-curable compound used for polymerization may be of one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected.

The composition (III) and the energy ray-curable resin (H) contained in the thermosetting protective film-forming film may be of only one type, may be of two or more types, or may be of two or more types. In that case, their combination and ratio can be arbitrarily selected.

When using the energy ray-curable resin (H), the ratio of the content of the energy ray-curable resin (H) to the total mass of the thermosetting protective film-forming film in the thermosetting protective film-forming film is 1 to It is preferably 30% by mass, more preferably 5 to 25% by mass, even more preferably 10 to 20% by mass.

[Photoinitiator (I)]
When the composition (III) and the thermosetting protective film-forming film contain the energy ray-curable resin (H), a photopolymerization initiator is added to efficiently promote the polymerization reaction of the energy ray-curable resin (H). (I) may be contained.

Examples of the photopolymerization initiator (I) in the composition (III) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-1-(4-( Acetophenone compounds such as 4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4, acylphosphine oxide compounds such as 6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azobisisobutyronitrile and the like azo compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; -methyl-1-[4-(1-methylvinyl)phenyl]propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Moreover, as a photoinitiator (I), photosensitizers, such as an amine, can also be used, for example.

The composition (III) and the photopolymerization initiator (I) contained in the thermosetting protective film-forming film may be only one type, or may be two or more types. , their combination and ratio can be arbitrarily selected.

When the photopolymerization initiator (I) is used, the content of the photopolymerization initiator (I) in the composition (III) is 0.5 parts per 100 parts by mass of the energy ray-curable resin (H). It is preferably 1 to 20 parts by mass.

[General purpose additive (K)]
The composition (III) and the thermosetting protective film-forming film may contain a general-purpose additive (K) within a range that does not impair the effects of the present invention.
The general-purpose additive (K) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited, but preferable examples include plasticizers, antistatic agents, antioxidants, gettering agents, UV absorbers, tackifiers and the like can be mentioned.

The general-purpose additive (K) contained in the composition (III) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds. Any combination and ratio thereof can be selected.
The contents of the composition (III) and the general-purpose additive (K) in the thermosetting protective film-forming film are not particularly limited, and may be appropriately selected according to the purpose.

[solvent]
Composition (III) preferably further contains a solvent. Composition (III) containing a solvent has good handleability.
Although the solvent is not particularly limited, preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone;
Composition (III) may contain only one kind of solvent, or two or more kinds thereof.

Among the solvents contained in the composition (III), more preferable solvents include, for example, methyl ethyl ketone, toluene, ethyl acetate, etc., since the components contained in the composition (III) can be more uniformly mixed.

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

<Method for producing composition for forming thermosetting protective film>
A composition for forming a thermosetting protective film such as composition (III) is obtained by blending each component for constituting the composition.
There are no particular restrictions on the order of addition of each component when blending, and two or more components may be added at the same time.
The method of mixing each component at the time of blending is not particularly limited, and may be selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves. It can be selected as appropriate.
The temperature and time at which each component is added and mixed are not particularly limited as long as each compounded component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30°C.

◎ Energy ray-curable protective film-forming film The curing conditions when energy ray-curing the energy ray-curable protective film-forming film to form a protective film are the degree of curing that the protective film can fully demonstrate its function. It is not particularly limited as long as it is used, and may be appropriately selected according to the type of the energy ray-curable protective film-forming film.
For example, when the energy ray-curable protective film-forming film is cured with the energy ray, the illuminance of the energy ray is preferably 60 to 320 mW/cm ² . It is preferable that the light quantity of the energy beam during the curing is 100 to 1000 mJ/cm ² .

Examples of the energy ray-curable protective film-forming film include those containing an energy ray-curable component (a) and a colorant.
In the energy ray-curable protective film-forming film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.

<Composition (IV) for forming energy ray-curable protective film>
Preferred energy ray-curable protective film-forming compositions include, for example, the energy ray-curable protective film-forming composition (IV) containing the energy ray-curable component (a) and a colorant (in the present specification, , sometimes simply abbreviated as “composition (IV)”) and the like.

[Energy ray-curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and imparts film forming properties, flexibility, etc. to the energy ray-curable protective film-forming film, and forms a hard protective film after curing. It is also a component for forming
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a polymer (a1) having an energy ray-curable group and having a molecular weight of 100 to 80,000. A compound (a2) can be mentioned. At least a part of the polymer (a1) may be crosslinked with a crosslinking agent, or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000)
As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, and the functional Examples include acrylic resins (a1-1) having a structure in which a group that reacts with a group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond have reacted.

Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). groups), epoxy groups, and the like. However, from the viewpoint of preventing corrosion of circuits such as wafers and chips, the functional group is preferably a group other than the carboxyl group.
Among these, the functional group is preferably a hydroxyl group.

- Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. Furthermore, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be employed.

Examples of acrylic monomers having functional groups include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, substituted amino group-containing monomers, and epoxy group-containing monomers.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; non-(meth)acrylic unsaturated such as vinyl alcohol and allyl alcohol alcohol (unsaturated alcohol having no (meth)acryloyl skeleton) and the like.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as acids; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate; be done.

The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.

The acrylic monomer having the functional group, which constitutes the acrylic polymer (a11), may be only one kind, or may be two or more kinds. Any ratio can be selected.

Examples of acrylic monomers having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. Butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate ) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic undecyl acid, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylate The alkyl group constituting the alkyl ester, such as hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), has 1 to 1 carbon atoms. A (meth)acrylic acid alkyl ester having a chain structure of 18 and the like can be mentioned.

Examples of acrylic monomers having no functional group include alkoxyalkyls such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Group-containing (meth)acrylic acid ester; (meth)acrylic acid ester having an aromatic group, including (meth)acrylic acid aryl ester such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and its Derivatives; (meth)acrylic acid esters having a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomer having no functional group, which constitutes the acrylic polymer (a11), may be only one kind, or may be two or more kinds, and when two or more kinds, a combination thereof and ratio can be selected arbitrarily.

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
The non-acrylic monomers constituting the acrylic polymer (a11) may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary You can choose.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural units derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is 0.1 to 50% by mass. preferably 1 to 40% by mass, particularly preferably 3 to 30% by mass. When the ratio is within such a range, the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be cured with energy rays. The content of the functional group makes it possible to adjust the degree of curing of the protective film within a preferred range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one type, or may be of two or more types. Any ratio can be selected.

In the energy ray-curable protective film-forming film, the content ratio of the acrylic resin (a1-1) with respect to the total weight of the energy ray-curable protective film-forming film is preferably 1 to 70% by mass, and 5 to It is more preferably 60% by mass, and particularly preferably 10 to 50% by mass.

- Energy ray-curable compound (a12)
In the energy ray-curable compound (a12), one or more selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with a functional group possessed by the acrylic polymer (a11). and more preferably an isocyanate group as the group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group readily reacts with the hydroxyl group of the acrylic polymer (a11) having the hydroxyl group as the functional group.

The number of energy ray-curable groups in one molecule of the energy ray-curable compound (a12) is not particularly limited. can be selected as appropriate.
For example, the energy ray-curable compound (a12) preferably has 1 to 5, more preferably 1 to 3, energy ray-curable groups in one molecule.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, and the like.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be of only one type, or may be of two or more types. Any combination and ratio can be selected.

In the acrylic resin (a1-1), the ratio of the content of energy ray-curable groups derived from the energy ray-curable compound (a12) to the content of the functional groups derived from the acrylic polymer (a11). is preferably 20 to 120 mol %, more preferably 35 to 100 mol %, particularly preferably 50 to 100 mol %. When the ratio of the content is within such a range, the adhesive strength of the cured product of the energy ray-curable protective film-forming film is further increased. When the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more of the above groups in one molecule), the upper limit of the content ratio may exceed 100 mol %.

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

The polymer (a1) contained in the composition (IV) and the energy ray-curable protective film-forming film may be of only one type, or may be of two or more types, and may be of two or more types. , their combination and ratio can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferred examples include (meth ) acryloyl group, vinyl group and the like.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, but it is a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and an energy ray-curable group. A phenol resin etc. are mentioned.

Among the compounds (a2), low-molecular-weight compounds having an energy ray-curable group include, for example, polyfunctional monomers or oligomers, and acrylate compounds having a (meth)acryloyl group are preferred.
Examples of the acrylate compound include compounds described in paragraph 0195 of “International Publication No. 2017-188197”.

Among the compounds (a2), the epoxy resin having an energy ray-curable group and the phenolic resin having an energy ray-curable group are described, for example, in paragraph 0043 of "JP-A-2013-194102". can use things. Such a resin also corresponds to a resin constituting a thermosetting component to be described later, but is treated as the compound (a2) in the composition (IV).

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

The compound (a2) contained in the composition (IV) and the energy ray-curable protective film-forming film may be only one kind, or may be two or more kinds. Any combination and ratio thereof can be selected.

[Polymer (b) having no energy ray-curable group]
When the composition (IV) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), they further contain a polymer (b) having no energy ray-curable group. It is also preferred to contain
At least a part of the polymer (b) may be crosslinked with a crosslinking agent, or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.
Among these, the polymer (b) is preferably an acrylic resin (hereinafter sometimes abbreviated as “acrylic resin (b-1)”).

Examples of the acrylic resin (b-1) include those similar to the acrylic resin (A1) described above.

The polymer (b) having no energy ray-curable group, contained in the composition (IV) and the energy ray-curable protective film-forming film, may be of one type or two or more types. Well, when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

Examples of the composition (IV) include those containing either one or both of the polymer (a1) and the compound (a2). When the composition (IV) contains the compound (a2), it is preferable that the composition (IV) also contains the polymer (b) having no energy ray-curable group. Moreover, the composition (IV) may contain both the polymer (a1) and the polymer (b) having no energy ray-curable group without containing the compound (a2).

In the energy ray-curable protective film-forming film, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with respect to the total mass of the energy ray-curable protective film-forming film is preferably 5 to 90% by mass. When the ratio is in such a range, it is easy to obtain a uniformly formed protective film-forming film.

[Coloring agent]
The coloring agent is a component for adjusting the light reflectance of the energy ray-curable protective film-forming film and the protective film. A protective film containing a coloring agent is more easily visible under normal conditions, and a protective film provided anywhere on the workpiece is also easier to be visually recognized under normal conditions. is.

The colorant contained in the composition (IV) and the energy ray-curable protective film-forming film is the same as the colorant (J) contained in the composition (III) and the thermosetting protective film-forming film described above. be.

The mode of containing the coloring agent in the composition (IV) and the energy ray-curable protective film-forming film is the same as the mode of containing the coloring agent (J) in the composition (III) and the heat-curable protective film-forming film. you can

For example, the composition (IV) and the energy ray-curable protective film-forming film may contain only one colorant, or two or more colorants. can be selected arbitrarily.
For example, the composition (IV) and the energy ray-curable protective film-forming film may contain, as a coloring agent, only one or two or more organic pigments, or one or more inorganic pigments. It may contain one or more kinds of organic dyes and inorganic pigments.

It is preferable that the colorant is a white pigment, that is, the energy ray-curable protective film-forming film contains a white pigment. In the protective film obtained using such an energy ray-curable protective film-forming film, the reflectance of light (400 to 700 nm) is higher, and the value can be easily adjusted to 20% or more. It is also easy to adjust the maximum reflectance of light (400-700 nm) to 25% or more. Also, a protective film containing a white pigment has such a higher reflectance of light (400-700 nm) that the light output from the light emitting device when the light emitting device is provided with a work piece with the protective film. In addition to being highly effective in suppressing the decrease in the amount of light emitted from the light-emitting device, the effect of suppressing the appearance of dark shadows in the protective film in the light-emitting device is also high. The visible effect is also increased.
Preferred white pigments include, for example, titanium oxide-based pigments (pigments containing titanium oxide).

The colorant contained in composition (IV) can be classified according to its type, and its content can be adjusted as appropriate.
For example, when the colorant is a white pigment, or when the colorant is a component other than the white pigment, the content is the same as the content of the colorant (J) in the composition (III) above. Additionally, the content of the colorant in composition (IV) can be adjusted.
The effect obtained by adjusting the content of the coloring agent in composition (IV) is the same as the effect obtained by adjusting the content of coloring agent (J) in composition (III).

The composition (IV) and the energy ray-curable protective film-forming film correspond to any of the energy ray-curable component (a), the polymer (b), and the colorant, depending on the purpose. It may contain one or more selected from the group consisting of thermosetting components, thermosetting agents, fillers, coupling agents, cross-linking agents, photopolymerization initiators and general-purpose additives.

The thermosetting components, thermosetting agents, fillers, coupling agents, cross-linking agents, photopolymerization initiators and general-purpose additives in the composition (IV) include thermosetting components in the composition (III) ( B), thermosetting agent (C), filler (E), coupling agent (F), cross-linking agent (G), photopolymerization initiator (I) and general-purpose additive (K).

For example, when the composition (IV) contains a thermosetting component, the energy ray-curable protective film-forming film formed by using such a composition (IV) is adhered to an adherend by heating. The force is improved, and the strength of the protective film formed from this energy ray-curable protective film-forming film is also improved.

In the composition (IV), each of the thermosetting component, thermosetting agent, filler, coupling agent, cross-linking agent, photopolymerization initiator, and general-purpose additive may be used alone, or Two or more kinds may be used in combination, and when two or more kinds are used together, the combination and ratio thereof can be arbitrarily selected.

The content of the thermosetting component, thermosetting agent, filler, coupling agent, cross-linking agent, photopolymerization initiator and general-purpose additive in the composition (IV) may be appropriately adjusted according to the purpose, especially Not limited.

The composition (IV) preferably further contains a solvent because its handling properties are improved by dilution.
Examples of the solvent contained in composition (IV) include the same solvents as in composition (III).
Composition (IV) may contain only one kind of solvent, or two or more kinds thereof.
The content of the solvent in composition (IV) is not particularly limited, and may be appropriately selected, for example, according to the types of components other than the solvent.

<Method for producing composition for forming energy ray-curable protective film>
An energy ray-curable protective film-forming composition such as composition (IV) is obtained by blending each component for constituting the composition.
The energy ray-curable protective film-forming composition can be produced, for example, in the same manner as the thermosetting protective film-forming composition described above, except that the types of ingredients are different.

◎Non-curable Protective Film-Forming Film Preferred non-curable protective film-forming films include, for example, those containing a polymer component and a colorant.

<Composition for forming a non-curable protective film (V)>
Preferred non-curable protective film-forming compositions include, for example, the non-curable protective film-forming composition (V) containing the polymer component and the colorant (hereinafter simply referred to as "composition (V )” may be abbreviated).

[Polymer component]
The polymer component is not particularly limited.
More specifically, the polymer component includes, for example, the same non-curable resins as the polymer component (A) exemplified as the component contained in the composition (III).

The polymer components contained in the composition (V) and the non-curable protective film-forming film may be one type or two or more types. Any combination and ratio can be selected.

The content ratio of the polymer component in the non-curable protective film-forming film is preferably 25 to 75% by mass with respect to the total mass of the non-curable protective film-forming film.

[Coloring agent]
The coloring agent is a component for adjusting the light reflectance of the non-curable protective film-forming film and the protective film. A protective film containing a coloring agent is more easily visible under normal conditions, and a protective film provided anywhere on the workpiece is also more easily visible under normal conditions. is.

In this embodiment, the non-curable protective film-forming film is attached to any part of the work (for example, the back surface of a wafer), that is, to the intended part of the object to be protected. assume there is.

The coloring agent contained in the composition (V) and the non-curable protective film-forming film is the same as the coloring agent (J) contained in the composition (III) and the thermosetting protective film-forming film described above. .

The mode of containing the composition (V) and the colorant in the non-curable protective film-forming film is the same as the mode of containing the composition (III) and the colorant (J) in the thermosetting protective film-forming film. good.

For example, the composition (V) and the non-curable protective film-forming film may contain only one colorant or two or more colorants. Any combination and ratio can be selected.
For example, the composition (V) and the non-curable protective film-forming film may contain only one or two or more organic pigments or one or more inorganic pigments as colorants. Alternatively, one or more organic pigments and inorganic pigments may be contained.

It is preferable that the colorant is a white pigment, that is, the non-curable protective film-forming film contains a white pigment. In the protective film obtained using such a non-curable protective film-forming film, the reflectance of light (400 to 700 nm) is higher, and it is easy to adjust the value to 20% or more. It is also easy to adjust the maximum reflectance of light (400-700 nm) to 25% or more. Also, a protective film containing a white pigment has such a higher reflectance of light (400-700 nm) that the light output from the light emitting device when the light emitting device is provided with a work piece with the protective film. In addition to being highly effective in suppressing the decrease in the amount of light emitted from the light-emitting device, the effect of suppressing the appearance of dark shadows in the protective film in the light-emitting device is also high. The visible effect is also increased.
Preferred white pigments include, for example, titanium oxide-based pigments (pigments containing titanium oxide).

The colorant contained in composition (V) can be classified according to its type, and its content can be adjusted as appropriate.
For example, when the colorant is a white pigment, or when the colorant is a component other than the white pigment, the content is the same as the content of the colorant (J) in the composition (III) above. Additionally, the content of the coloring agent in composition (V) can be adjusted.
The effect obtained by adjusting the content of the coloring agent in composition (V) is the same as the effect obtained by adjusting the content of coloring agent (J) in composition (III).

The composition (V) may contain other components that are neither the polymer component nor the colorant, depending on the purpose.
The other components are not particularly limited and can be arbitrarily selected according to the purpose.

Examples of other components in the composition (V) include fillers, coupling agents, cross-linking agents and general-purpose additives.
The filler, coupling agent, cross-linking agent and general-purpose additive in composition (V) include filler (E), coupling agent (F), cross-linking agent (G) and cross-linking agent (G) in composition (III), respectively. The same as general-purpose additives (K) can be mentioned.

The other components contained in the composition (V) and the non-curable protective film-forming film may be one kind or two or more kinds. Any combination and ratio can be selected.

The content of the other components in composition (V) may be appropriately adjusted depending on the purpose, and is not particularly limited.

The composition (V) preferably further contains a solvent because its handling properties are improved by dilution.
The solvent contained in composition (V) includes, for example, the same solvent as in composition (III) described above.
Composition (V) may contain only one kind of solvent, or two or more kinds thereof.
The content of the solvent in composition (V) is not particularly limited, and may be appropriately selected, for example, according to the types of components other than the solvent.

<Method for producing a composition for forming a non-curable protective film>
A composition for forming a non-curable protective film such as composition (V) is obtained by blending each component for constituting the composition.
The non-curable protective film-forming composition can be produced in the same manner as the thermosetting protective film-forming composition described above, except that the types of ingredients are different.

⊚ Example of Protective Film-Formed Film FIG. 1 is a cross-sectional view schematically showing an example of a protective film-formed film according to one embodiment of the present invention. In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there are cases where the main parts are enlarged for convenience, and the dimensional ratios of each component are the same as the actual ones. not necessarily.

The protective film-forming film 13 shown here has a first release film 151 on one surface (in this specification, sometimes referred to as "first surface") 13a, and the first surface 13a is A second peeling film 152 is provided on the other surface (in this specification, sometimes referred to as a "second surface") 13b on the opposite side.
Such a protective film-forming film 13 is suitable for storage as a roll, for example.

When the protective film-forming film 13 is curable, the cured product of the protective film-forming film 13 has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm, and the protective film-forming film 13 is When it is non-curable, the protective film-forming film 13 has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm.
The protective film-forming film 13 can be formed using the protective film-forming composition described above.

Both the first release film 151 and the second release film 152 may be known ones.
The first peeling film 151 and the second peeling film 152 may be the same, or may be different from each other, for example, the peeling force required when peeling from the protective film forming film 13 is different. good too.

In the protective film forming film 13 shown in FIG. 1, one of the first peeling film 151 and the second peeling film 152 is removed, and the resulting exposed surface becomes the surface to be attached to any part of the work. Then, the remaining other of the first peeling film 151 and the second peeling film 152 is removed, and the resulting exposed surface becomes the surface to which a support sheet or dicing sheet to be described later is adhered.

FIG. 1 shows an example in which the release films are provided on both sides (the first surface 13a and the second surface 13b) of the protective film-forming film 13. It may be provided only on one surface, that is, only on the first surface 13a or only on the second surface 13b.

The protective film-forming film of the present embodiment can be attached to any part of the workpiece (the back surface of the semiconductor wafer when the workpiece is a semiconductor wafer) without being used together with a support sheet to be described later. In that case, a release film may be provided on the surface of the protective film-forming film opposite to the surface to be attached to the work, and this release film may be removed at an appropriate timing.

On the other hand, the protective film-forming film of the present embodiment can constitute a protective film-forming composite sheet on which both protective film formation and dicing can be performed by using the protective film-forming film in combination with a support sheet to be described later. Hereinafter, such a protective film-forming composite sheet will be described.

◇ Protective film-forming composite sheet A protective film-forming composite sheet according to an embodiment of the present invention comprises a support sheet and a protective film-forming film provided on one surface of the support sheet, The protective film-forming film is the protective film-forming film according to one embodiment of the present invention described above.

In this specification, as long as the laminated structure of the support sheet and the cured product of the protective film-forming film is maintained even after the protective film-forming film is cured, the laminated structure is referred to as a "protective film. "Forming Composite Sheet".

Each layer constituting the protective film-forming composite sheet will be described in detail below.

⊚ Support Sheet The support sheet may consist of one layer (single layer), or may consist 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, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

The support sheet may be transparent, opaque, or colored depending on the purpose.
For example, when the protective film-forming film has energy ray-curable properties, the support sheet preferably transmits energy rays.

Examples of the support sheet include those comprising a substrate and a pressure-sensitive adhesive layer provided on one surface of the substrate; those comprising only a substrate; and the like. When the support sheet has a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is arranged between the substrate and the protective film-forming film in the protective film-forming composite sheet.

When a support sheet comprising a substrate and an adhesive layer is used, the adhesion and peelability between the support sheet and the protective film-forming film can be easily adjusted in the protective film-forming composite sheet.
When a support sheet consisting of only a substrate is used, a composite sheet for forming a protective film can be produced at low cost.

Examples of the protective film-forming composite sheet of the present embodiment will be described below for each type of support sheet, with reference to the drawings.

⊙ Example of Protective Film-Forming Composite Sheet FIG. 2 is a cross-sectional view schematically showing an example of a protective film-forming composite sheet according to an embodiment of the present invention.
In the drawings after FIG. 2, the same constituent elements as those shown in already explained figures are given the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.

The composite sheet 101 for forming a protective film shown here includes a support sheet 10 and a protective film provided on one surface (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10. and a forming film 13 .
The support sheet 10 includes a substrate 11 and an adhesive layer 12 provided on one surface (first surface) 11 a of the substrate 11 . In the protective film-forming composite sheet 101 , the pressure-sensitive adhesive layer 12 is arranged between the substrate 11 and the protective film-forming film 13 .
That is, the protective film-forming composite sheet 101 is configured by laminating a substrate 11, an adhesive layer 12, and a protective film-forming film 13 in this order in the thickness direction.
The first surface 10a of the support sheet 10 is the same as the surface 12a of the pressure-sensitive adhesive layer 12 on the side opposite to the substrate 11 side (in this specification, this may be referred to as the "first surface").

The protective film-forming composite sheet 101 further includes a jig adhesive layer 16 and a release film 15 on the protective film-forming film 13 .
In the protective film-forming composite sheet 101, the protective film-forming film 13 is laminated on the entire surface or substantially the entire surface of the first surface 12a of the adhesive layer 12, and the adhesive layer 12 side of the protective film-forming film 13 is opposite to the adhesive layer 12 side. A jig adhesive layer 16 is laminated on a portion of the surface 13a (which may be referred to herein as a "first surface"), that is, a region in the vicinity of the peripheral edge. Furthermore, of the first surface 13 a of the protective film forming film 13 , the region where the jig adhesive layer 16 is not laminated and the surface of the jig adhesive layer 16 opposite to the protective film forming film 13 side are formed. A release film 15 is laminated on 16a (which may be referred to as a "first surface" in this specification).

Not only in the case of the protective film-forming composite sheet 101, but in the protective film-forming composite sheet of the present embodiment, the release film (for example, the release film 15 shown in FIGS. 3 to 5 described later) has an arbitrary configuration. The protective film-forming composite sheet of the present embodiment may or may not have a release film.

The jig adhesive layer 16 is used to fix the protective film-forming composite sheet 101 to a jig such as a ring frame.
The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. You may have a structure.

The protective film forming film 13 can suppress the absorption of light as a protective film, and can form a film that is easily visible under normal conditions.

The protective film-forming composite sheet 101 is a state in which the release film 15 is removed, and any part of the work is attached to the first surface 13 a of the protective film-forming film 13 , and the jig adhesive layer 16 is attached. The first surface 16a of is attached to a jig such as a ring frame for use. When the workpiece is a semiconductor wafer, the back surface of the semiconductor wafer is attached to the first surface 13 a of the protective film forming film 13 .

FIG. 3 is a cross-sectional view schematically showing another example of the protective film-forming composite sheet according to one embodiment of the present invention.
In the protective film-forming composite sheet 102 shown here, the protective film-forming film has a different shape and size, and the jig adhesive layer is not on the first surface of the protective film-forming film, but on the first surface of the pressure-sensitive adhesive layer. It is the same as the protective film-forming composite sheet 101 shown in FIG. 1 except that it is laminated.

More specifically, in the protective film-forming composite sheet 102, the protective film-forming film 23 extends in a partial region of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 ( left-to-right direction). Further, a jig adhesive layer 16 is laminated on a region of the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated, that is, a region in the vicinity of the peripheral portion. Then, the surface of the protective film forming film 23 opposite to the pressure-sensitive adhesive layer 12 side (one surface, in this specification, may be referred to as "first surface") 23a, and the jig adhesive layer A peeling film 15 is laminated on the first surface 16a of 16 .
Reference numeral 23b denotes a surface (the other surface) opposite to the first surface 23a of the protective film-forming film 23 (in other words, the pressure-sensitive adhesive layer 12 side). ).

FIG. 4 is a cross-sectional view schematically showing still another example of the protective film-forming composite sheet according to one embodiment of the present invention.
The protective film-forming composite sheet 103 shown here is the same as the protective film-forming composite sheet 102 shown in FIG. 3 except that the jig adhesive layer 16 is not provided.

FIG. 5 is a cross-sectional view schematically showing still another example of the protective film-forming composite sheet according to one embodiment of the present invention.
The protective film-forming composite sheet 104 shown here is the same as the protective film-forming composite sheet 101 shown in FIG.
The support sheet 20 consists of the base material 11 only.
That is, the protective film-forming composite sheet 104 is configured by laminating the substrate 11 and the protective film-forming film 13 in the thickness direction thereof.
A surface (first surface, one surface) 20 a of the support sheet 20 on the side of the protective film-forming film 13 is the same as the first surface 11 a of the substrate 11 .
The base material 11 has adhesiveness at least on its first surface 11a.

The composite sheet for forming a protective film of the present embodiment is not limited to those shown in FIGS. 2 to 5, and part of the configuration of those shown in FIGS. Alternatively, it may be deleted, or another configuration may be added to what has been described so far.

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

○ Substrate The substrate is sheet-like or film-like, and examples of its constituent materials include various resins.
Examples of the resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); Polyolefin; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene (copolymer obtained using); polyvinyl chloride, vinyl chloride resin such as vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Polyesters such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylate; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin;
Examples of the resin include polymer alloys such as mixtures of the polyester and other resins. The polymer alloy of the polyester and the resin other than polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; Also included are resins.

The number of resins constituting the base material may be one, or two or more, and if two or more, the combination and ratio thereof can be arbitrarily selected.

The substrate may consist of one layer (single layer) or may consist of a plurality of layers of two or more layers. The combination of these multiple layers is not particularly limited.

The thickness of the substrate is preferably 50-300 μm, more preferably 60-100 μm. When the thickness of the substrate is within such a range, the flexibility of the protective film-forming composite sheet and the aptitude for application to a wafer are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material. means.

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

The substrate may be transparent or opaque, colored according to purpose, or may be deposited with other layers.
For example, when the protective film-forming film has energy ray-curable properties, the substrate preferably transmits energy rays.

The substrate is roughened by sandblasting, solvent treatment, etc., in order to adjust the adhesiveness with the layer provided thereon (e.g., adhesive layer, protective film-forming film, or other layer); corona Oxidation treatment such as discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; lipophilic treatment; hydrophilic treatment, etc. may be applied to the surface. Further, the substrate may have a primer-treated surface.

The base material may have tackiness on at least one surface by containing a specific range of components (eg, resin, etc.).

A base material can be manufactured by a well-known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

O Adhesive Layer The adhesive layer is sheet-like or film-like and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins.

The pressure-sensitive adhesive layer may consist of one layer (single layer) or may consist of two or more layers. The combination of these multiple layers is not particularly limited.

Although the thickness of the adhesive layer is not particularly limited, it is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer. means the thickness of

The pressure-sensitive adhesive layer may be either energy ray-curable or non-energy ray-curable. The energy ray-curable pressure-sensitive adhesive layer can adjust physical properties before and after curing.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the pressure-sensitive adhesive layer can be formed on the target site by applying the pressure-sensitive adhesive composition to the surface on which the pressure-sensitive adhesive layer is to be formed, and drying it as necessary. The content ratio of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer.

In the pressure-sensitive adhesive layer, the ratio of the total content of one or more components described later in the pressure-sensitive adhesive layer to the total weight of the pressure-sensitive adhesive layer is 100% by mass or less.
Similarly, in the pressure-sensitive adhesive composition, the ratio of the total content of one or more components described later in the pressure-sensitive adhesive composition to the total weight of the pressure-sensitive adhesive composition is 100% by mass or less.

The coating and drying of the pressure-sensitive adhesive composition can be carried out, for example, in the same manner as in the coating and drying of the protective film-forming composition described above.

When a pressure-sensitive adhesive layer is provided on a substrate, for example, the pressure-sensitive adhesive composition may be applied onto the substrate and dried as necessary. Further, for example, the adhesive composition is applied on the release film and dried as necessary to form an adhesive layer on the release film, and the exposed surface of the adhesive layer is applied to the substrate. You may laminate|stack an adhesive layer on a base material by bonding together to one surface of. In this case, the release film may be removed either during the manufacturing process or during the use process of the protective film-forming composite sheet.

When the pressure-sensitive adhesive layer is energy ray-curable, the energy ray-curable pressure-sensitive adhesive composition includes, for example, non-energy ray-curable adhesive resin (I-1a) (hereinafter referred to as “adhesive resin (I- 1a)") and an energy ray-curable compound (I-1); A pressure-sensitive adhesive composition (I- 2); an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.

When the pressure-sensitive adhesive layer is non-energy ray-curable, the non-energy ray-curable pressure-sensitive adhesive composition includes, for example, the pressure-sensitive adhesive composition containing the non-energy ray-curable adhesive resin (I-1a). (I-4) and the like.

[Non-energy ray-curable adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from a (meth)acrylic acid alkyl ester.
Examples of the (meth)acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. is preferred.

It is preferable that the acrylic polymer further has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group reacts with a cross-linking agent described later to become a starting point for cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. and those capable of introducing an unsaturated group into the side chain of the acrylic polymer.

Examples of functional group-containing monomers include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.

The acrylic polymer may further have structural units derived from other monomers in addition to structural units derived from (meth)acrylic acid alkyl esters and structural units derived from functional group-containing monomers.
The other monomer is not particularly limited as long as it is copolymerizable with (meth)acrylic acid alkyl ester or the like.
Examples of the other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile and acrylamide.

The pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), the pressure-sensitive adhesive composition (I-3) and the pressure-sensitive adhesive composition (I-4) (hereinafter, including these pressure-sensitive adhesive compositions and abbreviated as “adhesive compositions (I-1) to (I-4)”), the structural units of the acrylic resin such as the acrylic polymer may be only one type, or two types. or more, and when there are two or more kinds, their combination and ratio can be arbitrarily selected.

In the acrylic polymer, the content of structural units derived from functional group-containing monomers is preferably 1 to 35% by mass with respect to the total amount of structural units.

The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4) may be one type, two or more types, or two or more types. In that case, their combination and ratio can be arbitrarily selected.

In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-4), the content ratio of the adhesive resin (I-1a) with respect to the total mass of the adhesive layer is preferably 5 to 99% by mass.

[Energy ray-curable adhesive resin (I-2a)]
The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.

The unsaturated group-containing compound is capable of bonding with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group. It is a compound having a group.
Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth)acryloyl group is preferred.
Groups capable of bonding with functional groups in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group. etc.

Examples of the unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloylisocyanate, glycidyl (meth)acrylate, and the like.

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) or (I-3) may be only one type, may be two or more types, or may be two or more types. , the combination and ratio thereof can be arbitrarily selected.

In the adhesive layer formed from the adhesive composition (I-2) or (I-3), the content ratio of the adhesive resin (I-2a) with respect to the total mass of the adhesive layer is 5 to It is preferably 99% by mass.

[Energy ray-curable compound]
Examples of the energy ray-curable compound in the pressure-sensitive adhesive compositions (I-1) and (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by energy ray irradiation. be done.

Among energy ray-curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4 -polyvalent (meth)acrylates such as butylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; urethane (meth)acrylates; polyester (meth)acrylates; polyether (meth)acrylates; meth)acrylate and the like.
Among energy ray-curable compounds, oligomers include, for example, oligomers obtained by polymerizing the above-exemplified monomers.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one kind, may be two or more kinds, or may be two or more kinds. In that case, their combination and ratio can be arbitrarily selected.

In the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (I-1) or (I-3), the content ratio of the energy ray-curable compound to the total weight of the pressure-sensitive adhesive layer is 1 to 95 mass. %.

[Crosslinking agent]
As the adhesive resin (I-1a), in addition to the structural unit derived from the (meth)acrylic acid alkyl ester, when using the acrylic polymer having a structural unit derived from a functional group-containing monomer, the adhesive composition (I -1) or (I-4) preferably further contains a cross-linking agent.
Further, as the adhesive resin (I-2a), for example, when using the acrylic polymer having the same structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a), the adhesive composition (I-2) or (I-3) may further contain a cross-linking agent.

The cross-linking agent, for example, reacts with the functional group to cross-link the adhesive resins (I-1a) or the adhesive resins (I-2a).
Examples of cross-linking agents include tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents (cross-linking agents having isocyanate groups) such as adducts of these diisocyanates; epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( aziridinyl cross-linking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine (cross-linking agents having an aziridinyl group); metal chelate cross-linking agents such as aluminum chelate (metal cross-linking agents having a chelate structure); isocyanurate-based cross-linking agents (cross-linking agents having an isocyanuric acid skeleton);

The cross-linking agents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be of only one type, or may be of two or more types. You can choose.

In the adhesive composition (I-1) or (I-4), the content of the cross-linking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin (I-1a). is preferably
In the adhesive composition (I-2) or (I-3), the content of the cross-linking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). is preferably

[Photoinitiator]
Adhesive compositions (I-1), (I-2) and (I-3) (hereinafter, these adhesive compositions are collectively referred to as "adhesive compositions (I-1) to (I-3) ”) may further contain a photopolymerization initiator. The adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator undergo sufficient curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include those similar to the photopolymerization initiator (I) described above.

The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be only one kind, or may be two or more kinds, and when they are two or more kinds, their combination and ratio are Can be selected arbitrarily.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray-curable compound.
In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). .
In the adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 0.01 with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. It is preferably 20 parts by mass.

[Other additives]
The pressure-sensitive adhesive compositions (I-1) to (I-4) may contain other additives that do not fall under any of the above components within the range that does not impair the effects of the present invention.
Examples of other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. , a reaction retardant, a cross-linking accelerator (catalyst), and other known additives.
Note that the reaction retarder is, for example, the adhesive composition (I-1) to (I-4) during storage due to the action of a catalyst mixed in the adhesive composition (I-1) to (I-4). In I-4), it is a component that suppresses the progress of an unintended cross-linking reaction. Examples of the reaction retarder include those that form a chelate complex by chelating the catalyst, more specifically those having two or more carbonyl groups (-C(=O)-) in one molecule. mentioned.

The other additives contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be one type or two or more types, and when there are two or more types, their combination and ratio are Can be selected arbitrarily.

The content of other additives in the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately selected according to the type.

[solvent]
The adhesive compositions (I-1) to (I-4) may contain a solvent. Since the pressure-sensitive adhesive compositions (I-1) to (I-4) contain a solvent, the coating suitability to the surface to be coated is improved.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, n-hexane, and the like. aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

The solvents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be one kind, or may be two or more kinds, and when there are two or more kinds, combinations thereof and ratio can be selected arbitrarily.

The solvent content of the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited, and may be adjusted as appropriate.

○ Manufacturing method of adhesive composition The adhesive composition such as the adhesive compositions (I-1) to (I-4) includes the adhesive and, if necessary, components other than the adhesive. It is obtained by blending each component for constituting the agent composition.
The pressure-sensitive adhesive composition can be produced, for example, in the same manner as in the case of the thermosetting protective film-forming composition described above, except that the types of ingredients are different.

◇Method for producing a composite sheet for forming a protective film In the composite sheet for forming a protective film, the above layers are laminated so as to have a corresponding positional relationship, and if necessary, the shape of some or all of the layers is adjusted. Therefore, it can be manufactured. The method for forming each layer is as described above.

For example, when a pressure-sensitive adhesive layer is laminated on a substrate when producing a support sheet, the above-described pressure-sensitive adhesive composition may be applied onto the substrate and dried as necessary.
Alternatively, the adhesive composition is applied onto the release film and dried as necessary to form an adhesive layer on the release film, and the exposed surface of the adhesive layer is placed on one side of the substrate. A pressure-sensitive adhesive layer can also be laminated on a base material by the method of bonding to the surface of . At this time, the pressure-sensitive adhesive composition is preferably applied to the release-treated surface of the release film.
So far, the case of laminating the pressure-sensitive adhesive layer on the substrate has been exemplified, but the above-described method can also be applied, for example, to the case of laminating the intermediate layer or the other layers on the substrate.

On the other hand, for example, when a protective film-forming film is laminated on the adhesive layer already laminated on the substrate, the protective film-forming composition is applied onto the adhesive layer to form a protective film. It is possible to form films directly. Layers other than the protective film-forming film can also be laminated on the adhesive layer in the same manner using the composition for forming this layer. In this way, a new layer (hereinafter abbreviated as "second layer") is formed on any layer (hereinafter abbreviated as "first layer") laminated on the base material, When forming a continuous two-layer laminated structure (in other words, a laminated structure of a first layer and a second layer), a composition for forming the second layer is applied onto the first layer. Then, if necessary, a method of drying can be applied.
However, the second layer is formed in advance on a release film using a composition for forming it, and the side opposite to the side of the formed second layer that is in contact with the release film It is preferable to form a continuous two-layer laminated structure by bonding the exposed surface of the first layer to the exposed surface of the first layer. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after the laminated structure is formed.
Here, the case of laminating the protective film-forming film on the pressure-sensitive adhesive layer is taken as an example, but for example, when laminating the intermediate layer or the other layer on the pressure-sensitive adhesive layer, the target laminated structure is Can be selected arbitrarily.

In this way, all layers other than the base material constituting the protective film-forming composite sheet can be formed in advance on a release film and laminated by a method of bonding them to the surface of the desired layer. A composite sheet for forming a protective film may be produced by appropriately selecting a layer that employs such a step as leverage.

The protective film-forming composite sheet is usually stored with a release film attached to the surface of the outermost layer (for example, protective film-forming film) opposite to the support sheet. Therefore, on this release film (preferably its release-treated surface), a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of this layer opposite to the side in contact with the release film by any of the above methods. Then, the protective film-forming composite sheet with the release film is obtained by leaving the release film in a bonded state without removing the release film.

◇Method for manufacturing a workpiece with a protective film (method for using a composite sheet for forming a protective film)
The composite sheet for forming a protective film can be used for manufacturing a workpiece with a protective film.
As an example of a method for manufacturing a work piece with a protective film, a work piece obtained by processing a work piece and a protective film provided at any part of the work piece piece are protected. In the method for manufacturing a film-attached workpiece, the protective film is formed from the protective film-forming film in the protective film-forming composite sheet according to the embodiment of the present invention, and the protective film is When the forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, it is attached to any part of the work. The protective film-forming film after being coated is the protective film, and the manufacturing method includes attaching the protective film-forming film in the protective film-forming composite sheet to a target location of the work, A pasting step of producing a first laminate in which the composite sheet for forming a protective film is provided (laminated) on the work, and after the pasting step, the work is processed to produce the workpiece. and a cutting step of cutting the protective film-forming film or the protective film after the sticking step, and when the protective film-forming film is curable, the sticking step is further performed. and a curing step of subsequently forming the protective film by curing the protective film-forming film.

Which of the protective film-forming film and the protective film is handled in each step after the sticking step is determined by the timing of forming the protective film. When the protective film-forming film is non-curing, it is the protective film that is handled after the application step in any step. When the protective film-forming film is curable, it is the protective film-forming film that is handled before the curing step, and the protective film is handled after the curing step.

As an example of a method for manufacturing a protective film-attached work piece when the work is a semiconductor wafer, that is, a method for manufacturing a protective film-attached semiconductor chip, a semiconductor chip and a protective film provided on the back surface of the semiconductor chip are provided, A method for manufacturing a semiconductor chip with a protective film, wherein the protective film is formed from the protective film-forming film in the protective film-forming composite sheet according to the embodiment of the present invention, and the protective film is When the forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, it is attached to the back surface of the semiconductor wafer. The subsequent protective film-forming film is the protective film, and the manufacturing method includes attaching the protective film-forming film in the protective film-forming composite sheet to the back surface of the semiconductor wafer, thereby removing the protective film from the semiconductor wafer. A bonding step of manufacturing a first laminate having the protective film-forming composite sheet provided on the back surface (laminated), and the semiconductor chip is manufactured by dividing the semiconductor wafer after the bonding step. A dividing step, and a cutting step of cutting the protective film or the protective film after the attaching step, and when the protective film forming film is curable, further after the attaching step and a curing step of forming the protective film by curing the protective film-forming film.

According to the above manufacturing method, it is possible to obtain a protective film-attached workpiece having a protective film that can suppress the absorption of light and is easily visible under normal conditions.

The manufacturing method includes a manufacturing method with the curing step (in this specification, may be referred to as "manufacturing method (1)") and a manufacturing method without the curing step (in this specification, may be referred to as "manufacturing method (2)").
These manufacturing methods will be described in sequence below.

<<Manufacturing method (1)>>
The manufacturing method (1) manufactures a workpiece with a protective film, which includes a workpiece obtained by machining a workpiece and a protective film provided at any part of the workpiece. In the method, the protective film is formed from the protective film-forming film in the protective film-forming composite sheet according to one embodiment of the present invention, and the protective film-forming film is curable. Therefore, the cured product of the protective film-forming film is the protective film, and the manufacturing method includes attaching the protective film-forming film in the protective film-forming composite sheet to a target location on the work. a lamination step of producing a first laminate in which the composite sheet for forming a protective film is provided (laminated) on the work; and a cutting step of cutting the protective film-forming film or the protective film after the pasting step, and curing the protective film-forming film after the pasting step to form the protective film. and a curing step.

When the workpiece is a semiconductor wafer, the manufacturing method (1) is a method for manufacturing a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. , the protective film is formed from the protective film-forming film in the protective film-forming composite sheet, and since the protective film-forming film is curable, the cured product of the protective film-forming film is the The protective film is a protective film, and the manufacturing method is such that the protective film-forming composite sheet is provided on the semiconductor wafer by attaching the protective film-forming film in the protective film-forming composite sheet to the back surface of the semiconductor wafer. a bonding step of fabricating a first stacked body (laminated); after the bonding step, a dividing step of fabricating the semiconductor chips by dividing the semiconductor wafer; Manufacture of a semiconductor chip with a protective film, comprising: a protective film-forming film or a cutting step of cutting the protective film; and a curing step of curing the protective film-forming film after the attaching step to form the protective film. method.

When the workpiece is a semiconductor wafer, the order of performing the dividing step and the cutting step can be arbitrarily selected according to the purpose. Alternatively, the dividing step may be performed after performing the cutting step.
In the present embodiment, when the division of the semiconductor wafer and the cutting of the protective film-forming film or the protective film are performed continuously by the same operation without interruption regardless of the order, the dividing step and the cutting It is assumed that the processes are carried out simultaneously.

Both the dividing step and the cutting step can be performed by known methods depending on the order in which they are performed.

When the cutting step is performed after the dividing step, the semiconductor wafer can be divided (in other words, separated into individual pieces) by, for example, stealth dicing (registered trademark) or laser dicing.
Stealth dicing (registered trademark) is the following method. That is, first, in the interior of the semiconductor wafer, a location to be divided is set, and with this location as a focal point, laser light is irradiated so as to converge on this focal point, thereby forming a modified layer inside the semiconductor wafer. . Unlike other parts of the semiconductor wafer, the modified layer of the semiconductor wafer has been modified by the irradiation of the laser beam and has a weaker strength. Therefore, when a force is applied to the semiconductor wafer, a crack extending in the direction of both sides of the semiconductor wafer is generated in the modified layer inside the semiconductor wafer, and becomes a starting point for splitting (cutting) the semiconductor wafer. Then, a force is applied to the semiconductor wafer to divide the semiconductor wafer at the portion of the modified layer to fabricate semiconductor chips.

When the cutting step is performed after the dividing step, the protective film-forming film or the protective film is cut by, for example, cutting the protective film-forming film or the protective film in a direction parallel to the bonding surface of the semiconductor chip. It can be done by pulling, so-called expanding. The expanded protective film-forming film or protective film is cut along the outer periphery of the semiconductor chip. Cutting by such expansion is preferably performed at a low temperature such as -20 to 5°C.

When the dividing step and the cutting step are performed simultaneously, the semiconductor wafer is divided and the protective film is formed by dicing such as blade dicing using a blade, laser dicing by laser irradiation, or water dicing by spraying water containing an abrasive. cutting of the film or overcoat can be performed at the same time.
In addition, by expanding both the semiconductor wafer on which the modified layer is formed by Stealth Dicing (registered trademark) and which is not divided, and the protective film-forming film or protective film in the same manner as above, the semiconductor The division of the wafer and the cutting of the protective film forming film or protective film can also be performed at the same time.

When the dividing step is performed after the cutting step, the protective film-forming film or the protective film can be cut without dividing the semiconductor wafer by the same dicing method as described above. Wafers can be separated by breaking.

FIG. 6 is a cross-sectional view for schematically explaining an example of the manufacturing method (1) in which the work is a semiconductor wafer. Here, a manufacturing method using the protective film-forming composite sheet 101 shown in FIG. 2 will be described.

<Affixing process>
In the affixing step, the protective film-forming composite sheet 101 from which the release film 15 has been removed is used, and as shown in FIG. , is attached to the back surface 9b of the semiconductor wafer 9 as a work. As a result, a first laminate 901 including the semiconductor wafer 9 and the protective film forming composite sheet 101 provided on the back surface 9b of the semiconductor wafer 9 is produced.

In the attaching step, the protective film forming film 13 may be heated to be softened and attached to the semiconductor wafer 9 .
Here, in the semiconductor wafer 9, illustration of bumps and the like on the circuit surface 9a is omitted. This also applies to subsequent drawings.

The semiconductor wafer 9 may have its back surface ground so as to have a desired thickness. That is, the back surface 9b of the semiconductor wafer 9 may be a ground surface.

<Curing process>
After the sticking process, in the curing process, a protective film 13' is formed by curing the protective film forming film 13, as shown in FIG. 6(b).
In this embodiment, the cured product obtained by curing the protective film forming film 13 after being attached to the semiconductor wafer 9 is used as the protective film regardless of whether or not it is cut.

By performing the curing step, the protective film-forming composite sheet 101 becomes a protective film-forming composite sheet 1011 in which the protective film-forming film 13 serves as the protective film 13 ′, and the semiconductor wafer 9 and the back surface 9 b thereof are provided. A cured first laminate 9011 is obtained, which is composed of the composite sheet 1011 for forming a protective film.
Reference numeral 13a' indicates the first surface of the protective film 13' corresponding to the first surface 13a of the protective film-forming film 13, and reference numeral 13b' indicates the second surface 13b of the protective film-forming film 13. The second side of membrane 13' is shown.

In the curing step, when the protective film-forming film 13 is thermosetting, the protective film 13 ′ is formed by heating the protective film-forming film 13 . When the protective film-forming film 13 is energy ray-curable, the protective film 13 ′ is formed by irradiating the protective film-forming film 13 with energy rays through the support sheet 10 .

In the curing step, the curing conditions for the protective film-forming film 13, that is, the heating temperature and heating time during thermosetting, and the illuminance and light intensity of energy rays during curing with energy rays are as described above.

<Dividing process, cutting process>
In the present embodiment, after the bonding process, a dividing process for fabricating semiconductor chips by dividing the semiconductor wafer 9 and a cutting process for cutting the protective film 13' are performed.
The order of performing the dividing step and the cutting step is not limited as described above.
The method of performing the dividing step and the cutting step is as described above.
By performing the dividing step and the cutting step, as shown in FIG. 6(c), a semiconductor chip 90 as a workpiece, a protective film 130' after cutting provided on the back surface 90b of the semiconductor chip 90, A plurality of semiconductor chips 91 with a protective film are obtained. A semiconductor chip 91 with a protective film is a workpiece with a protective film. The plurality of semiconductor chips 91 with protective films are all aligned on one support sheet 10, and these semiconductor chips 91 with protective films and the support sheet 10 form a semiconductor chip group 910 with protective films. Configure.

Reference numeral 130a' indicates the first surface of the protective film 130' after cutting corresponding to the first surface 13a' of the protective film 13', and reference numeral 130b' corresponds to the second surface 13b' of the protective film 13'. The second surface of the protective film 130' after cutting is shown.
A reference numeral 90 a denotes a circuit surface of the semiconductor chip 90 corresponding to the circuit surface 9 a of the semiconductor wafer 9 .

<Pickup process>
After the dividing step and the cutting step, as shown in FIG. 6D, a semiconductor chip 91 with a protective film (a semiconductor chip 90 having a protective film 130' after cutting) is separated from the support sheet 10 and picked up. The semiconductor chip 91 with the protective film can be taken out from the semiconductor chip group 910 with the protective film by performing the pick-up process.
Here, an arrow P indicates the direction of pick-up.

A well-known method can be used to pick up the semiconductor chip 91 with a protective film. For example, the separation means 7 for separating the semiconductor chip 91 with the protective film from the support sheet 10 may be a vacuum collet or the like.

<Other processes>
The manufacturing method (1) may have other processes that do not correspond to any of the sticking process, the curing process, the dividing process, the cutting process, and the picking up process.
The types of the other steps and the timing of performing them can be arbitrarily selected according to the purpose, and are not particularly limited.

As the other step, for example, the second surface of the protective film-forming film or the protective film (in FIG. 6, for example, the second surface 13b of the protective film-forming film 13 or the second surface 13b' of the protective film 13') ) is irradiated with a laser beam to print on the protective film-forming film or the protective film (not shown). The print is applied to the second surface of the protective film-forming film or protective film.

In the printing step, the protective film-forming film or the second surface of the protective film can be irradiated with a laser beam from the outside of the protective film-forming composite sheet on the support sheet side through the support sheet.

A printing process can be performed by a well-known method.

In this embodiment, the printing process can be performed after the attaching process, and is preferably performed between the curing process and the dividing process, and between the curing process and the cutting process.

<Timing for performing the curing step>
So far, the case where the curing process is performed between the attaching process and the dividing process and between the attaching process and the cutting process has been described, but in the manufacturing method (1), the timing of performing the curing process is limited to this. not. For example, in the production method (1), the curing step includes between the printing step and the dividing step, between the printing step and the cutting step, between the dividing step and the cutting step, between the dividing step and the pick-up step, and cutting. It may be performed either between the process and the pick-up process, or after the pick-up process.

<<Manufacturing method (2)>>
The manufacturing method (2) manufactures a workpiece with a protective film, which includes a workpiece obtained by machining a workpiece and a protective film provided at any part of the workpiece. In the method, the protective film is formed from the protective film-forming film in the protective film-forming composite sheet according to one embodiment of the present invention, and the protective film-forming film is non-curable. Therefore, the protective film-forming film after being attached to any part of the work is the protective film, and the manufacturing method includes: A pasting step of producing a first laminate in which the protective film-forming composite sheet is provided (laminated) on the work by pasting it to a target location on the work; and after the pasting step, the A processing step of fabricating the workpiece by processing the workpiece, and a cutting step of cutting the protective film after the attaching step. In the manufacturing method (2), the protective film-forming film after being adhered to the work in the adhering step is the protective film.
Manufacturing method (2) is the same as manufacturing method (1), except that the protective film-forming film after being attached to the work is used as the protective film as it is, regardless of the type of work and does not include the curing step. is.

When the workpiece is a semiconductor wafer, the manufacturing method (2) is a method of manufacturing a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. The protective film is formed from the protective film-forming film in the protective film-forming composite sheet, and since the protective film-forming film is non-curable, the semiconductor wafer for obtaining the semiconductor chip The protective film-forming film after being attached to the back surface of the semiconductor wafer is the protective film, and the manufacturing method includes attaching the protective film-forming film in the protective film-forming composite sheet to the back surface of the semiconductor wafer. By, a bonding step of producing a first laminate in which the protective film forming composite sheet is provided (laminated) on the semiconductor wafer, and the semiconductor wafer is divided after the bonding step, thereby A method for manufacturing a semiconductor chip with a protective film includes a dividing step for producing chips, and a cutting step for cutting the protective film after the attaching step.

Up to this point, the method for manufacturing a protective film-attached work piece using the protective film-forming composite sheet 101 shown in FIG. 2 has been mainly described. is not limited to this.
For example, even if a protective film-forming composite sheet other than the protective film-forming composite sheet 101 shown in FIG. 2, such as the protective film-forming composite sheet shown in FIGS. can be manufactured.

◇Method for manufacturing workpiece with protective film (How to use protective film forming film)
A protective film-forming film that does not constitute the protective film-forming composite sheet can also be used for the production of the protective film-attached workpiece.
Another example of the method for manufacturing a workpiece with a protective film includes a workpiece obtained by machining a workpiece, and a protective film provided on any part of the workpiece. A method for manufacturing a workpiece with a protective film, wherein the protective film is formed from the protective film-forming film according to one embodiment of the present invention, which does not constitute the protective film-forming composite sheet When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, the work The protective film-forming film after being attached to any part of the workpiece is the protective film. affixing step of producing a second laminate in which the protective film-forming film or protective film is provided (laminated), and after the affixing step, fabricating the workpiece by processing the workpiece and a cutting step of cutting the protective film-forming film or the protective film after the pasting step, and when the protective film-forming film is curable, further after the pasting step and a curing step of forming the protective film by curing the protective film-forming film.

Which of the protective film-forming film and the protective film is handled in each step after the sticking step is determined by the timing of forming the protective film. When the protective film-forming film is non-curing, it is the protective film that is handled after the application step in any step. When the protective film-forming film is curable, it is the protective film-forming film that is handled before the curing step, and the protective film is handled after the curing step.

Another example of a method for manufacturing a work piece with a protective film when the work is a semiconductor wafer, that is, a semiconductor chip with a protective film, includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. Further, in the method for manufacturing a semiconductor chip with a protective film, the protective film is formed from the protective film-forming film according to one embodiment of the present invention, which does not constitute the protective film-forming composite sheet. When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, the semiconductor The protective film-forming film after being attached to the back surface of the wafer is the protective film, and the manufacturing method includes attaching the protective film-forming film to the back surface of the semiconductor wafer so that the protective film is attached to the back surface of the semiconductor wafer. A bonding step of fabricating a second laminate provided (laminated) with the protective film-forming film or protective film, and a division of fabricating the semiconductor chips by splitting the semiconductor wafer after the bonding step and a cutting step of cutting the protective film-forming film or the protective film after the pasting step, and when the protective film-forming film is curable, further after the pasting step, and a curing step of forming the protective film by curing the protective film-forming film.

According to the above manufacturing method, it is possible to obtain a protective film-attached workpiece having a protective film that can suppress the absorption of light and is easily visible under normal conditions.

A method for manufacturing a workpiece with a protective film in the case of using a protective film-forming film that does not constitute a protective film-forming composite sheet uses such a protective film-forming film instead of the protective film-forming composite sheet. Except for the above, the method for manufacturing a workpiece with a protective film is the same as the method for producing a work piece with a protective film when using the above-mentioned composite sheet for forming a protective film. may be performed by adding the step of

For example, the manufacturing method in the case of using a protective film-forming film that does not constitute a protective film-forming composite sheet is the manufacturing method in the case of having the curing step (in this specification, "manufacturing method (3)" (sometimes referred to as "manufacturing method (4)") and a manufacturing method without the curing step (in this specification, sometimes referred to as "manufacturing method (4)").
These manufacturing methods will be described in sequence below.

<<Manufacturing method (3)>>
The manufacturing method (3) manufactures a workpiece with a protective film, which includes a workpiece obtained by machining a workpiece and a protective film provided at any part of the workpiece. In the method, the protective film is formed from the protective film-forming film according to one embodiment of the present invention, which does not constitute the protective film-forming composite sheet, and the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and the manufacturing method includes attaching the protective film-forming film to a target location of the work, thereby attaching the protective film to the work. A pasting step of producing a second laminate provided (laminated) with the protective film forming film; and a processing step of producing the workpiece by processing the workpiece after the pasting step; A cutting step of cutting the protective film-forming film or protective film after the sticking step, and a curing step of curing the protective film-forming film to form the protective film after the sticking step. .

When the workpiece is a semiconductor wafer, the manufacturing method (3) is a method of manufacturing a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. , the protective film is formed from the protective film-forming film that does not constitute the protective film-forming composite sheet, and since the protective film-forming film is curable, curing of the protective film-forming film The object is the protective film, and the manufacturing method includes attaching the protective film-forming film to the back surface of the semiconductor wafer, thereby providing (laminating) the protective film-forming film on the semiconductor wafer. a lamination step of producing two laminates; a division step of producing the semiconductor chips by dividing the semiconductor wafer after the lamination step; and a protective film-forming film or a protective film after the lamination step. and a curing step of curing the protective film-forming film after the attaching step to form the protective film.

FIG. 7 is a cross-sectional view for schematically explaining an example of the manufacturing method (3) in which the workpiece is a semiconductor wafer. Here, a manufacturing method using the protective film forming film 13 shown in FIG. 1 will be described.

<Affixing process>
In the affixing step of the manufacturing method (3), the first release film 151 is removed as the protective film forming film 13, and as shown in FIG. 9 is pasted on the back surface 9b. As a result, a second laminate 902 including the semiconductor wafer 9 and the protective film forming film 13 provided on the back surface 9b thereof is produced. The protective film forming film 13 in the second laminate 902 further has a second release film 152 on its second surface 13b.

In the attaching step of the manufacturing method (3), the protective film forming film 13 may be heated to be softened and attached to the semiconductor wafer 9 .

<Lamination process>
After the affixing step, as shown in FIG. A lamination process can be performed in which a dicing sheet 80 is adhered to the surface 13b for lamination.

The dicing sheet 80 includes a base material 81 and an adhesive layer 82 provided on one surface 81 a of the base material 81 . In this step, the surface 82a of the pressure-sensitive adhesive layer 82 on the side opposite to the substrate 81 side (in this specification, may be referred to as the "first surface") is placed on the second surface of the protective film forming film 13. 13b. The first surface 82 a of the adhesive layer 82 is the same as the first surface 80 a of the dicing sheet 80 .

The dicing sheet 80 may have the same structure as the support sheet in the protective film-forming composite sheet.
Here, the case of using the dicing sheet 80 provided with the adhesive layer 82 is shown, but in the manufacturing method (3), for example, a known dicing sheet other than the dicing sheet 80, such as a dicing sheet consisting only of a base material, is used. A sheet may be used.

The dicing sheet 80 can be attached to the protective film forming film 13 by a known method. can be done in the same way as for

<Curing process>
After the sticking step of the manufacturing method (3), in the curing step, as shown in FIG. 7C, the protective film forming film 13 is cured to form a protective film 13'.
In this embodiment, the cured product obtained by curing the protective film forming film 13 after being attached to the semiconductor wafer 9 is used as the protective film regardless of whether or not it is cut.

By performing the curing step, a cured second laminate 9021 including the semiconductor wafer 9 and the protective film 13′ (cured protective film forming film 13) provided on the back surface 9b thereof is obtained. can get.

<Dividing process, cutting process>
In the present embodiment, after the bonding process, a dividing process for fabricating semiconductor chips by dividing the semiconductor wafer 9 and a cutting process for cutting the protective film 13' are performed.
By performing the dividing step and the cutting step, as shown in FIG. 7D, a semiconductor chip 90 and a protective film 130′ after cutting provided on the back surface 90b of the semiconductor chip 90 are formed. Also, a plurality of semiconductor chips 91 with protective films are obtained. These plurality of semiconductor chips 91 with protective films are all aligned on one dicing sheet 80, and these semiconductor chips 91 with protective films and the dicing sheet 80 form a semiconductor chip group 920 with protective films. Configure.
The semiconductor chip 91 with a protective film obtained by the manufacturing method (3) is the same as the semiconductor chip 91 with a protective film obtained by the manufacturing method (1).

<Pickup process>
After the dividing step and the cutting step, as shown in FIG. 7E, a semiconductor chip 91 with a protective film (a semiconductor chip 90 having a protective film 130' after cutting) is separated from the dicing sheet 80 and picked up. The semiconductor chip 91 with the protective film can be taken out from the semiconductor chip group 920 with the protective film by performing the pick-up process.
The pick-up step in manufacturing method (3) can be performed in the same manner as the pick-up step in manufacturing method (1).

<Other processes>
The manufacturing method (3) may have other processes that do not correspond to any of the attaching process, the laminating process, the curing process, the dividing process, the cutting process, and the picking up process.
The types of the other steps and the timing of performing them can be arbitrarily selected according to the purpose, and are not particularly limited.

Examples of the other process include a printing process similar to that in the manufacturing method (1) (not shown). In the printing step, from the side opposite to the protective film forming film side of the dicing sheet, or from the outside opposite to the protective film side, through the dicing sheet, to the second surface of the protective film forming film or protective film , can be irradiated with laser light.

In this embodiment, the printing process can be performed after the attaching process, and is preferably performed between the curing process and the dividing process, and between the curing process and the cutting process.

<Timing for performing the curing step>
So far, in the manufacturing method (3), the case where the curing step is performed between the stacking step and the dividing step and between the stacking step and the cutting step has been described. The timing of performing is not limited to this. For example, in the manufacturing method (3), the curing step is performed between the attaching step and the laminating step, between the printing step and the dividing step, between the printing step and the cutting step, between the dividing step and the cutting step, and between the dividing step and the dividing step. It may be performed either between the process and the pick-up process, between the cutting process and the pick-up process, or after the pick-up process.

<<Manufacturing method (4)>>
The manufacturing method (4) manufactures a workpiece with a protective film, which includes a workpiece obtained by machining a workpiece and a protective film provided at any part of the workpiece. In the method, the protective film is formed from the protective film-forming film according to one embodiment of the present invention, which does not constitute the protective film-forming composite sheet, and the protective film-forming film is non-curing, the protective film-forming film after being attached to any part of the work is the protective film, and the manufacturing method uses the protective film-forming film as the object of the work. affixing step of fabricating a second laminate in which the protective film is provided (laminated) on the work by affixing the protective film to the work, and processing the work after the affixing step, the work A processing step of fabricating a workpiece, and a cutting step of cutting the protective film after the attaching step. In the manufacturing method (4), the protective film-forming film after being adhered to the work in the adhering step is the protective film.
Manufacturing method (4) is the same as manufacturing method (3), except that the protective film-forming film after being attached to the work is used as the protective film as it is, regardless of the type of work, without the curing step. is.

When the workpiece is a semiconductor wafer, the manufacturing method (4) is a method for manufacturing a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. , the protective film is formed from a protective film-forming film that does not constitute the protective film-forming composite sheet, and since the protective film-forming film is non-curing, it is necessary to obtain the semiconductor chip. The protective film-forming film after being attached to the back surface of the semiconductor wafer is the protective film, and the manufacturing method includes attaching the protective film-forming film to the back surface of the semiconductor wafer, thereby forming the protective film on the semiconductor wafer. a bonding step of fabricating a second laminate provided (laminated) with a protective film forming film; a dividing step of fabricating the semiconductor chips by dividing the semiconductor wafer after the bonding step; and a cutting step of cutting the protective film after the attaching step.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is by no means limited to the examples shown below.

<Raw materials for resin production>
The official names of raw materials for resin production, which are abbreviated in the present examples and comparative examples, are shown below.
BA: n-butyl acrylate MA: methyl acrylate GMA: glycidyl methacrylate HEA: 2-hydroxyethyl acrylate

<Raw materials for manufacturing protective film-forming composition>
Raw materials used for producing the composition for forming a protective film are shown below.
[Polymer component (A)]
(A)-1: Acrylic resin ("Teisan Resin SG-P3" manufactured by Nagase ChemteX Corporation)
(A)-2: Acrylic resin obtained by copolymerizing BA (12 parts by mass), MA (65 parts by mass), GMA (7 parts by mass) and HEA (16 parts by mass) (weight average molecular weight 500000, glass transition temperature -2°C).
(A)-3: Acrylic resin obtained by copolymerizing MA (87 parts by mass) and HEA (13 parts by mass) (weight average molecular weight: 450,000, glass transition temperature: 6°C).
(A)-4: Acrylic resin obtained by copolymerizing BA (60 parts by mass), MA (10 parts by mass), GMA (17 parts by mass) and HEA (13 parts by mass) (weight average molecular weight 500000, glass transition temperature -31°C).
[Thermosetting component (B)]
(B)-1: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "jER828", epoxy equivalent 184 to 194 g / eq)
(B)-2: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200" manufactured by DIC, epoxy equivalent 254 to 264 g/eq)
[Heat curing agent (C)]
(C)-1: dicyandiamide (manufactured by Mitsubishi Chemical Corporation "DICY7")
[Curing accelerator (D)]
(D)-1: 2-phenyl-4,5-dihydroxymethylimidazole (“Curesol 2PHZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
[Filler (E)]
(E)-1: Silica filler (“SC2050MA” manufactured by Admatechs, silica filler surface-modified with an epoxy-based compound, average particle size 0.5 μm)
[Coupling agent (F)]
(F)-1: an oligomeric silane coupling agent having an epoxy group, a methyl group and a methoxy group ("X-41-1056" manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 280 g/eq)
[Crosslinking agent (G)]
(G)-1: tolylene diisocyanate-based trifunctional cross-linking agent ("Coronate L" manufactured by Tosoh Corporation)
[Colorant (J)]
(J) -1: Titanium oxide white pigment ("NX-501 White" manufactured by Dainichiseika Kogyo Co., Ltd.)
(J)-2: Organic black pigment (manufactured by Dainichiseika Kogyo Co., Ltd. "6377 Black")

[Example 1]
<<Production of Protective Film Forming Film>>
<Production of protective film-forming composition (III)>
Polymer component (A)-1 (125 parts by mass), thermosetting component (B)-1 (60 parts by mass), thermosetting component (B)-2 (30 parts by mass), thermosetting agent (C) -1 (2 parts by mass), curing accelerator (D) -1 (2 parts by mass), filler (E) -1 (360 parts by mass), coupling agent (F) -1 (2 parts by mass), cross-linking Agent (G)-1 (2 parts by mass) and coloring agent (J)-1 (2.3 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23° C. to remove all components other than the solvent. A thermosetting protective film-forming composition (III) having a total concentration of 45% by mass was obtained. All of the blending amounts of the components other than the solvent shown here are the blending amounts of the target product containing no solvent.

<Production of protective film-forming film>
A release film (second release film, “SP-PET50 1031” manufactured by Lintec Co., Ltd., thickness 50 μm) in which one side of a polyethylene terephthalate film is release-treated by silicone treatment is used, and the above-obtained release film is applied to the release-treated surface. A thermosetting protective film-forming film having a thickness of 25 μm was produced by applying the protective film-forming composition (III) and drying at 100° C. for 2 minutes.

Furthermore, a release film (first release film, “SP-PET38 1031” manufactured by Lintec Co., Ltd., thickness 38 μm) release-treated surface was attached. At this time, the temperature of the laminate roll was set at 60° C., the application pressure was set at 0.4 MPa, and the application speed was set at 1 m/min. As described above, the protective film-forming film, the first release film provided on one surface of the protective film-forming film, and the second release film provided on the other surface of the protective film-forming film A structured laminate film was obtained.

<<Manufacturing chip with protective film>>
The first release film was removed from the laminated film obtained above, and the exposed surface of the resulting protective film forming film was equivalent to the back surface of an 8-inch silicon wafer (thickness: 300 μm) having no bumps (protruding electrodes). It was affixed to the entire mirror-polished surface. The sticking at this time was performed using a laminate roll, the temperature of the laminate roll was 23° C., the sticking pressure was 0.3 MPa, and the sticking speed was 50 mm/s. Further, the second release film was removed from the attached protective film-forming film to obtain the second laminate composed of the protective film-forming film and the silicon wafer laminated together (adhering step).
Then, by heat-treating this laminate at 140° C. for 2 hours using an oven manufactured by Espec Co., Ltd., the protective film-forming film was thermally cured to form a protective film (curing step).
Next, after slowly cooling the second laminate after heat curing, a dicing sheet (manufactured by Lintec Corporation) is applied to the exposed surface of the protective film (that is, the surface opposite to the side on which the silicon wafer is provided). "Adwill G-562"), a dicing sheet, a protective film and a silicon wafer are laminated in this order in the thickness direction to obtain a laminated body (the hardened second laminated body). (lamination process). Using a dicing blade, the silicon wafer was divided (diced) into pieces having a size of 2 mm×2 mm to prepare silicon chips, and the protective film was also cut into pieces having the same size. As a result, a large number of protective film-attached silicon chips each having the silicon chip and the protective film provided on the back surface of the silicon chip after being cut are held in alignment on the dicing sheet. A silicon chip group with a protective film was produced (dividing step, cutting step).
Next, the protective film-attached silicon chips in the protective film-attached silicon chip group were separated from the dicing sheet and picked up (pick-up step).

<<Evaluation of Protective Film Forming Film>>
<Measurement of reflectance of light (400 to 700 nm) of cured product>
The first release film is removed from the laminated film comprising the first release film, the protective film-forming film, and the second release film obtained above, and the protective film-forming film is thermoset by heating at 140 ° C. for 2 hours. to obtain a cured product (that is, a protective film). Specularly reflected light (specularly reflected light) is obtained by the SCI method every 1 nm in the wavelength range of 380 to 780 nm for the exposed surface of the obtained cured product (the surface opposite to the side provided with the second release film). The amount of total reflected light, which is a combination of diffusely reflected light and diffusely reflected light, was measured. Furthermore, the amount of total reflected light was measured for the reference plate made of barium sulfate in the same manner as described above. In each case, the amount of total reflected light was measured using a UV-Vis spectrophotometer ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation). In addition, as the sample holder, "Large sample chamber MPC-3100" manufactured by Shimadzu Corporation is used, and as the integrating sphere, "Integrating sphere accessory ISR-3100" manufactured by Shimadzu Corporation is used. The incident angle of light was 8°. Then, the ratio of the measured value of the cured product to the measured value of the reference plate ([measured value of the amount of light reflected by the cured product of the protective film forming film] / [total reflected light on the reference plate Measured amount of light]×100), that is, the relative total light reflectance of the cured product of the protective film-forming film was obtained, and this was adopted as the reflectance of light (400 to 700 nm). Table 1 shows the results.

<Calculation of Y value, x value and y value in the Yxy color system of the cured product>
Using the measured value of the reflectance of the above light (400 to 700 nm), the Y value in the Yxy color system of the cured product of the protective film-forming film (that is, the protective film) under the conditions of the C light source (2 ° field of view), The x and y values were calculated. Table 1 shows the results.

<Measurement of Sa on the surface of the cured product>
The first release film is removed from the laminated film obtained above, and the resulting exposed surface (the surface opposite to the side provided with the second release film) is covered with a laminate roll using an 8-inch silicon wafer. (thickness: 300 μm) was applied to the entire mirror-polished surface. At this time, the temperature of the laminate roll was set at 23° C., the application pressure was set at 0.3 MPa, and the application speed was set at 50 mm/s. Next, the second release film is removed from the protective film-forming film, and the obtained silicon wafer with the protective film-forming film (laminate of the protective film-forming film and the silicon wafer) is heated at 140° C. for 2 hours, The protective film-forming film was thermally cured. Regarding the exposed surface (the surface opposite to the side attached to the silicon wafer) of the cured product (that is, the protective film) of the obtained protective film-forming film, the arithmetic mean height Sa was measured in accordance with ISO 25178. bottom. A more specific measurement of Sa is as follows.
That is, using a scanning white interference microscope ("VS-1550" manufactured by Hitachi High-Tech Science Co., Ltd.), the surface of the cured product of the protective film forming film to be measured is observed at a magnification of 50 times and in multiple viewing mode. bottom. At this time, in the observation field of view, set a region with a length of 0.36 mm in the X-axis direction and a length of 0.27 mm in the Y-axis direction, and observe three columns in the X-axis direction and four rows in the Y-axis direction. , a total of 12 cells were observed. Then, the images for 12 cells were synthesized to form one image of 1.0 mm×1.0 mm, and Sa was measured for the entire area of the synthesized image. Table 1 shows the results.

<Evaluation of Visibility of Laser Marking on Cured Material>
A laminate of a cured protective film-forming film and a silicon wafer (i.e., a silicon wafer with a protective film) on which Sa was measured above was placed in a laser printer ("CSM300M" manufactured by EO Technics). . Then, laser marking was performed on the surface of the cured product (ie, protective film) opposite to the silicon wafer side (ie, exposed surface) by directly irradiating a laser beam. At this time, the laser wavelength was set to 532 nm, the scan speed was set to 300 mm/s, and the character string "ABCDEF" was printed. The character size was set to 400 μm in length and 300 μm in width per character, and the character spacing was set to 50 μm. Then, three evaluators visually observed the laser-printed characters, and evaluated the laser-print visibility of the cured product according to the following criteria. Table 1 shows the results.
[Evaluation criteria]
A: All three evaluators could visually recognize all characters.
B: Only one out of three evaluators could not visually recognize at least one character.
C: Two or more of the three evaluators could not visually recognize at least one character.

<Evaluation of Visibility Suppression of Chip with Protective Film in Light Emitting Device>
Using the protective film-attached silicon chip having a size of 2 mm×2 mm obtained above, a structure for pseudo-evaluation including a light-emitting device shown below was produced.
That is, a surface-mounted white LED package (size: length 3.2 mm×width 2.8 mm×height 2 mm, luminous intensity: 230 mcd (typical)) was placed on a white substrate (size: 50 mm×50 mm). At this time, the light emission direction of the LED package was arranged to be opposite to the white substrate side. One silicon chip with a protective film is installed at a position 2 mm away from one width direction end of the LED package, and one protective film is placed at a position 10 mm away from the other width direction end of the LED package. A total of two protective film-attached silicon chips were placed on the white substrate by placing the film-attached silicon chips. At this time, both of the two protective film-attached silicon chips were placed on the white substrate with the silicon chip inside facing the white substrate side and the protective film inside facing the side opposite to the white substrate side. . A white resin housing (size: 40 mm × 40 mm) with a height of 15 mm is installed at a position 20 mm away from the center of the LED package in a total of four directions in the length direction and width direction of the LED package. By placing a light diffusion plate (size: 45 mm×45 mm) with a haze of 50% thereon, a structure for pseudo evaluation including a light emitting device was produced.
Next, the structure is placed in a dark room, the LED package is caused to emit light at a current value of 20 mA, and the light-emitting device in this state is visually observed from a position of 70 cm directly above it. The visual deterrence of the chip with a protective film was evaluated. Table 1 shows the results.
[Evaluation criteria]
A: When the LED package was illuminated, the two silicon chips with protective film were not visible.
B: Only one silicon chip with a protective film was visible when the LED package was illuminated.
C: Two silicon chips with a protective film were visible when the LED package was illuminated.

<Evaluation of Visibility of Protective Film in Chip with Protective Film>
In a room lit by a fluorescent lamp for general lighting, three evaluators visually observed the silicon chip with a protective film having a size of 2 mm × 2 mm obtained above from a position of 50 cm directly above it for 3 seconds. It was observed whether or not the presence of the protective film was visible, and the visibility of the protective film on the chip with the protective film was evaluated according to the following criteria. Table 1 shows the results.
[Evaluation criteria]
A: All three evaluators could visually recognize the protective film.
B: Only one of the three evaluators could not visually recognize the protective film.
C: Two or more of the three evaluators could not visually recognize the protective film.

<<Production of protective film-formed film, production of chip with protective film, and evaluation of protective film-formed film>>
[Examples 2-6, Comparative Examples 1-2]
The types and contents of the ingredients in the protective film-forming composition (III) during the production of the protective film-forming composition (III) are adjusted so that the types and contents of the components contained in the protective film-forming composition (III) are as shown in Tables 1 and 2. A protective film-forming film and a chip with a protective film were produced in the same manner as in Example 1, except that one or both of the compounding amounts were changed, and the protective film-forming film was evaluated. The results are shown in Tables 1-2.
In addition, the description of "-" in the column of the component contained in the composition for forming a protective film means that the component is not blended (does not contain the component).

As is clear from the above results, in Examples 1 to 6, the visibility deterrence of the protective film-attached chip in the light-emitting device is high, the absorption of light by the protective film is suppressed, and furthermore, under normal conditions The visibility of the protective film on the chip with the protective film was high at .
In Examples 1 to 6, the cured product of the protective film-forming film had a sufficiently high reflectance of 20.5% or more for light (400 to 700 nm). The protective film-forming films of Examples 1 to 6 contained a white pigment (coloring agent (J)-1).

In Examples 1 to 6, the cured product of the protective film-forming film has a Y value of 25.1 or more in the Yxy color system, an x value of 0.29 to 0.32, and a y value of It was 0.30-0.33. Further, the maximum value of reflectance of light (400 to 700 nm) of the cured product was 26.2% or more.

Furthermore, in Examples 1 to 6, the visibility of laser printing of the protective film was high, and the protective film-formed film had excellent properties.
In Examples 1 to 6, Sa of the cured product of the protective film-forming film was 65.1 nm or less.

On the other hand, in Comparative Example 1, the protective film-attached chip in the light-emitting device had a low visual deterrence, and the absorption of light by the protective film was not suppressed.
In Comparative Example 1, the cured product of the protective film-forming film had a low reflectance of 11.0% or less for light (400 to 700 nm). The protective film-forming film of Comparative Example 1 did not contain a white pigment (coloring agent (J)-1) but contained a black pigment (coloring agent (J)-2).

In Comparative Example 2, the visibility of the protective film in the protective film-attached chip was low under normal conditions.
In Comparative Example 2, the cured product of the protective film-forming film had a low reflectance of 18.1% or less for light (400 to 700 nm). The protective film-forming film of Comparative Example 2 contained neither a white pigment (coloring agent (J)-1) nor a black pigment (coloring agent (J)-2).

INDUSTRIAL APPLICABILITY The present invention can be used to manufacture various substrate devices including semiconductor devices.

101, 102, 103, 104, 1011... Composite sheet for forming a protective film, 10, 20... Support sheet, 10a, 20a... One surface (first surface) of the support sheet, 11... Substrate 12... Adhesive layer 13, 23... Protective film-forming film 13a, 23a... One surface (first surface) of protective film-forming film 13b, 23b... Protective film The other surface (second surface) of the forming film, 13'... protective film, 130'... protective film after cutting, 9... semiconductor wafer (work), 90... semiconductor chip (work processing object), 9b... back surface of semiconductor wafer, 90b... back surface of semiconductor chip, 901... first laminate, 9011... hardened first laminate, 902... second laminate, 9021... Hardened second laminate, 91... Semiconductor chip with protective film (work piece with protective film)

Claims (10)

A protective film-forming film for forming a protective film on any part of a workpiece obtained by processing the workpiece,
When the protective film-forming film is curable, the cured product of the protective film-forming film has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm,
When the protective film-forming film is non-curing, the protective film-forming film has a reflectance of 20% or more for light in the entire wavelength range of 400 to 700 nm. When the protective film-forming film is curable, the arithmetic mean height Sa of one surface or both surfaces of the cured product of the protective film-forming film is 100 nm or less,
2. The protective film according to claim 1, wherein when the protective film-forming film is non-curing, the arithmetic mean height Sa of one surface or both surfaces of the protective film-forming film is 100 nm or less. forming film. The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film contains a white pigment. When the protective film-forming film is curable, the x value in the Yxy color system, calculated from the reflectance of light in the wavelength range of 380 to 780 nm, of the cured product of the protective film-forming film is 0. .26 to 0.34, and the y value in the Yxy color system is 0.26 to 0.34,
When the protective film-forming film is non-curing, the x value in the Yxy color system calculated from the reflectance of light in the wavelength range of 380 to 780 nm of the protective film-forming film is 0.26. 0.34, and the y value in the Yxy color system is 0.26 to 0.34, according to any one of claims 1 to 3. When the protective film-forming film is curable, the Y value in the Yxy color system, calculated from the reflectance of light in the wavelength range of 380 to 780 nm, of the cured product of the protective film-forming film is 20. and
When the protective film-forming film is non-curable, the protective film-forming film has a Y value of 20 or more in the Yxy color system, which is calculated from the reflectance of light in the wavelength range of 380 to 780 nm. The protective film-forming film according to any one of claims 1 to 4. When the protective film-forming film is curable, the maximum reflectance of light in the wavelength range of 400 to 700 nm of the cured product of the protective film-forming film is 25% or more,
When the protective film-forming film is non-curable, the protective film-forming film has a maximum reflectance of 25% or more for light in a wavelength range of 400 to 700 nm. The protective film-forming film according to any one of the items. The protective film-forming film according to any one of claims 1 to 6, wherein the workpiece is a chip in a light-emitting device. A support sheet and a protective film-forming film provided on one surface of the support sheet,
A composite sheet for forming a protective film, wherein the protective film-forming film is the protective film-forming film according to any one of claims 1 to 7. A method for manufacturing a work piece with a protective film, comprising:
The work piece with a protective film includes a work piece obtained by processing a work piece, and a protective film provided on any part of the work piece,
The protective film is formed from the protective film-forming film in the protective film-forming composite sheet according to claim 8,
When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, any one of the works The protective film-forming film after being attached to the location is the protective film,
In the manufacturing method, the protective film-forming film in the protective film-forming composite sheet is attached to a target portion of the work, whereby the work is provided with the protective film-forming composite sheet. An affixing step of producing a laminate,
a processing step of fabricating the workpiece by processing the workpiece after the attaching step;
After the attaching step, a cutting step of cutting the protective film-forming film or protective film,
A work with a protective film, further comprising a curing step of forming the protective film by curing the protective film-forming film after the attaching step, when the protective film-forming film is curable. A method of manufacturing a workpiece. A method for manufacturing a work piece with a protective film, comprising:
The work piece with a protective film includes a work piece obtained by processing a work piece, and a protective film provided on any part of the work piece,
The protective film is formed from the protective film-forming film according to any one of claims 1 to 7,
When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, any one of the works The protective film-forming film after being attached to the location is the protective film,
The manufacturing method includes an attaching step of attaching the protective film-forming film to a target portion of the work to produce a second laminate in which the protective film-forming film or the protective film is provided on the work. ,
a processing step of fabricating the workpiece by processing the workpiece after the attaching step;
After the attaching step, a cutting step of cutting the protective film-forming film or protective film,
A work with a protective film, further comprising a curing step of forming the protective film by curing the protective film-forming film after the attaching step, when the protective film-forming film is curable. A method of manufacturing a workpiece.

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