JP2021158181A - Protective film formation film, composite sheet for protective film formation, and transport method for work with protective film formation film - Google Patents

Abstract

To provide a protective film formation film for suppressing generation or visibility of a contact mark caused by a contact of transport means when the film is formed by the transport means while being stuck to a rear face of a work for forming a split, the protective film formation film being configured to form a protective film on the rear face of the split of the work.SOLUTION: In a protective film formation film, a plurality of protective film formation films are laminated, thereby creating a test piece with a width of 4 mm and a thickness of 200±20 μm, the test piece is held, and a storage elastic modulus of the test piece is measured in a tension mode of a frequency 11 Hz and under a measurement condition of a temperature rise speed of 3°C/min. When the storage elastic modulus at the time when a temperature of the test piece is 70°C is defined as E'70 and a maximum value of reflectance of light of a wavelength 380-780 nm in the protective film formation film is defined as Rmax, a Y value calculated by formula: Y=(log10E'70)2×Rmax is equal to or greater than 260 and an X value calculated by formula: X=(log10E'70)2 is equal to or greater than 33.SELECTED DRAWING: None

Description

The present invention relates to a protective film forming film, a composite sheet for forming a protective film, and a method for transporting a work with a protective film forming film.

Some wafers such as semiconductor wafers and insulator wafers have a circuit formed on one surface (circuit surface) and further have a protruding electrode such as a bump on the surface (circuit surface). Such a wafer is divided into chips, and its protruding electrodes are connected to a connection pad on the circuit board to be mounted on the circuit board.
In such wafers and chips, the surface (rear surface) opposite to the circuit surface may be protected by a protective film in order to suppress damage such as cracks (see Patent Document 1).

In order to form such a protective film, a protective film forming film for forming the protective film is attached to the back surface of the wafer. Next, the wafer having the protective film forming film on the back surface (wafer with the protective film forming film) undergoes various subsequent steps, and the chip having the protective film on the back surface (chip with the protective film (for example, wafer level with the protective film)). It is processed into a chip size package)). During that time, the wafer with the protective film-forming film needs to be transported to a target place such as a place where the next process is performed or a place where the wafer is stored.

International Publication No. 2015/111632

When transporting a work with a protective film-forming film, for example, a wafer with a protective film-forming film, the transport means is brought into contact with an exposed surface on the side opposite to the work side of the protective film-forming film, and the transport means protects the work. The work with the film-forming film is conveyed in a fixed state. As the transporting means, for example, one that fixes the work with the protective film-forming film by adsorbing it at a contact portion with the work with the protective film-forming film is known, but this is an example.

When the work with the protective film-forming film is conveyed using such a conveying means, the conveying means conveys the protective film-forming film to a fixed portion by the conveying means, more specifically, to a contacting portion of the fixing portion in the conveying means. Contact marks (the fixed portion) may be formed. For example, when the fixing portion is a suction plate having a circular planar shape, circular suction marks may be formed on the exposed surface of the protective film forming film. This is because the protective film forming film at the transport stage is relatively soft. A work with a protective film-forming film in which such contact marks are clearly visible has a problem in appearance. The protective film-forming film disclosed in Patent Document 1 cannot always solve such a problem.

The present invention is a protective film forming film for forming a protective film on the back surface of a divided product of a work using a chip as an example, and is conveyed in a state of being attached to the back surface of the work for forming the divided product. Provided are a protective film-forming film in which the generation or visibility of contact marks due to contact with the transport means is suppressed when transported by the means, and a protective film-forming composite sheet provided with the protective film-forming film. The purpose is.

The present invention is a protective film-forming film for forming a protective film on the back surface of a divided piece of work, and by laminating a plurality of the protective film-forming films, the width is 4 mm and the thickness is 200 ±. A test piece within a range of 20 μm was prepared, the test piece was held, and the storage elasticity of the test piece was measured under the measurement conditions of a tensile mode with a frequency of 11 Hz and a heating rate of 3 ° C./min, and the test was performed. when the temperature of the pieces is an E _'70 to the storage modulus when it is 70 ° C., the protective film forming film, the maximum value of the reflectance of light having a wavelength of 380~780nm was R _max, the protective film forming film Is the following formula:
Y = (log _{10 E'70} ) ² x R _max
The Y value calculated by is 260 or more, and the following formula:
X = (log _{10 E'70} ) ²
Provided is a protective film forming film having an X value of 33 or more calculated by.

In the protective film-forming film of the present invention, the R _max may be 5% or more.
The protective film-forming film of the present invention is preferably thermosetting or energy ray-curable.
The protective film-forming film of the present invention may contain a white pigment.
The protective film-forming film of the present invention may contain a laser marking color former.

In the protective film-forming film of the present invention, it is preferable that at least both sides thereof have a single color tone.
The protective film-forming film of the present invention preferably has one layer.
The present invention includes a support sheet and a protective film-forming film provided on one surface of the support sheet, and the protective film-forming film is the protective film-forming film of the present invention described above. A composite sheet for forming is provided.
The present invention is a method for transporting a work with a protective film-forming film comprising a work and a protective film-forming film provided on the back surface of the work, wherein the protective film-forming film is the above-mentioned protection of the present invention. It is a film-forming film, and in the transport method, the transport means is brought into contact with the exposed surface of the protective film-forming film in the work with the protective film-forming film, and the work with the protective film-forming film is fixed by the transport means. Provided is a method for transporting a work with a protective film forming film, which comprises a step of transporting the work in a state.

According to the present invention, it is a protective film forming film for forming a protective film on the back surface of a divided product of a work using a chip as an example, and is conveyed in a state of being attached to the back surface of the work for forming the divided product. Provided are a protective film-forming film in which the generation or visibility of contact marks due to contact with the transport means is suppressed when transported by the means, and a protective film-forming composite sheet provided with the protective film-forming film. NS.

It is sectional drawing which shows typically an example of the protective film forming film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically an example of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows typically another example of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows still another example schematically of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing which shows still another example schematically of the composite sheet for forming a protective film which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining an example of the transfer method of the wafer with the protective film forming film which concerns on one Embodiment of this invention.

Protective film-forming film The protective film-forming film according to an embodiment of the present invention is a protective film-forming film for forming a protective film on the back surface of a divided piece of work, and a plurality of the protective film-forming films are formed. By laminating, a test piece having a width of 4 mm and a thickness within the range of 200 ± 20 μm is produced, the test piece is held, a tension mode with a frequency of 11 Hz, and a measurement condition of a temperature rising rate of 3 ° C./min. in measures the storage modulus of the test piece, a storage elastic modulus when the temperature of the test piece is 70 ° C. and E _'70, the protective film formation film, the wavelength 380~780nm light (herein In the book, when the maximum value of the reflectance of "light (380 to 780 nm)" is abbreviated as R _max , the protective film-forming film has the following formula:
Y = (log _{10 E'70} ) ² x R _max
The Y value calculated by is 260 or more, and the following formula:
X = (log _{10 E'70} ) ²
The X value calculated by is 33 or more.
The protective film-forming film of the present embodiment can form a protective film-forming composite sheet by laminating it with a support sheet, for example, as will be described later.

The protective film-forming film of the present embodiment is a film used to protect the divided parts of the work by providing a protective film on the back surface of the divided parts of the work.
The protective film-forming film is soft and can be attached to the work before being divided into the divided products.

In the present embodiment, examples of the work include wafers and panels, and more specifically, semiconductor wafers and semiconductor panels.
Examples of the work division include a chip which is a wafer division, and more specifically, a semiconductor chip.
Examples of the protective film forming film or the adherend of the protective film include a work and a divided product of the work, and more specifically, a wafer and a chip.
The front surface of the work and the divided product of the work means the surface on which the circuit of the work and the divided product of the work, the projecting electrodes, etc. are formed, and the back surface of the work and the divided product of the work is the divided product of the work and the work. It means a surface on which the circuit and the like of the above are not formed.

Hereinafter, the present embodiment will be described by taking up a wafer as an example of a work, taking up a chip as an example of a divided work piece, and taking up a wafer or a chip as an example of an adherend.

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 by its curing, 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, and may have both thermosetting and energy ray curable properties.

As used herein, the term "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
Further, in the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" is a property of not being cured by irradiating with energy rays. Means.
Further, "non-curable" means a property of not being cured by any means such as heating or irradiation with energy rays. The non-curable protective film-forming film can be regarded as a protective film after the stage of being provided (formed) on the target object.

In the present specification, the "wafer" is a semiconductor wafer composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; sapphire, glass, and the like. An insulator wafer composed of an insulator can be mentioned.
A circuit is formed on one surface of these wafers, and in the present 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 referred to as the "back surface".
The wafer is divided into chips by means such as dicing. In the present specification, as in the case of the wafer, the surface of the chip on the side where the circuit is formed is referred to as a “circuit surface”, and the surface of the chip opposite to the circuit surface is referred to as a “back surface”.
Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars. The projecting electrode is preferably made of solder.

By using the protective film-forming film of the present embodiment or the protective film-forming composite sheet provided with the protective film-forming film, 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 the protective film, by using the protective film-forming film, a wafer with the protective film-forming film including the wafer and the protective film-forming film provided on the back surface of the wafer is manufactured. can.

Further, the substrate device can be manufactured by using the chip with the protective film.
As used herein, the term "board device" means a chip having a protective film, which is formed by flip-chip connecting a chip with a protective film to a connection pad on a circuit board at a protruding electrode on the circuit surface. For example, when a semiconductor wafer is used as the wafer, a semiconductor device can be mentioned as the substrate device.

The protective film-forming film of the present embodiment _{is attached to the back surface of the wafer when the Y value (= XR max} ) is 260 or more and the X value is 33 or more (the protective film-forming film). In the state of the attached wafer), when the film is conveyed by the conveying means, the generation or visibility of contact marks due to the contact of the conveying means is suppressed.
In the present specification, the suppression of the occurrence or visual recognition of such contact marks may be simply referred to as "suppression of contact marks".

In terms of increasing the above-mentioned effect, the Y value may be, for example, any of 300 or more, 400 or more, 600 or more, 1000 or more, 1500 or more, 2000 or more, and 2500 or more.

The upper limit of the Y value is not particularly limited. The Y value is preferably 3200 or less in that it is easier to form a protective film that satisfies the above conditions of the Y value.

The Y value can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the Y value is preferably 260 to 3200, and is any of 300 to 3200, 400 to 3200, 600 to 3200, 1000 to 3200, 1500 to 3200, 2000 to 3200, and 2500 to 3200. It may be. However, these are examples of Y values.

The protective film forming film the X value is 33 or more, the E _'70 is at 5.55 × ¹⁰ 5 Pa or more, without excessively soft, having an appropriate hardness. Therefore, the protective film-forming film is structurally less likely to generate contact marks due to contact with the transport means. The larger the X value ( _E'70 ), the higher the hardness of the protective film-forming film.
In the protective film-forming film, the X value may be, for example, 35 or more, 40 or more, 45 or more, and 50 or more in that the effect of suppressing the occurrence of the contact marks is higher.

The X value may be, for example, 59 or less, but is 56 or less in that the hardness of the protective film-forming film is in a more appropriate range and the suitability for attaching the protective film-forming film to the wafer is higher. It is preferably 51 or less, more preferably 47 or less, and even more preferably 47 or less.

The X value can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and any of the upper limit values. For example, in one embodiment, the X value may be any of 33-59, 33-56, 33-51, and 33-47. However, these are examples of X values.

Wherein E _'70, as described above, is 5.55 × ¹⁰ 5 Pa or more.
E _'70 is, as described above, were prepared using the protective layer forming film, a width of 4 mm, is 200 ± 20 [mu] m thickness (i.e., 180～220Myuemu) a measure of the test piece is in the range of be. By using such a test piece, the elastic properties of the protective film-forming film can be measured with high accuracy.
E _'70 is, for example, the test piece, apart 15mm held at two locations, said between two positions, a tensile mode frequency 11 Hz, the measurement conditions of heating rate 3 ° C. / min, it can be measured ..

_{The E'70} and X values of the protective film-forming film (the test piece) are, for example, the components contained in the protective film-forming composition described later, particularly the polymer component (polymer component (A), energy ray-curable component). (A), thermoplastic resin) and the like, and the content thereof can be adjusted. For example, by having a glass transition temperature (Tg) using a high polymer component, it can be increased E _'70 and X values.

The R _max is not particularly limited as long as the Y value satisfies the above conditions.
The R _max may be, for example, 5% or more, and the Y value can be easily adjusted according to the desired value, and even if the protective film-forming film has contact marks due to the contact of the conveying means. _{However, the R max} is preferably 6% or more in that the visibility of the contact marks is suppressed (the contact marks are difficult to see) due to the high reflectance of light (380 to 780 nm). It is more preferably 5% or more, further preferably 7% or more, for example, any one of 7.5% or more, 10% or more, 20% or more, 30% or more, and 40% or more. May be good.
Further, when many kinds of packages are mounted on the substrate device, since the normal package is dark black, the _{larger the R max} , the easier it is to distinguish the package provided with the protective film from other packages. It becomes. Further, the _{larger the R max} , the more the visibility of the roughness of the surface of the protective film forming film or the protective film caused by other than the contact of the above-mentioned transport means is suppressed (the roughness becomes hard to see).

The R _max may be, for example, 60% or less, but is preferably 53% or less, for example, 40% or less, in terms of increasing the visibility of the laser printing applied to the protective film. It may be either 30% or less and 20% or less.

R _max can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and any of the upper limit values. For example, in one embodiment, the R _max may be 5 to 60%, preferably 6 to 53%, more preferably 6.5 to 53%, and 7 to 53%. Is more preferable, for example, it may be any of 7.5-53%, 10-53%, 20-53%, 30-53%, and 40-53%.

For R _max , the angle of incidence of the incident light on the object to be measured is 8 ° for the protective film forming film and the reference plate made of barium sulfate, respectively, and SCI (SCI) is used in the wavelength range of 780 to 380 nm using an integrating sphere. The amount of total light reflected light, which is a combination of specular reflected light (normally reflected light) and diffusely reflected light, is measured by the Special Component Inc. method, and the measured value with the protective film forming film is compared with the measured value with the reference plate. ([Measured value of total light reflected light from the protective film-forming film] / [Measured value of total light reflected light from the reference plate] x 100), that is, relative total light of the protective film-forming film. The reflectance can be obtained, and this can be adopted as the reflectance of light (380 to 780 nm), and the maximum value thereof can be adopted as _{R max.}

_{The R max} of the protective film-forming film is, for example, the components contained in the protective film-forming composition described later, particularly the type and content of the colorant (colorant (J)) and the like, and the color former (color former). (K)) and the like, and the content thereof can be adjusted.

The color tone of at least both sides of the protective film-forming film of the present embodiment is preferably single, and the overall color tone of the protective film-forming film may be single. Such a protective film-forming film is advantageous in that the printing can be clearly visually confirmed in the state of the protective film finally subjected to laser printing. Further, such a protective film-forming film is advantageous in that it is easy to manufacture and that the color tones of the protective film-forming chips produced from one wafer with the protective film-forming film are all homogeneous. be.
Both sides of the protective film forming film are the same as, for example, the first surface and the second surface described later.

The fact that both sides of the protective film-forming film have a single color tone means that both sides of the protective film-forming film have a single color tone (same color tone) over the entire area.
Further, the fact that the entire color tone of the protective film-forming film is single means that not only the entire area on both sides of the protective film-forming film but also the entire area inside has a single color tone (the color tone is the same). Means that.

The color tone of the protective film-forming film can be adjusted, for example, by the type of the component of the protective film-forming composition described later, particularly the type of the colorant (colorant (J)), and the content thereof.

When the protective film-forming film is thermally cured to form the protective film, unlike the case where the protective film-forming film is cured by irradiation with energy rays, the protective film-forming film is sufficiently heated even if its thickness becomes thicker. Since it is cured, a protective film having a high protective ability can be formed. Further, by using a normal heating means such as a heating oven, a large number of protective film-forming films can be collectively heated and thermoset.
When the protective film-forming film is cured by irradiation with energy rays to form a protective film, unlike the case of thermosetting, the protective film-forming composite sheet does not need to have heat resistance and has a wide range. A composite sheet for forming a protective film can be constructed. In addition, it can be cured in a short time by irradiating with energy rays.
When the protective film-forming film is used as a protective film without being cured, the curing step can be omitted, so that a chip with a protective film can be manufactured by 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 to a wafer, but can also form a protective film having a higher protective ability by curing.

The protective film-forming film may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the protective film-forming film is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

In the present specification, not only in the case of the protective film forming film, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It may mean that only some of the layers may be the same, and further, "multiple layers are different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other". Means that.

When the protective film-forming film is composed of two or more layers, the adhesiveness between the layers is inferior, or the protective film is warped due to the difference in the easiness of expansion and contraction of each layer, and the protective film is formed. Problems such as peeling from the back surface of the chip may occur, and the protective film-forming film preferably has one layer in terms of suppressing such problems.
Further, the one-layer protective film-forming film is preferable in that it can be easily manufactured with high uniformity and 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, and for example, 10 to 50 μm, 15 to 40 μm, 17 to. It may be either 38 μm or 20 to 30 μm. When the thickness of the protective film forming film is at least the above lower limit value, a protective film having higher protective ability can be formed. When the thickness of the protective film-forming film is not more than the above upper limit value, it is possible to prevent the thickness of the chip with the protective film from becoming excessive.
Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film, and for example, the thickness of the protective film-forming film composed of a plurality of layers is all that constitute the protective film-forming film. Means the total thickness of the layers of.

<< Composition for forming a protective film >>
The protective film-forming film can be formed by using a protective film-forming composition containing the constituent material. For example, the protective film-forming film can be formed by applying a protective film-forming composition to the surface to be formed and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the ratio of the contents of the components in the protective film-forming film. In the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 18 to 28 ° C.

The thermosetting protective film forming film can be formed by using the composition for forming a thermosetting protective film, and the energy ray curable protective film forming film can be formed by using the composition for forming an energy ray curable protective film. The non-curable protective film forming film can be formed by using the non-curable protective film forming composition. In the present specification, when the protective film-forming film has both thermosetting and energy ray-curable properties, the contribution of thermosetting of the protective film-forming film to the formation of the protective film is energy. If it is greater than the contribution of linear curing, the protective film-forming film is treated as thermosetting. On the contrary, when the contribution of energy ray curing of the protective film forming film to the formation of the protective film is larger than the contribution of thermosetting, the protective film forming film is treated as one of energy ray curing.

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

The drying conditions of the protective film-forming composition are not particularly limited. However, when the protective film-forming composition contains a solvent described later, it is preferably heat-dried. Then, the composition for forming a protective film containing a solvent is preferably heat-dried at 70 to 130 ° C. for 10 seconds to 5 minutes, for example. However, the thermosetting protective film-forming composition is preferably heat-dried so that the composition itself and the thermosetting protective film-forming film formed from the composition are not thermoset.

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 for forming a protective film by thermosetting the thermosetting protective film forming film are as long as the degree of curing is such that the protective film fully exerts its function. It is not particularly limited, and may be appropriately selected depending on the type of the thermosetting protective film forming film.
For example, the heating temperature of the thermosetting protective film forming film at the time of thermosetting is preferably 100 to 200 ° C., more preferably 110 to 170 ° C., and particularly preferably 120 to 150 ° C. The heating time during the 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 may be allowed to cool.

A 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 hardness of the protective film-forming film after heating and cooling. When the hardness of the protective film-forming film before heating and the hardness of the protective film-forming film before heating are compared 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 capable of undergoing a curing (polymerization) reaction using heat as a trigger for the reaction. In the present specification, the polymerization reaction also includes a polycondensation reaction.

<Composition for forming a thermosetting protective film (III-1)>
As a preferable composition for forming a thermosetting protective film, for example, the composition for forming a thermosetting protective film (III) containing the polymer component (A), the thermosetting component (B) and the colorant (J). -1) (In this specification, it may be simply abbreviated as "composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) imparts film-forming property, flexibility, toughness, malleability, etc. to the thermosetting protective film-forming film, and imparts flexibility, toughness, malleability, etc. to the protective film. It is an ingredient.
The polymer component (A) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

Examples of the polymer component (A) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin and the like, and acrylic resin is preferable. In the present 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 1000 to 2000000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin (A1) is at least the above lower limit value, the _E'70 and X values of the thermosetting protective film forming film can be increased. In addition, 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 not more than the above upper limit value, the thermosetting protective film forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film forming film are easily followed. The generation of voids and the like is further suppressed.
In the present specification, the "weight average molecular weight" is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, more preferably -30 to 50 ° C, further preferably -20 to 40 ° C, and -15 to 30 ° C. The temperature is more preferably -10 to 20 ° C, particularly preferably -5 to 10 ° C. By Tg of the acrylic resin (A1) is not less than the lower limit, it is possible to increase the E _'70 and X values of the thermosetting protective film formation film. In addition, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability is appropriately improved. When the Tg of the acrylic resin (A1) is not more than the above upper limit value, the adhesive strength of the thermosetting protective film-forming film with the adherend and the adhesive strength of the protective film with the adherend are improved.

The acrylic resin (A1) has m-type (m is an integer of 2 or more) constituent units, and for each of the m-type monomers that induce these constituent units, any one of 1 to m overlaps. The glass transition temperature (Tg) of the acrylic resin (A1) can be calculated by using the Fox formula shown below when the numbers are sequentially assigned and named “monomer m”.

（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。）

(In the formula, 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, where W _k satisfies the following equation.)

（式中、ｍ及びＷ_ｋは、前記と同じである。）

(In the formula, m and W _k are the same as described above.)

As the Tg _k , a value described in a polymer data handbook, an adhesive handbook, a Molecule Handbook, or the like can be used. For example, a homopolymer of methyl acrylate _{has a Tg k} of 10 ° C, a homopolymer of methyl methacrylate _{has a Tg k} of 105 ° C, and a homopolymer of 2-hydroxyethyl acrylate _{has a Tg k} of -15 ° C. The homopolymer of n-butyl acrylate _{has a Tg k} of −54 ° C., and the homopolymer of glycidyl methacrylate _{has a Tg k} of 41 ° C.

Examples of the acrylic resin (A1) include a polymer of one or more (meth) acrylic acid esters; one or more (meth) acrylic acid esters, and (meth) acrylic acid and itaconic acid. , A copolymer of one or more monomers selected from vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide and the like.

Examples of the (meth) acrylic acid ester constituting the acrylic resin (A1) include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. 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 acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate (lauryl acrylate (meth), Tridecyl (meth) acrylate, Tetradecyl (meth) acrylate (myristyl (meth) acrylate), (meth) Alkyl groups constituting alkyl esters such as pentadecyl acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate) However, a (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms;
(Meta) Acrylic acid cycloalkyl esters such as (meth) acrylate isobornyl, (meth) acrylate dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meta) Acrylic acid cycloalkenyloxyalkyl ester such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meta) acrylate imide;
A glycidyl group-containing (meth) acrylic acid ester 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-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) acrylic acid. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom.

The monomer constituting the acrylic resin (A1) may be only one type, may be 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 a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin (A1) may be bonded to another compound via a cross-linking agent (G) described later, or may be directly bonded to another compound without a cross-linking agent (G). May be good. When the acrylic resin (A1) is bonded to another compound by the functional group, the adhesion reliability of the protective film to the adherend tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (A1) (hereinafter, may be simply abbreviated as “thermoplastic resin”) is used without using the acrylic resin (A1). It may be used alone or in combination with an 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, so that the adherend and the thermosetting film are thermosetting. The generation of voids and the like with the protective film-forming film may be further suppressed.

The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 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, saturated polyester resin and the like.

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all the components other than the solvent is 5 to 80% by mass regardless of the type of the polymer component (A). It is preferably 10 to 65% by mass, and for example, it may be any of 15 to 50% by mass and 15 to 35% by mass.
The content of 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 irrespective of the type of the polymer component (A). It is preferably 5 to 80% by mass, more preferably 10 to 65% by mass, and is synonymous with, for example, 15 to 50% by mass and 15 to 35% by mass. be.
This is based on the fact that the amount of components other than the solvent usually does not change in the process of removing the solvent from the resin composition containing the solvent to form the resin film. Then, the ratio of the contents of the components other than the solvent is the same. Therefore, in the present specification, not only in the case of the thermosetting protective film forming film, but also the content of the components other than the solvent will be described only in the resin film in which the solvent is removed from the resin composition. ..

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

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing a thermosetting protective film-forming film, which has thermosetting property.
The thermosetting component (B) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

Examples of the thermosetting component (B) include an epoxy resin, a thermosetting polyimide resin, an unsaturated polyester resin, and the like, and an epoxy resin is preferable.
In the present specification, the epoxy resin as the thermosetting component (B) may be referred to as "epoxy resin (B1)".
Further, the thermosetting polyimide resin is a general term for a polyimide precursor that forms a polyimide resin by heat curing and a thermosetting polyimide.

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

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 30,000 from the viewpoint of the curability of the thermosetting protective film forming film and the strength and heat resistance of the cured protective film. It is preferably 300 to 10000, more preferably 300 to 3000, and particularly preferably 300 to 3000.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, more preferably 150 to 950 g / eq.

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

[Thermosetting agent (C)]
When the thermosetting component (B) is an epoxy resin (B1), the composition (III-1) and the thermosetting protective film-forming film preferably contain a 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 carboxy group, a group in which an acid group is annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

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

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

Among the thermosetting agents (C), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000. , 400 to 10000, more preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (C) is not particularly limited, but is preferably 60 to 500, for example.

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

In the composition (III-1) and the thermosetting protective film forming film, the content of the thermosetting agent (C) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (B1). It is preferably 0.1 to 200 parts by mass, further preferably 0.1 to 100 parts by mass, and particularly preferably 0.5 to 50 parts by mass, for example. It may be any of 0.5 to 25 parts by mass, 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 value, the curing of the thermosetting protective film forming film becomes easier to proceed. When the content of the thermosetting agent (C) is not more than the upper limit value, the hygroscopicity of the thermosetting protective film forming film is reduced, and the adhesion reliability of the protective film to the adherend is further improved.

The ratio of the total contents of the thermosetting component (B) and the thermosetting agent (C) to the total mass of the thermosetting protective film-forming film in the thermosetting protective film-forming film is 3 to 50% by mass. It is preferably 5 to 35% by mass, further preferably 7 to 25% by mass, and particularly preferably 9 to 20% by mass. When the ratio is in such a range, the performance of the protective film to protect the chips and the like is further improved. In addition, the adhesion reliability of the protective film to the adherend is further improved. In addition, the adhesive force between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability is appropriately improved.

In the composition (III-1) and the thermosetting protective film forming film, the thermosetting component (B) and the thermosetting component (B) which are solid at room temperature with respect to the total contents of the thermosetting component (B) and the thermosetting agent (C). The ratio of the total content of the solid thermosetting agent (C) is preferably 20 to 100% by mass, more preferably 40 to 100% by mass, for example, 60 to 100% by mass, 75 to 100% by mass. It may be either 100% by mass and 85 to 100% by mass. When the ratio is at least the lower limit value, the _E'70 and X values of the thermosetting protective film forming film can be increased.

[Colorant (J)]
The colorant (J) is a component for adjusting the light reflectance of the thermosetting protective film forming film and the protective film.

Examples of the colorant (J) include organic pigments and inorganic pigments.

Examples of the organic dye include diimonium dye, aminium dye, cyanine dye, merocyanine dye, croconium dye, squalium dye, azurenium dye, polymethine dye, naphthoquinone dye, pyrylium dye, and phthalocyanine dye. 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 salt dyes), dithiol metal complex dyes, indolphenol dyes, triallylmethane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes, azomethine dyes. , Benzimidazolone dyes, spirone dyes, pyranthron dyes, slene 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; and titanium-based materials. Here, the lanthanum-based material, tin-based material, antimony-based material, tungsten-based material, and titanium-based material include lanthanum-containing material, tin-containing material, antimony-containing material, tungsten-containing material, and titanium, respectively. Means material.

The colorant (J) is preferably a white pigment, that is, the protective film-forming film preferably contains a white pigment. In such a protective film-forming film, the reflectance of light (380 to 780 nm) is high, the R _max is higher, and the visibility of contact marks due to the contact of the conveying means is further suppressed.
Preferred white pigments include, for example, titanium oxide-based pigments (pigments containing titanium oxide) and the like.

On the other hand, the colorant (J) is preferably a carbon material, and more preferably carbon black, in terms of further improving the visibility of the laser printing applied to the protective film.

The colorant (J) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.
For example, the composition (III-1) and the heat-curable protective film-forming film may contain one or more organic pigments as the colorant (J), or may contain only one inorganic pigment. Alternatively, it may contain two or more kinds, or may contain one kind or two or more kinds of both an organic pigment and an inorganic pigment.
Further, for example, the composition (III-1) and the thermosetting protective film-forming film may contain both a white pigment and a carbon material as the colorant (J).

The content of the colorant (J) in the composition (III-1) can be appropriately adjusted depending on, for example, the type of the colorant (J).

For example, when the colorant (J) is a white pigment, the ratio of the content of the colorant (J) to the total mass of the heat-curable protective film-forming film in the heat-curable protective film-forming film is 0. It is preferably 1 to 20% by mass, more preferably 0.3 to 17.5% by mass, and even more preferably 0.5 to 15% by mass. When the ratio is at least the lower limit value, the effect of using the colorant (J), that is, the effect of suppressing the visual recognition of the contact marks can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the colorant (J) is suppressed.

For example, when the colorant (J) is a carbon material, the ratio of the content of the colorant (J) to the total mass of the heat-curable protective film-forming film in the heat-curable protective film-forming film is 0. It is preferably .05 to 5% by mass, more preferably 0.05 to 2.5% by mass, and even more preferably 0.05 to 1.5% by mass. When the ratio is at least the lower limit value, the effect of using the colorant (J), that is, the effect of improving the visibility of laser printing can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the colorant (J) is suppressed.

For example, when the colorant (J) is a component that does not correspond to any of the white pigment and the carbon material, it is based on the total mass of the thermosetting protective film-forming film in the thermosetting protective film-forming film. The ratio of the content of the colorant (J) may be, for example, 0.1 to 15% by mass. When the ratio is at least the lower limit value, the effect of using the colorant (J) can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the colorant (J) is suppressed.

[Curing Accelerator (D)]
The composition (III-1) and the thermosetting protective film-forming film may contain a curing accelerator (D). The curing accelerator (D) is a component for adjusting the curing rate of the composition (III-1).
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 and other imidazoles (one or more hydrogen atoms other than hydrogen atoms) (Imidazole substituted with an organic group); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (phosphine in which one or more hydrogen atoms are substituted with an organic group); tetraphenylphosphonium tetraphenylborate, triphenylphosphine Examples thereof include tetraphenylborone salts such as tetraphenylborate.

The curing accelerator (D) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the curing accelerator (D) is used, the content of the curing accelerator (D) in the composition (III-1) and the thermosetting protective film forming film is the thermosetting component (B) and the thermosetting agent ( The total content of C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass. When the content of the curing accelerator (D) is at least the lower limit value, the effect of using the curing accelerator (D) can be obtained more remarkably. When the content of the curing accelerator (D) is not more than the above upper limit value, for example, the highly polar curing accelerator (D) is adhered to the thermosetting protective film forming film under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion 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-1) and the thermosetting protective film-forming film may contain a filler (E). Since the thermosetting protective film-forming film contains the filler (E), the thermosetting protective film-forming film and its cured product (that is, the protective film) can easily adjust the thermal expansion coefficient, and this thermal expansion coefficient By optimizing for the object to be formed of the protective film, the adhesion reliability of the protective film to the adherend is further improved. Further, when the thermosetting protective film forming film contains the filler (E), the hygroscopicity 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.
Preferred inorganic fillers include, for example, powders of silica, stainless steel, alumina and the like; spherical beads of these inorganic fillers; surface modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers. And so on.
Among these, the inorganic filler is preferably silica or alumina, and 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. 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.
In the present specification, the "average particle size" means the value _{of the particle size (D 50} ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction / scattering method unless otherwise specified. ..

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

When the 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 15 to 75% by mass. Is preferable, and it is more preferably 20 to 70% by mass, and for example, it may be any of 30 to 65% by mass and 40 to 60% by mass. When the ratio is in such a range, it becomes easier to adjust the thermal expansion coefficient of the thermosetting protective film forming film and the protective film. Further, when the ratio is equal to or more than the lower limit value, the _E'70 and X values of the thermosetting protective film forming film can be increased.

[Coupling agent (F)]
The composition (III-1) 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 groups of the polymer component (A), the thermosetting component (B) and the like, and is preferably a silane coupling agent. More preferred.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

The coupling agent (F) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the coupling agent (F) is used, in the composition (III-1) and the thermosetting protective film-forming film, the content of the coupling agent (F) is the polymer component (A) and the thermosetting component ( The total content of 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 parts by mass with respect to 100 parts by mass. It is particularly preferable that the amount is ~ 2 parts by mass. When the content of the coupling agent (F) is equal to or higher than the lower limit value, the dispersibility of the filler (E) in the resin is improved, and the adhesion reliability of the protective film to the adherend is improved. The effect of using the ring agent (F) is more remarkable. Further, when the content of the coupling agent (F) is not more than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (G)]
As the polymer component (A), it has a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, an isocyanate group and other functional groups that can be bonded to other compounds such as the acrylic resin (A1) described above. When used, the composition (III-1) and the thermosetting protective film-forming film may contain a cross-linking agent (G). The cross-linking agent (G) is a component for bonding the functional group in the polymer component (A) with another compound to cross-link, and by cross-linking in this way, the thermosetting protective film forming film can be crosslinked. The adhesiveness and cohesive force when attached to the 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. Can be mentioned.

The cross-linking agent (G) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.

When the cross-linking agent (G) is used, the content of the cross-linking agent (G) in the composition (III-1) is 0.01 to 20 mass by mass with respect to 100 parts by mass of the content of the polymer component (A). It is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (G) is at least the lower limit value, the effect of using the cross-linking agent (G) can be obtained more remarkably. Further, when the content of the cross-linking agent (G) is not more than the upper limit value, the excessive use of the cross-linking agent (G) is suppressed.

[Energy ray curable resin (H)]
The composition (III-1) 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 characteristics 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-based compounds having a (meth) acryloyl group are preferable.

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

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

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

The energy ray-curable resin (H) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If, the combination and ratio thereof can be arbitrarily selected.

When the energy ray-curable resin (H) is used, 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 1. It is preferably 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

[Photopolymerization Initiator (I)]
When the composition (III-1) and the thermosetting protective film-forming film contain the energy ray-curable resin (H), they are photopolymerized in order to efficiently proceed with the polymerization reaction of the energy ray-curable resin (H). It may contain an initiator (I).

Examples of the photopolymerization initiator (I) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. Benzoin compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- (4) -(4- (2-Hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one and other acetophenone compounds; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, Acylphosphine oxide compounds such as 4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone; azobisisobutyro Azo compounds such as nitrile; Titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy -2-Methyl-1- [4- (1-methylvinyl) phenyl] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.
Further, as the photopolymerization initiator (I), for example, a photosensitizer such as amine can be used.

The photopolymerization initiator (I) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

When the photopolymerization initiator (I) is used, in the composition (III-1), the content of the photopolymerization initiator (I) is based on 100 parts by mass of the content of the energy ray-curable resin (H). It is preferably 0.1 to 20 parts by mass.

[Color former (K)]
The composition (III-1) and the thermosetting protective film-forming film may contain a color former (K). The color former (K) is a component that develops color (discolors) by irradiation with light. The irradiated portion of the thermosetting protective film-forming film and the protective film containing the color-developing agent (K) is colored by irradiation with light. For example, a thermosetting protective film-forming film and a protective film containing a color-developing agent (K) that develops color by laser irradiation are highly suitable for printing by laser irradiation (laser printing), and the printed printing is made clearer. It is visible.

As the color former (K) that develops color by laser irradiation, for example, one that changes color to black by laser irradiation is known, and a commercially available laser marking color former can be used.

It is preferable that the coloring agent (K) is the laser marking coloring agent, that is, the protective film forming film contains the laser marking coloring agent. Such a protective film-forming film has higher laser printing visibility.

The color former (K) contained in the composition (III-1) and the thermosetting protective film forming film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.

In the composition (III-1), the ratio of the content of the color former (K) to the total mass of the heat-curable protective film-forming film in the heat-curable protective film-forming film is 0.1 to 30% by mass. It is preferably 1 to 25% by mass, and may be, for example, 3 to 20% by mass and 5 to 15% by mass. When the ratio is at least the lower limit value, the effect of using the color former (K) can be obtained more remarkably. When the ratio is not more than the upper limit value, the excessive use of the color former (K) is suppressed.

[General-purpose additive (L)]
The composition (III-1) and the thermosetting protective film-forming film may contain the general-purpose additive (L) as long as the effects of the present invention are not impaired.
The general-purpose additive (L) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited. Examples include an ultraviolet absorber and an antistatic agent.

The general-purpose additive (L) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.
The content of the composition (III-1) and the general-purpose additive (L) of the thermosetting protective film-forming film is not particularly limited and may be appropriately selected depending on the intended purpose.

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

Among the solvents contained in the composition (III-1), more preferable ones include, for example, methyl ethyl ketone, toluene, ethyl acetate and the like from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly. Be done.

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

<Manufacturing method of composition for forming a thermosetting protective film>
A composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending each component for forming the composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◎ Energy ray-curable protective film forming film When the energy ray-curable protective film forming film is energy-cured to form a protective film, the curing conditions are such that the protective film fully exerts its function. It is not particularly limited as much as possible, and may be appropriately selected depending on the type of the energy ray-curable protective film-forming film.
For example, the illuminance of the energy ray at the time of energy ray curing of the energy ray curable protective film forming film is preferably ^{60 to 320 mW / cm 2.} The amount of light of the energy rays at the time of curing is preferably ^{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 has adhesiveness, and more preferably uncured and has adhesiveness.

<Composition for forming an energy ray-curable protective film (IV-1)>
As a preferable composition for forming an energy ray-curable protective film, for example, the composition for forming an energy ray-curable protective film (IV-1) containing the energy ray-curable component (a) and a colorant (the present specification). In the above, it may be simply abbreviated as "composition (IV-1)") 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 property, flexibility, etc. to the energy ray-curable protective film forming film, and is 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 2000000, and an energy ray-curable group having a molecular weight of 100 to 80,000. The compound (a2) can be mentioned. The polymer (a1) may be at least partially crosslinked by 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 2000000)
Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and the above-mentioned functional group. Examples thereof include an acrylic resin (a1-1) formed by reacting with 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.

Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxy 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 the hydrogen atom. Group), epoxy group and the like. However, in terms of preventing corrosion of circuits such as wafers and chips, the functional group is preferably a group other than the carboxy 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 the functional group include those obtained by copolymerizing the acrylic monomer having the functional group and the acrylic monomer having no functional group, and other than these monomers. Further, a monomer other than the acrylic monomer (non-acrylic monomer) may be copolymerized.
Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method can be adopted as the polymerization method.

Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

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

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

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one kind, two or more kinds, and when two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

Examples of the acrylic monomer 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) ) 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) n-octyl acrylate, (meth) n-nonyl acrylate, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) Alkyl groups constituting alkyl esters such as hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate) have 1 to 1 carbon atoms. Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of 18.

Examples of the acrylic monomer 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) acrylic acid; non-crosslinkable (meth) acrylamide and its Derivatives; (meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl and the like can also be mentioned.

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

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

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having a functional group to the total amount of the structural unit constituting the acrylic polymer (a11) is 0.1 to 50% by mass. It is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and particularly preferably 3 to 30% by mass. When the ratio is in such a range, the energy ray-curable in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12). The content of the sex group can adjust the degree of curing of the protective film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one type, may be of two or more types, and when there are two or more types, a combination thereof and The ratio can be selected arbitrarily.

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

-Energy ray curable compound (a12)
The energy ray-curable compound (a12) is 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 the functional group of the acrylic polymer (a11). The one having an isocyanate group is preferable, and the one having an isocyanate group as the group is more preferable. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The number of the energy ray-curable groups contained in one molecule of the energy ray-curable compound (a12) is not particularly limited, and for example, in consideration of physical properties such as shrinkage rate required for the target protective film. Can be selected as appropriate.
For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably 1 to 3 groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl). Ethyl isocyanate;
Acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and a hydroxyethyl (meth) acrylate.
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 only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

The ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) in the acrylic resin (a1-1). Is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in such a range, the adhesive force of the cured product of the energy ray-curable protective film-forming film becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one 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 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 100,000 to 20,000, more preferably 300,000 to 1,500,000.
Here, the "weight average molecular weight" is as described above.

The polymer (a1) contained in the composition (IV-1) and the energy ray-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

(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 80,000 include a group containing an energy ray-curable double bond, and preferred ones are (meth). ) Acryloyl group, vinyl group and the like can be mentioned.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, but has 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. Examples include phenol resin.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate-based compound include the 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 phenol resin having an energy ray-curable group are described in, for example, paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102". Can be used. Such a resin also corresponds to a resin constituting a thermosetting component described later, but is treated as the compound (a2) in the composition (IV-1).

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

The compound (a2) contained in the composition (IV-1) and the energy ray-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

[Polymer without energy ray-curable group (b)]
When the composition (IV-1) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), the polymer (IV-1) and the energy ray-curable protective film-forming film further do not have an energy ray-curable group. b) is also preferably contained.
The polymer (b) may be at least partially crosslinked by a crosslinking agent or may not be crosslinked.

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

Examples of the acrylic resin (b-1) include the same as the above-mentioned acrylic resin (A1).

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

Examples of the composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). When the composition (IV-1) contains the compound (a2), it is preferable that the composition (IV-1) also contains a polymer (b) having no energy ray-curable group. Further, the composition (IV-1) does not contain the compound (a2), and may contain both the polymer (a1) and the polymer (b) having no energy ray-curable group. ..

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 in the energy ray-curable protective film-forming film. The ratio of is preferably 5 to 90% by mass. When the ratio of the content of the energy ray-curable component is in such a range, it is easy to obtain a uniformly formed protective film-forming film.

[Colorant]
The colorant is a component for adjusting the light reflectance of the energy ray-curable protective film forming film and the protective film.

The colorant contained in the composition (IV-1) and the energy ray-curable protective film-forming film is a colorant (J) contained in the composition (III-1) and the thermosetting protective film-forming film described above. ) Is the same.

The mode of containing the colorant of the composition (IV-1) and the energy ray-curable protective film-forming film is the mode of containing the colorant (J) of the composition (III-1) and the thermosetting protective film-forming film. May be similar to.

For example, the colorant contained in the composition (IV-1) and the energy ray-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds. , Their combinations and ratios can be arbitrarily selected.
For example, the composition (IV-1) and the energy ray-curable protective film-forming film may contain one or more organic pigments as colorants, or one or two inorganic pigments only. It may contain more than one kind, or may contain one kind or two or more kinds of both organic pigment and inorganic pigment.
For example, the composition (IV-1) and the energy ray-curable protective film-forming film may contain both a white pigment and a carbon material as a colorant.

The colorants contained in the composition (IV-1) can be classified according to the type thereof, and the content thereof can be adjusted as appropriate.
For example, it is classified into either a case where the colorant is a white pigment, a case where the colorant is a carbon material, and a case where the colorant is a component that does not correspond to any of the white pigment and the carbon material. However, the content of the colorant in the composition (IV-1) can be adjusted in the same manner as the content of the colorant (J) in the composition (III-1) described above.
The effect obtained when the content of the colorant (IV-1) of the composition (IV-1) is adjusted is the same as the effect obtained when the content of the colorant (J) of the composition (III-1) is adjusted. be.

The composition (IV-1) and the energy ray-curable protective film-forming film can be added to any of the energy ray-curable component (a), the polymer (b), and the colorant, depending on the purpose. Contains one or more selected from the group consisting of thermosetting components, thermosetting agents, fillers, coupling agents, cross-linking agents, photopolymerization initiators, color formers and general-purpose additives. You may be.

The thermosetting component, the thermosetting agent, the filler, the coupling agent, the cross-linking agent, the photopolymerization initiator, the color former, and the general-purpose additive in the composition (IV-1) are the compositions (III-1), respectively. ), Thermosetting component (B), thermosetting agent (C), filler (E), coupling agent (F), cross-linking agent (G), photopolymerization initiator (I), color former (K) and The same as the general-purpose additive (L) can be mentioned.

For example, when the composition (IV-1) contains a thermosetting component, the energy ray-curable protective film-forming film formed by using such a composition (IV-1) is covered by heating. The adhesive force to the body 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-1), one type of the thermosetting component, the filler, the coupling agent, the cross-linking agent, the photopolymerization initiator, the color former and the general-purpose additive may be used alone. Two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

The contents of the thermosetting component, filler, coupling agent, cross-linking agent, photopolymerization initiator, color former and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the intended purpose. There is no particular limitation.

The composition (IV-1) is preferably further containing a solvent because its handleability is improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (IV-1) may be only one kind or two or more kinds.
The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on, for example, the type of component other than the solvent.

<Manufacturing method of composition for forming energy ray-curable protective film>
A composition for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by blending each component for forming the composition.
The energy ray-curable protective film-forming composition can be produced, for example, by the same method as in the case of the thermosetting protective film-forming composition described above, except that the types of compounding components are different.

◎ Non-curable protective film-forming film Preferred non-curable protective film-forming film includes, for example, a film containing a polymer component, a colorant and a filler.

<Composition for forming a non-curable protective film (V-1)>
As a preferable composition for forming a non-curable protective film, for example, a composition for forming a non-curable protective film (V-1) containing the polymer component and a colorant (in the present specification, simply "composition". (V-1) ”may be abbreviated).

[Polymer component]
The polymer component is not particularly limited.
More specifically, examples of the polymer component include those similar to non-curable resins such as the polymer component (A) mentioned as the component contained in the composition (III-1) described above. ..

The polymer component contained in the composition (V-1) and the non-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds, when it is two or more kinds. The combination and ratio thereof can be arbitrarily selected.

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

[Colorant]
The colorant is a component for adjusting the light reflectance of the non-curable protective film forming film and the protective film.
In the present embodiment, the non-curable protective film-forming film is regarded as a protective film after being attached to a target portion of the object to be protected, such as the back surface of a wafer.

The colorant contained in the composition (V-1) and the non-curable protective film-forming film is the colorant (J) contained in the composition (III-1) and the thermosetting protective film-forming film described above. Is the same as.

The mode of containing the colorant of the composition (V-1) and the non-curable protective film-forming film is the mode of containing the colorant (J) of the composition (III-1) and the thermosetting protective film-forming film. It may be similar.

For example, the colorant contained in the composition (V-1) and the non-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds. The combination and ratio thereof can be arbitrarily selected.
For example, the composition (V-1) and the non-curable protective film-forming film may contain one or more organic pigments as colorants, or one or two inorganic pigments only. The above may be contained, or both the organic pigment and the inorganic pigment may be contained in one kind or two or more kinds.
For example, the composition (V-1) and the non-curable protective film-forming film may contain both a white pigment and a carbon material as a colorant.

The colorants contained in the composition (V-1) can be classified according to the type thereof, and the content thereof can be adjusted as appropriate.
For example, it is classified into either a case where the colorant is a white pigment, a case where the colorant is a carbon material, and a case where the colorant is a component that does not correspond to any of the white pigment and the carbon material. However, the content of the colorant in the composition (V-1) can be adjusted in the same manner as the content of the colorant (J) in the composition (III-1) described above.
The effect obtained when the content of the colorant (V-1) of the composition (V-1) is adjusted is the same as the effect obtained when the content of the colorant (J) of the composition (III-1) is adjusted. be.

The composition (V-1) may contain other components that do not fall under any of the polymer component and the colorant, depending on the purpose.
The other components are not particularly limited and can be arbitrarily selected depending on the intended purpose.

Examples of the other components in the composition (V-1) include fillers, coupling agents, cross-linking agents, color formers, general-purpose additives and the like.
The filler, coupling agent, cross-linking agent, color former and general-purpose additive in the composition (V-1) include the filler (E) and the coupling agent (F) in the composition (III-1), respectively. , The same as the cross-linking agent (G), the color former (K) and the general-purpose additive (L).

The other components contained in the composition (V-1) and the non-curable protective film forming film may be only one kind, two or more kinds, or two or more kinds, when there are two or more kinds. The combination and ratio thereof can be arbitrarily selected.

The content of the other component of the composition (V-1) may be appropriately adjusted according to the intended purpose, and is not particularly limited.

The composition (V-1) is preferably further containing a solvent because its handleability is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the above-mentioned composition (III-1).
The solvent contained in the composition (V-1) may be only one kind or two or more kinds.
The content of the solvent in the composition (V-1) is not particularly limited, and may be appropriately selected depending on, for example, the type of component other than the solvent.

<Manufacturing method of non-curable protective film forming composition>
A composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending each component for forming the composition.
The non-curable protective film-forming composition can be produced, for example, by the same method as in the case of the thermosetting protective film-forming composition described above, except that the types of compounding components are different.

FIG. 1 is a cross-sectional view schematically showing an example of a protective film forming film according to an embodiment of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio and the like of each component are the same as the actual ones. Is not always the case.

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

The protective film forming film 13 has the above-mentioned characteristics.
The protective film forming film 13 can be formed by using the above-mentioned protective film forming composition.

Both the first release film 151 and the second release film 152 may be known.
The first release film 151 and the second release film 152 may be the same as each other, or are different from each other, for example, the release forces required for peeling from the protective film forming film 13 are different from each other. May be good.

In the protective film-forming film 13 shown in FIG. 1, either the first release film 151 or the second release film 152 is removed, and the resulting exposed surface becomes a surface to be attached to the back surface of the wafer (not shown). Then, the other remaining of the first release film 151 and the second release film 152 is removed, and the generated exposed surface becomes a sticking surface of a support sheet or a dicing sheet, which will be described later.

FIG. 1 shows an example in which the release film is provided on both sides (first surface 13a, second surface 13b) of the protective film forming film 13, but the release film is any one of the protective film forming films 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 the back surface of the wafer without being used in combination with the support sheet described later. In that case, a release film may be provided on the surface of the protective film-forming film opposite to the surface on which the protective film-forming film is attached to the wafer, and the release film may be removed at an appropriate timing.

On the other hand, the protective film-forming film of the present embodiment can be used in combination with a support sheet described later to form a protective film-forming composite sheet capable of both forming the protective film and dicing. Hereinafter, such a composite sheet for forming a protective film will be described.

Protective Film Forming Composite Sheet The protective film forming composite sheet according to the embodiment of the present invention includes 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 the above-described embodiment of the present invention.

Since the protective film-forming composite sheet of the present embodiment includes the protective film-forming film, the protective film-forming composite sheet is conveyed in the same manner as when the wafer with the protective film-forming film is conveyed by the above-mentioned conveying means. At the time of transportation by the means, in the protective film forming film, the generation or visibility of contact marks due to the contact of the transportation means is suppressed.

In the present 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, this laminated structure is referred to as "protective film". It is called a "composite sheet for forming".

Hereinafter, each layer constituting the protective film forming composite sheet will be described in detail.

◎ Support sheet The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and the thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the 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 curability, the support sheet preferably allows energy rays to pass through.

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

When a support sheet provided with a base material 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 composed of only a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.

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

FIG. 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
In the drawings after FIG. 2, the same components as those shown in the already explained figures are designated by the same reference numerals as in the case of the already explained figures, and detailed description thereof will be omitted.

The protective film forming composite sheet 101 shown here is a protective film provided on the support sheet 10 and one surface of the support sheet 10 (sometimes referred to as a "first surface" in the present specification) 10a. It is configured to include the forming film 13.
The support sheet 10 includes a base material 11 and an adhesive layer 12 provided on one surface (first surface) 11a of the base material 11. In the protective film-forming composite sheet 101, the pressure-sensitive adhesive layer 12 is arranged between the base material 11 and the protective film-forming film 13.
That is, the protective film-forming composite sheet 101 is configured by laminating the base material 11, the pressure-sensitive adhesive layer 12, and the 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 opposite to the base material 11 side (sometimes referred to as the “first surface” in the present specification).

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 almost the entire surface of the first surface 12a of the pressure-sensitive adhesive layer 12, and the side of the protective film-forming film 13 opposite to the pressure-sensitive adhesive layer 12 side. The adhesive layer 16 for jigs is laminated on a part of the surface (sometimes referred to as “first surface” in the present specification) 13a, that is, in a region near the peripheral edge portion. Further, of the first surface 13a of the protective film forming film 13, the area 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. The release film 15 is laminated on 16a (sometimes referred to as the "first surface" in the present specification).

Not limited to the case of the protective film forming composite sheet 101, in the protective film forming composite sheet of the present embodiment, the release film (for example, the release film 15 shown in FIG. 1) has an arbitrary configuration, and the present embodiment has an arbitrary configuration. The composite sheet for forming a protective film may or may not include 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 adhesive layer 16 for jigs 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. It may have a structure.

The protective film-forming film 13 suppresses the occurrence or visibility of the above-mentioned contact marks.

In the protective film forming composite sheet 101, the back surface of the wafer is attached to the first surface 13a of the protective film forming film 13 with the release film 15 removed, and further, the first surface of the jig adhesive layer 16 is attached. 16a is attached to a jig such as a ring frame and used.

FIG. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention.
The protective film-forming composite sheet 102 shown here has a different shape and size of the protective film-forming film, and the adhesive layer for jigs is not on the first surface of the protective film-forming film but on the first surface of the 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 is a part of a region of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the width direction of the pressure-sensitive adhesive layer 12 (in FIG. 3). It is laminated in the area on the center side in the left-right direction). Further, the jig adhesive layer 16 is laminated on the first surface 12a of the pressure-sensitive adhesive layer 12 in the region where the protective film forming film 23 is not laminated, that is, in the region near the peripheral edge portion. Then, the surface of the protective film forming film 23 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in the present specification) 23a and the first of the jig adhesive layer 16. The release film 15 is laminated on the surface 16a.

FIG. 4 is a cross-sectional view schematically showing still another example of the protective film forming composite sheet according to the 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 the 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. 2, except that the support sheet 20 is provided in place of the support sheet 10.
The support sheet 20 is composed of only the base material 11.
That is, the protective film forming composite sheet 104 is formed by laminating the base material 11 and the protective film forming film 13 in the thickness direction thereof.
The surface (first surface) 20a of the support sheet 20 on the protective film forming film 13 side is the same as the first surface 11a of the base material 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 the one shown in FIGS. 1 to 5, and a part of the configuration shown in FIGS. 1 to 5 is changed within a range not impairing the effect of the present invention. Alternatively, it may be deleted, or may have other configurations added to those described above.

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

○ Base material The base material is in the form of a sheet or a film, and examples of the constituent material thereof 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); other than polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, and ethylene-norbornene copolymer (ethylene as monomer) (Copolymers obtained using); Vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefins; Polyethylene terephthalate, polyethylene Polymers such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and all aromatic polyesters in which all constituent units have an aromatic cyclic group; Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
Further, as the resin, for example, a crosslinked resin in which one or more of the resins exemplified above are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

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

The base material may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers are the same or different from each other. The combination of these plurality of layers may be not particularly limited.

The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming the protective film and the suitability for sticking to the wafer are further improved.
Here, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material. means.

In addition to the main constituent materials such as the resin, the base material may contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

The base material may be transparent, opaque, colored depending on the purpose, or another layer may be vapor-deposited.
For example, when the protective film-forming film has energy ray curability, the base material is preferably one that allows energy rays to pass through.

The base material is subjected to a sandblasting treatment, a solvent treatment or the like to make the base material uneven in order to adjust the adhesiveness with a layer provided on the base material (for example, an adhesive layer, a protective film forming film, or the other layer); The surface may be subjected to an oxidation treatment such as a discharge treatment, an electron beam irradiation treatment, a plasma treatment, an ozone / ultraviolet irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment; a base oil treatment; a hydrophilic treatment or the like. Further, the surface of the base material may be primed.

The base material may have adhesiveness on at least one surface by containing a specific range of components (for example, resin or the like).

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

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

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

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but 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, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the sum of all the layers constituting the 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 the physical properties before and after curing.

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

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

When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive composition may be applied onto the base material and dried if necessary. Further, for example, the pressure-sensitive adhesive composition is applied onto the release film and dried as necessary to form a pressure-sensitive adhesive layer on the release film, and the exposed surface of the pressure-sensitive adhesive layer is used as a base material. The pressure-sensitive adhesive layer may be laminated on the base material by adhering it to one surface. In this case, the release film may be removed at any timing of the manufacturing process or 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, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, "sticky resin (I-)". 1a) ”) and an energy ray-curable compound are contained in the pressure-sensitive adhesive composition (I-1); on the side chain of the non-energy ray-curable pressure-sensitive adhesive resin (I-1a). An adhesive composition (I-) containing an energy ray-curable adhesive resin (I-2a) into which an unsaturated group has been introduced (hereinafter, may be abbreviated as "adhesive resin (I-2a)"). 2); Examples thereof include a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive 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 non-energy ray-curable pressure-sensitive adhesive resin (I-1a). (I-4) and the like can be mentioned.

[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 a structural unit derived from at least 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 preferable.

The acrylic polymer preferably 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 may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

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

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, these pressure-sensitive adhesive compositions are included). (Abbreviated as "Adhesive Compositions (I-1) to (I-4)"), the constituent unit of the acrylic resin such as the acrylic polymer may be only one type or two types. The above may be sufficient, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

The pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, two or more types, or two or more types. If so, their combinations and ratios can be arbitrarily selected.

The ratio of the content of the adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4). Is preferably 5 to 99% by mass.

[Energy ray-curable adhesive resin (I-2a)]
The adhesive resin (I-2a) can be 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 can be bonded to the adhesive resin (I-1a) by further 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 preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

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

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

The ratio of the content of the adhesive resin (I-2a) to the total mass of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (I-2) or (I-3) is 5 to 5. 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 irradiation with energy rays. Be done.

Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (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) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) Acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one kind, two or more kinds, or two or more kinds. If so, their combinations and ratios can be arbitrarily selected.

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

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

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

The cross-linking agents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.

In the pressure-sensitive 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 content of the pressure-sensitive adhesive resin (I-1a). Is preferable.
In the pressure-sensitive 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 content of the pressure-sensitive adhesive resin (I-2a). Is preferable.

[Photopolymerization initiator]
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)". (Abbreviated as) may further contain a photopolymerization initiator. The pressure-sensitive adhesive compositions (I-1) to (I-3) containing the photopolymerization initiator sufficiently proceed with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include the same as the above-mentioned photopolymerization initiator (I).

The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are It can be selected arbitrarily.

In the pressure-sensitive 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 content of the energy ray-curable compound.
In the pressure-sensitive 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 content of the pressure-sensitive adhesive resin (I-2a). ..
In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total content of the pressure-sensitive 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-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction retarder is, for example, the pressure-sensitive adhesive compositions (I-1) to (I-1) to be stored due to the action of the catalyst mixed in the pressure-sensitive adhesive compositions (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 to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

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

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

[solvent]
The pressure-sensitive 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 suitability for coating on 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 such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane, n-hexane and the like. Hydrocarbons of the above; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol and the like can be mentioned.

The solvent contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

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

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

◇ Method for manufacturing a composite sheet for forming a protective film The composite sheet for forming a protective film is laminated so that the above-mentioned layers have a corresponding positional relationship, and the shape of a part or all of the layers is adjusted as necessary. It can be manufactured. The method of forming each layer is as described above.

For example, when a pressure-sensitive adhesive layer is laminated on a base material when manufacturing a support sheet, the above-mentioned pressure-sensitive adhesive composition may be applied onto the base material and dried if necessary.
Further, the pressure-sensitive adhesive composition is applied onto the release film and dried as necessary to form a pressure-sensitive adhesive layer on the release film, and the exposed surface of the pressure-sensitive adhesive layer is used as one of the base materials. The pressure-sensitive adhesive layer can also be laminated on the base material by the method of bonding to the surface of the above. At this time, it is preferable that the pressure-sensitive adhesive composition is applied to the peel-treated surface of the release film.
Up to this point, the case of laminating the pressure-sensitive adhesive layer on the base material has been described as an example, but the above method can also be applied to, for example, the case of laminating an intermediate layer or the other layer on the base material.

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

As described above, all the layers other than the base material constituting the protective film forming composite sheet can be laminated in advance by forming them on the release film and laminating them on the surface of the target layer, so that they can be laminated as needed. A layer for adopting such a process may be appropriately selected to produce a composite sheet for forming a protective film.

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

◇ How to transport a wafer with a protective film-forming film (How to use the protective film-forming film)
The protective film-forming film and the protective film-forming composite sheet can be used for manufacturing the chip with the protective film. Then, prior to the production of the chip with the protective film, the protective film-forming film can be used for producing the wafer with the protective film-forming film, and the produced wafer with the protective film-forming film can be used in a subsequent step. , It is transported to the target location by the transport means. At the time of this transfer, in the protective film-forming film in the wafer with the protective film-forming film, the generation or visibility of contact marks due to the contact of the transport means is suppressed.

That is, the method for transporting a wafer with a protective film-forming film according to an embodiment of the present invention is a method for transporting a wafer with a protective film-forming film including the wafer and the protective film-forming film provided on the back surface of the wafer. The protective film-forming film is the protective film-forming film according to the embodiment of the present invention, and the transport method is an exposed surface of the protective film-forming film in the wafer with the protective film-forming film. In addition, there is a step of bringing the transport means into contact with each other and transporting the wafer with the protective film forming film in a state of being fixed by the transport means (in this specification, it may be abbreviated as "convey step").

FIG. 6 is a cross-sectional view for schematically explaining an example of a method for transporting a wafer with a protective film-forming film according to an embodiment of the present invention.
In the transfer step, first, as shown in FIG. 6A, one surface (here, the first surface 13a) is provided with the release film 15, and the other surface (here, the second surface 13b) is exposed. As shown in FIG. 6B, a wafer 913 with a protective film-forming film is produced by sticking the second surface 13b of the protective film-forming film 13 to the back surface 9b of the wafer 9.
The arrow in FIG. 6A indicates the direction in which the protective film forming film 13 is attached to the wafer 9.

At this time, for example, as shown here, the wafer 9 is installed on a table 8 capable of controlling its own temperature, and the wafer 9 is heated by heating the table 8 and then heated. It is preferable to attach the protective film forming film 13 to the wafer 9 in the present state. By doing so, the protective film-forming film 13 heated by heat transfer from the wafer 9 and having improved flexibility can be attached to the wafer 9, so that the protective film-forming film 13 in the obtained wafer with the protective film-forming film 913 is protected. Residual air bubbles can be suppressed between the film-forming film 13 and the wafer 9, and the adhesiveness of the protective film-forming film 13 when attached to the wafer 9 can be improved.

The temperature of the wafer 9 at this time is preferably, for example, 65 to 75 ° C.
In this step, the protective film-forming film 13 before being attached to the wafer 9 may be preheated by another heating means, and the temperature of the protective film-forming film 13 in that case is, for example, 65. It is preferably ~ 75 ° C.

In order to attach the protective film forming film 13 to the back surface 9b of the wafer 9, the wafer 9 is installed on the table 8 with the circuit surface 9a side provided with the projecting electrode 90 facing the table 8. The circuit of the wafer 9 is not shown here.

As shown in FIG. 6B, the release film 15 is removed from the protective film-forming film 13 after being attached to the wafer 9.

In the transfer step, then, as shown in FIG. 6C, a protective film-forming film is attached to the exposed surface (here, the first surface 13a) of the protective film-forming film 13 in the wafer 913 with the protective film-forming film. The transport means 7 used for transporting the wafer 913 is brought into contact with the wafer 913, and the wafer 913 with the protective film forming film is fixed by the transport means 7.
The transporting means 7 may be a known one, and for example, a means (for example, a so-called suction arm) for fixing the transportable object by sucking it at a contact portion with the transportable object (here, a wafer with a protective film forming film 913). Etc.) can be used as the transport means 7. In this case, the contact portion includes a suction plate. However, the transporting means 7 is not limited to this, and the transporting object may be fixed by something other than adsorption.
Here, the cross-sectional display is omitted only for the transport means 7.

In the transfer step, then, as shown in FIG. 6D, the wafer 913 with the protective film forming film fixed by the transfer means 7 is separated from the table 8.
The arrow in FIG. 6D indicates the pulling direction of the wafer 913 with the protective film forming film from the table 8.

Then, as it is, as shown in FIG. 6E, the wafer 913 with the protective film forming film is conveyed in a state of being fixed by the conveying means 7. In FIG. 6E, the transport direction of the wafer 913 with the protective film forming film is indicated by an arrow, but this is an example of the transport direction, and the transport direction is not limited to this direction. ..

In the transfer step, then, as shown in FIG. 6 (f), in the wafer 913 with the protective film forming film after being transferred to the target location, the fixed state by the transfer means 7 is eliminated and the transfer means 7 is protected. It is separated from the wafer 913 with the film forming film.
With the above, the transfer process is completed.

After the transfer step is completed, the protective film-forming film 13 in the wafer 913 with the protective film-forming film, more specifically, the first surface 13a of the protective film-forming film 13 at the fixed portion by the transport means 7. The generation or visual recognition of contact marks caused by the contact of the transport means 7 is suppressed. When the transport means 7 is a means for sucking and fixing the object to be transported, the contact mark is a suction mark.
As described above, the wafer 913 with the protective film forming film in which the generation of contact marks or the visibility is suppressed has no problem in appearance.

The method for transporting the wafer with the protective film-forming film of the present embodiment is not limited to the one described so far, and a part of the configurations described so far may be changed or modified within a range not impairing the effect of the present invention. It may be deleted or added with other configurations.
For example, the transport method may have other processes not included in any of the above descriptions.

When the protective film-forming film of the present embodiment is non-curable, the protective film-forming film after being attached to the object to be attached (wafer) can be regarded as a protective film as described above. can. This is because the protective film-forming film after being attached to the object to be attached sufficiently functions as a protective film for protecting the back surface of the object to be protected (wafer and chip) without changing its characteristics. be. On the other hand, the characteristics of the non-curable protective film-forming film do not change clearly before and after being attached to the object to be attached. Therefore, in the present specification, the non-curable protective film-forming film until the transfer by the conveying means is completed can be regarded as a protective film-forming film, not a protective film.

◇ How to use a wafer with a protective film forming film (manufacturing method of chips with a protective film)
The wafer with the protective film-forming film of the present embodiment that has undergone the above-mentioned transport method can be used for manufacturing the chip with the protective film.
At this time, the method for manufacturing the chip with the protective film is the conventional method for manufacturing the chip with the protective film, except that the wafer with the protective film-forming film of the present embodiment is used instead of the conventional wafer with the protective film-forming film. Is the same as.

As an example, after passing through the transfer method, a dicing sheet is attached to the exposed surface of the protective film-forming film in the protective film-forming film on the opposite side to the wafer side to divide the wafer ( A chip is produced by dying), and the protective film-forming film is cut along the chip to form a protective film including the chip and a protective film-forming film after cutting provided on the back surface of the chip. A chip with a film is produced on a dicing sheet, and the chip with a protective film-forming film is pulled away from the dicing sheet and picked up. When a protective film is formed by curing the protective film-forming film at any stage after picking up the chip with the protective film-forming film before sticking, and the protective film-forming film is non-curable. Can manufacture a chip with a protective film by a method of treating the protective film-forming film as a protective film even before the dicing sheet is attached to the protective film-forming film.

Not limited to the above-mentioned method, a method for manufacturing a chip with a protective film is a method of manufacturing a chip with a protective film on a surface of the protective film forming film or protective film opposite to the wafer side or a surface opposite to the chip side. It may have a printing process for printing.
In the printed protective film produced by performing the printing step, when the protective film-forming film contains the coloring agent, the printed protective film can be visually recognized more clearly.

-Manufacturing method of substrate device After obtaining the chip with protective film of this embodiment by the above-mentioned manufacturing method, except that the chip with protective film of this embodiment is used instead of the conventional chip with protective film. , The substrate device can be manufactured by the same method as the conventional manufacturing method.

As a method for manufacturing such a substrate device, for example, the protruding electrode on a chip with a protective film obtained by using the protective film forming film is brought into contact with a connection pad on a circuit board to form the protruding shape. Examples thereof include a manufacturing method including a flip-chip connecting step of electrically connecting an electrode and a connection pad on the circuit board.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

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

<Raw material for manufacturing the composition for forming a protective film>
The raw materials used for producing the protective film forming composition are shown below.
[Polymer component (A)]
(A) -1: Acrylic resin (weight average molecular weight 700,000, glass) obtained by copolymerizing BA (10 parts by mass), MA (60 parts by mass), GMA (10 parts by mass) and HEA (20 parts by mass). Transition temperature -1 ° C).
(A) -2: Acrylic resin (weight average molecular weight 600,000, glass) obtained by copolymerizing BA (5 parts by mass), MA (65 parts by mass), GMA (20 parts by mass) and HEA (10 parts by mass). Transition temperature 9 ° C.).
[Thermosetting component (B)]
(B) -1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq, liquid at room temperature)
(B) -2: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800-900 g / eq, solid at room temperature)
(B) -3: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255-260 g / eq, solid at room temperature)
[Thermosetting agent (C)]
(C) -1: Dicyandiamide ("ADEKA Hardener EH-3636AS" manufactured by ADEKA, thermally active latent epoxy resin curing agent, active hydrogen amount 21 g / eq, solid at room temperature)
[Curing Accelerator (D)]
(D) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ-PW" manufactured by Shikoku Chemicals Corporation)
[Filler (E)]
(E) -1: Silica filler (“SC2050MA” manufactured by Admatex Co., Ltd., silica filler surface-modified with an epoxy compound, average particle size 0.5 μm)
[Coupling agent (F)]
(F) -1: 3-glycidyloxypropyltrimethoxysilane ("KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)
[Colorant (J)]
(J) -1: Carbon black (Mitsubishi Chemical Corporation "MA650", average particle size 28 nm)
(J) -2: Titanium oxide-based white pigment ("N-DYM8054" manufactured by Dainichiseika Co., Ltd.)
[Color former (K)]
(K) -1: Laser marking color former ("Elbima (registered trademark) Z117" manufactured by Toyo Ink Co., Ltd.)

[Example 1]
<< Manufacture of protective film forming film >>
<Production of composition for forming a protective film (III-1)>
Polymer component (A) -1 (150 parts by mass), thermosetting component (B) -1 (60 parts by mass), (B) -2 (10 parts by mass), (B) -3 (30 parts by mass) , (C) -1 (2 parts by mass), curing accelerator (D) -1 (2 parts by mass), filler (E) -1 (320 parts by mass), coupling agent (F) -1 (2 parts by mass) Parts), colorant (J) -1 (1.2 parts by mass) and colorant (J) -2 (5 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to remove the solvent. A thermocurable protective film-forming composition (III-1) having a total concentration of all the components of 45% by mass was obtained. The blending amounts of the components other than the solvent shown here are all the blending amounts of the target product containing no solvent.

<Manufacturing of protective film forming film>
A release film (second release film, "SP-PET50 1031" manufactured by Lintec Corporation, thickness 50 μm) in which one side of a polyethylene terephthalate film was peeled by a silicone treatment was used, and the peeled surface was obtained as described above. The protective film-forming composition (III-1) was applied and dried at 100 ° C. for 2 minutes to produce a thermosetting protective film-forming film having a thickness of 25 μm.

Further, the exposed surface of the obtained protective film forming film on the side not provided with the second release film is subjected to a release treatment of the release film (first release film, "SP-PET38 1031" manufactured by Lintec Co., Ltd., thickness 38 μm). By bonding the surfaces together, 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 , To obtain a laminated film constructed with.

<< Evaluation of protective film forming film >>
<Measurement of storage elastic modulus E _'70 of the protective film forming Film>
The first release film and the second release film are removed from the laminated film obtained above, and a plurality of remaining protective film-forming films are laminated to prepare a laminate having a thickness within the range of 200 ± 20 μm. Then, the laminate was cut to make the width 4 mm, thereby producing a test piece.
Next, using a viscoelastic property measuring device (“RHEOVIBRON DDV-01FP” manufactured by Orientec Co., Ltd.), the test piece was held, and a chuck-to-chuck distance of 15 mm, a tension mode with a frequency of 11 Hz, and a temperature rise rate of 3 ° C./min were measured. Under the conditions, the storage elastic modulus E'of the test piece from 0 ° C. to 100 ° C. was measured. Among them, Table 1 shows the measurements of the storage modulus E _'70 at 70 ° C..
Moreover, to calculate the X values from E _'70. The results are shown in Table 1.

<Measurement _{of R max} of protective film forming film>
The first release film was removed from the laminated film obtained above.
Next, using a UV-Vi specular photometer (“UV-VIS-NIR SPECTROPHOTOMETER UV-3600” manufactured by Shimadzu Corporation), the protective film-forming film is not provided with the second release film (exposed surface side). Therefore, in the wavelength range of 780 to 380 nm, the amount of total light reflected light including the specular reflected light (normally reflected light) and the diffusely reflected light was measured every 1 nm by the SCI method. Further, for the barium sulfate reference plate, the amount of total light reflected light was measured by the same method. In either case, the sample folder is the "Large Sample Room MPC-3100" manufactured by Shimadzu Corporation, and the integrating sphere is the "Integrating Sphere Attached Device ISR-3100" manufactured by Shimadzu Corporation. The incident angle of the incident light was set to 8 °. Then, the ratio of the measured value with the protective film-forming film to the measured value with the reference plate ([measured value of the total light reflected light with the protective film-forming film] / [total light reflected light with the reference plate]. [Measured value of the amount of light] × 100), that is, the relative total light reflectance of the protective film-forming film was obtained, and this was adopted as the light reflectance. _{Then, R max} was obtained from the measurement result. The results are shown in Table 1.
_Moreover, to calculate the Y value from the _{R max} and E _'70. The results are shown in Table 1.

<Evaluation of the effect of suppressing contact marks of transport means on the protective film-forming film>
The first release film was removed from the laminated film obtained above by using a 300 mm fully automatic LC tape laminator "RAD-3600F / 12" manufactured by Lintec Corporation in the specifications for a 200 mm wafer.
Next, the surface (exposed surface) of the protective film-forming film on the side not provided with the second release film is placed on one surface of an 8-inch silicon wafer (diameter 200 mm, thickness 350 μm, no bumps) in a size of 198 mm in diameter. I pasted it. At this time, the protective film-forming film was attached while heating the silicon wafer to 70 ° C. using a heating table. As a result, the protective film-forming film, the silicon wafer 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 are provided. Two silicon wafers with a protective film-forming film provided with a release film were produced.
Next, the second release film is removed from the silicon wafer with the protective film-forming film, and the obtained silicon wafer with the protective film-forming film is conveyed in the LC tape laminator using a suction arm which is a conveying means. It was stored in a wafer cassette. In this suction arm, the diameter of the circular suction area at the tip of the arm is 34 mm, and the pressure of the vacuum source is −84 ± 4 kPa. At this time, the transport means was brought into contact with the exposed surface of the protective film-forming film in the silicon wafer with the protective film-forming film.
By repeating the steps from the step of removing the first release film from the laminated film to the step of storing the silicon wafer with the protective film forming film in the wafer cassette 10 times in place of the silicon wafer, the inside of the wafer cassette is protected. Ten silicon wafers with a film-forming film were stored.

Next, 10 silicon wafers with a protective film-forming film after storage were manually taken out of the wafer cassette without using the transport means.
Next, the silicon wafer with the protective film-forming film taken out was placed on the evaluation table with the protective film-forming film facing upward (the silicon wafer facing downward toward the surface of the evaluation table). The height of the surface of the evaluation table (the surface on which the silicon wafer with the protective film-forming film was placed) from the floor was almost the same in all regions, and the surface was flat. A fluorescent lamp was installed at a position 1.7 m above the surface (exposed surface) of the protective film-forming film in the silicon wafer with the protective film-forming film placed on the evaluation table. Further, the evaluator was arranged so that the position of the middle portion of both eyes of the evaluator was directly above the surface (exposed surface) of the protective film forming film by 0.3 to 0.4 m. However, at this time, a line segment (1) extending upward at right angles to the surface of the protective film-forming film from the central portion of the protective film-forming film, the central portion of the protective film-forming film, and the fluorescence of the fluorescent lamp. The angle formed by the line segment (2) connecting the center of the surface and the center of the surface is set to 10 to 20 °. Further, the angle formed by the line segment (3) connecting the central portion of the protective film forming film and the intermediate portion of both eyes of the evaluator and the line segment (1) is set to 10 to 20 °. .. Further, the line segment (1), the line segment (2), and the line segment (3) are arranged to be located in the same plane. In such an arrangement state, the evaluator visually observed the exposed surface (the surface on the side not provided with the silicon wafer) of the protective film forming film. This visual observation was performed one by one for 10 silicon wafers with a protective film-forming film. Then, the degree of visual recognition of the contact marks of the transport means was quantified according to the following criteria.
[Quantification of the degree of visibility of contact marks]
0 point: Conspicuous contact marks were visually recognized.
1 point: Inconspicuous contact marks were visually recognized.
2 points: No contact marks were visible.

Next, the total value of these numerical values for 10 sheets was calculated, and the effect of suppressing the contact marks of the transport means on the protective film-forming film was evaluated according to the following criteria. The results are shown in Table 1.
[Evaluation of contact mark suppression effect]
A: The total value is 12 to 20 points.
B: The total value is 8 to 11 points.
C: The total value is 4 to 7 points.
D: The total value is 1 to 3 points.
E: The total value is 0 points.

<Evaluation of laser printing visibility of protective film>
One of the 10 silicon wafers with a protective film-forming film evaluated for the effect of suppressing contact marks of the above-mentioned transport means was heated at 130 ° C. for 2 hours to thermally cure the protective film-forming film. A silicon wafer with a protective film was used.
Next, using a laser printing device (“LP-V10” manufactured by SUNX) equipped with a fiber laser (wavelength 1.06 μm), under the conditions of laser power 10.0 (no unit) and scan speed 200 mm / s. The character string "ABCD" was laser-printed from the outside of the protective film side of the protective film on the surface (exposed surface) of the protective film opposite to the silicon wafer side, with a character size of 500 μm in length and 400 μm in width. ..

Next, each of the four evaluators visually observed the printed surface (exposed surface) of the protective film from the outside on the protective film side of the silicon wafer with the protective film, and quantified the visibility of laser printing according to the following criteria. bottom.
[Quantification of visibility of laser printing]
2 points: Laser printing was easily visible.
1 point: Laser printing was visible, though not easy.
0 point: Laser printing could not be visually recognized.

Next, the total value of these numerical values for four evaluators was calculated, and the laser printing visibility of the protective film was evaluated according to the following criteria. The results are shown in Table 1.
[Evaluation of laser printing visibility of protective film]
A: The total value is 6 to 8 points.
B: The total value is 4 to 5 points.
C: The total value is 2 to 3 points.
D: The total value is 0 to 1 point.

<Evaluation of suitability for attaching protective film forming film to wafer>
An 8-inch silicon wafer (diameter 200 mm, thickness 350 μm, no bumps) was fixed on the table.
Next, a 300 mm fully automatic LC tape laminator "RAD-3600F / 12" manufactured by Lintec Corporation was used in the specifications for a 200 mm wafer, and the first release film was removed from the laminated film obtained above.
Next, while heating the silicon wafer together with the table to 70 ° C., the surface (exposed surface) of the protective film-forming film on the side not provided with the second release film was placed on the # 2000 polished surface of the silicon wafer with a diameter of 198 mm. I pasted it in size.

Next, the obtained silicon wafer with the protective film-forming film was visually observed, and the presence or absence of air bubbles between the protective film-forming film and the silicon wafer, and if there were air bubbles, the location where the air bubbles exist (protective film-forming film). The number of places where the film was incompletely attached to the wafer) was confirmed, and the suitability for attaching the protective film-forming film to the wafer was evaluated according to the following criteria. The results are shown in Table 1.
[Evaluation of suitability for attaching protective film forming film to wafer]
A: There are no bubbles.
B: There are 1 or 2 bubbles.
C: There are 3 to 4 bubbles.
D: There are 5 or more bubbles.

<< Manufacture and evaluation of protective film forming film >>
[Examples 2 to 13, Comparative Examples 1 to 5]
The composition of the protective film-forming composition (III-1) at the time of production so that the types and contents of the components contained in the protective film-forming composition (III-1) are as shown in Tables 1 to 3. A protective film-forming film was produced and evaluated in the same manner as in Example 1 except that one or both of the types of components and the blending amount were changed. The results are shown in Tables 1-3.
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 (the component is not contained).

As is clear from the above results, in the protective film-forming films of Examples 1 to 13, the effect of suppressing the contact marks of the conveying means (adsorption marks of the suction arm) was high. In the protective film-forming film of Examples 1 to 13, the Y value was 273 or more.

In the protective film-forming films of Examples 1 to 13, the X value was 36 or more, and these protective film-forming films were not excessively soft and had hardness of a specific value or more. In particular, the protective film-forming films of Examples 1 to 11 have an X value of 36 to 45.9 and have a more appropriate hardness, and as a result, an X value of 53.6 to 57.8. The stickability was superior to that of the protective film-forming films of Examples 12 to 13, which were harder.

The protective film-forming films of Examples 1 to 13 had an R _max of 5.1 to 54%, but _{the protective film-forming films of Examples 1, 2 and 10 to 12 had an R max} of 5. Example 3 in which the light (380 to 780 nm) reflectance is low at _{1-14.2% and as a result, the R max} is 21.3 to 54% and the light (380 to 780 nm) reflectance is high. The laser printing visibility was superior to that of the protective films of ~ 9 and 13.
The protective film-forming film of Example 8 had the _{highest R max} of 54% and the lowest laser printing visibility of the protective film because the content of the colorant (J) -2 was the highest. The protective film-forming film of Example 9 having a composition in which a part thereof is replaced with a color former (K) -1 has a R _max reduced to 37%, and the laser printing visibility of the protective film is also improved. rice field.
_{Focusing on the R max} of the protective film forming film, the value in Example 9 is located between the value in Example 5 and the value in Example 6, but the protective film of Example 9 is. The laser printing visibility was better than that of the protective films of Examples 5 and 6. It was presumed that this was because the protective film-forming film and the protective film of Example 9 contained the color former (K).

In each of the protective film-forming films of Examples 1 to 13, not only the entire area on both sides but also the entire area inside (that is, the entire area) had a single color tone.

On the other hand, in the protective film-forming films of Comparative Examples 1 to 5, the effect of suppressing the contact marks of the conveying means was not observed.
In the protective film-forming films of Comparative Examples 1 to 4, the Y value was 251 or less. In Comparative Examples 1 to 4, the R _max of the protective film-forming film was relatively small, and the X value of the protective film-forming film was not large enough to mitigate the influence of the protective film-forming film. It was presumed that the inhibitory effect of the film was not observed.
In the protective film-forming film of Comparative Example 5, the X value was 32.7. Since this protective film-forming film was excessively soft, it was presumed that the effect of suppressing contact marks of the transport means was not observed.

INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing various substrate devices including semiconductor devices.

101, 102, 103, 104 ... Composite sheet for forming a protective film, 10, 20 ... Support sheet, 10a, 20a ... One surface (first surface) of the support sheet, 11 ... Base material , 12 ... Adhesive layer, 13, 23 ... Protective film forming film, 13a, 23a ... One surface (first surface) of the protective film forming film, 13b, 23b ... Protective film forming film The other surface (second surface), 7 ... Conveying means, 9 ... Wafer, 9b ... Back surface of wafer, 913 ... Wafer with protective film forming film

Claims (9)

It is a protective film forming film for forming a protective film on the back surface of the divided piece of the work.
By laminating a plurality of the protective film forming films, a test piece having a width of 4 mm and a thickness within the range of 200 ± 20 μm is produced, the test piece is held, and a tension mode having a frequency of 11 Hz is used. under the measurement conditions of rising rate of 3 ° C. / min, to measure the storage modulus of the test piece, a storage elastic modulus when the temperature of the test piece is 70 ° C. and E _'70, the protective film formation film, When the maximum value of the reflectance of light having a wavelength of 380 to 780 nm is R _max , the protective film-forming film has the following formula:
Y = (log _{10 E'70} ) ² x R _max
The Y value calculated by is 260 or more, and the following formula:
X = (log _{10 E'70} ) ²
A protective film-forming film having an X value of 33 or more calculated by. The protective film-forming film according to claim 1, wherein the R _{max is 5% or more.} The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film is thermosetting or energy ray-curable. The protective film-forming film according to any one of claims 1 to 3, wherein the protective film-forming film contains a white pigment. The protective film-forming film according to any one of claims 1 to 4, wherein the protective film-forming film contains a laser marking color former. The protective film-forming film according to any one of claims 1 to 5, wherein the protective film-forming film has a single color tone on at least both sides. The protective film-forming film according to any one of claims 1 to 6, wherein the protective film-forming film comprises one layer. A support sheet and a protective film-forming film provided on one surface of the support sheet are provided.
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 transporting a work with a protective film-forming film, comprising a work and a protective film-forming film provided on the back surface of the work.
The protective film-forming film is the protective film-forming film according to any one of claims 1 to 7.
The transport method is a step of bringing the transport means into contact with the exposed surface of the protective film-forming film in the work with the protective film-forming film, and transporting the work with the protective film-forming film in a state of being fixed by the transport means. A method for transporting a work with a protective film forming film.

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