JP6438181B1 - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

A method of manufacturing a semiconductor device, wherein at least a first surface having a bump in a semiconductor chip is provided with a first protective film, or a second surface on the second surface opposite to the first surface in the semiconductor chip is protected. Producing a semiconductor chip with a protective film comprising a film, and producing a laminated structure in which the semiconductor chip with protective film is bonded to a substrate via a bump; with the protective film In the production of a semiconductor chip, the first protective film is formed so that the upper part of the bump protrudes through the first protective film; the first protective film or the second protective film is a shear strength ratio of the laminated structure. A method for manufacturing a semiconductor device, which is a protective film having a characteristic that a rupture risk factor is −0.9 to 0.9 with a value of 1.05-2.

Description

The present invention relates to a semiconductor device and a manufacturing method thereof.
This application claims priority on May 17, 2017 based on Japanese Patent Application No. 2017-097994 for which it applied to Japan, and uses the content here.

  Conventionally, when a multi-pin LSI package used for an MPU, a gate array or the like is mounted on a printed wiring board, a projecting electrode (hereinafter referred to as eutectic solder, high temperature solder, gold, etc.) is formed as a semiconductor chip on a connection pad portion thereof. In the present specification, these are referred to as “bumps”, and the bumps are brought into contact with the corresponding terminal portions on the chip mounting substrate by a so-called face-down method so as to be melted / diffused. A flip chip mounting method for bonding is adopted.

  Bumps are formed on the circuit surface of the semiconductor chip used in this mounting method. A resin film may be formed on the circuit surface (in other words, the bump forming surface) or the back surface opposite to the circuit surface of this semiconductor chip depending on the purpose (see Patent Documents 1 to 3). ).

  For example, the above-described semiconductor chip can be obtained by dicing a semiconductor wafer having bumps formed on its circuit surface into pieces. Then, the surface of the semiconductor wafer opposite to the circuit surface (bump forming surface) may be ground. In the process of obtaining such a semiconductor chip, for the purpose of protecting the bump forming surface and the bump of the semiconductor wafer, a curable resin film is applied to the bump forming surface, and this film is cured to form a protective film on the bump forming surface. May form.

  When the flip chip mounting method is employed, the back surface opposite to the circuit surface (bump forming surface) of the semiconductor chip may be exposed. Therefore, when a semiconductor wafer with bumps formed on the circuit surface is diced, or when a semiconductor device obtained by dicing is packaged and a semiconductor device is manufactured, cracks are prevented from occurring in the semiconductor chip. Therefore, a resin film made of an organic material may be formed as a protective film on the back surface of the semiconductor chip.

  Such a semiconductor chip provided with the above-described protective film as a resin film is widely used in the manufacturing process of a semiconductor device and is particularly important.

JP 2012-169484 A JP 2013-030766 A Japanese Patent No. 3957244

On the other hand, when a semiconductor device is manufactured or when the obtained semiconductor device is used, a semiconductor chip provided with a protective film is placed under a high temperature condition or a low temperature condition while being bonded to a substrate. And may be exposed to severe temperature conditions. In that case, due to such a change in temperature, the bonding state between the semiconductor chip provided with the protective film and the substrate may be destroyed. Therefore, it is desirable for a semiconductor chip provided with a protective film to be maintained in a stable state with respect to the substrate even under conditions where temperature changes are severe.
However, it is not certain whether the semiconductor chips described in Patent Documents 1 to 3 have such stability.

  Therefore, an object of the present invention is to provide a semiconductor device in which the bonding of a semiconductor chip provided with a protective film to a substrate is maintained in a stable state even under a condition where the temperature change is severe, and a manufacturing method thereof.

In order to solve the above problems, the present invention includes the following aspects.
[1] A method of manufacturing a semiconductor device,
At least a first protective film is provided on the first surface of the semiconductor chip having bumps, or a second protective film is provided on the second surface of the semiconductor chip opposite to the first surface. Producing a semiconductor chip;
Producing a laminated structure in which the semiconductor chip with a protective film is bonded to a substrate via bumps;
In the production of the semiconductor chip with the protective film, the first protective film is formed such that the upper part of the bump protrudes through the first protective film,
The first protective film or the second protective film has a shear strength ratio of 1.05 to 2 when the shear strength ratio and fracture risk factor of the laminated structure are measured by the following method, and the fracture risk factor is A protective film having a characteristic of -0.9 to 0.9;
A method for manufacturing a semiconductor device.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state between the semiconductor chip with a protective film and the copper substrate is broken is applied to the shear strength (N )age,
Except that the first protective film and the second protective film are not provided, a comparative test piece having the same structure as the test piece of the laminated structure is produced, and the force is applied in the same manner as the test piece of the laminated structure. In addition, when the force when the bonded state between the semiconductor chip of the comparative test piece and the copper substrate is broken is set as the comparative shear strength (N) of the comparative laminated structure,
The value of [shear strength of the laminated structure] / [comparative shear strength of the comparative laminated structure] is defined as the shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
Test specimens having a width of 5 mm and a length of 20 mm of all layers constituting the laminated structure were prepared, and all the test specimens were increased from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min. A heating / cooling test is performed in which the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min, and the expansion amount Eμm of the test piece when the temperature is increased from 23 ° C. to 150 ° C. The amount of expansion / shrinkage ES μm, which is the total amount of the shrinkage amount Sμm of the test piece when the temperature is lowered to 65 ° C., is obtained, and further, [expansion / shrinkage amount ES of the test piece] × [thickness of the test piece] The expansion / contraction parameter P μm ² which is the value of
Subsequently, an expansion / contraction parameter difference ΔP1 μm ² which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate] is obtained,
Next, an expansion / contraction standard parameter difference which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate, the first protective film, and the second protective film]. When obtaining ΔP0 μm ² ,
The value of ΔP1 / ΔP0 is used as a risk factor for fracture of the laminated structure.
[2] A semiconductor device including a laminated structure in which a semiconductor chip with a protective film having a bump is bonded to a substrate via the bump,
The semiconductor chip with a protective film includes at least a first protective film on a first surface of the semiconductor chip having bumps, or a second protective film on a second surface of the semiconductor chip opposite to the first surface. With
In the first protective film, the upper part of the bump protrudes through the first protective film,
The first protective film or the second protective film has a shear strength ratio of 1.05 to 2 when the shear strength ratio and fracture risk factor of the laminated structure are measured by the following method, and the fracture risk factor is A semiconductor device which is a protective film having a characteristic of −0.9 to 0.9.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state between the semiconductor chip with a protective film and the copper substrate is broken is applied to the shear strength (N )age,
Except that the first protective film and the second protective film are not provided, a comparative test piece having the same structure as the test piece of the laminated structure is produced, and the force is applied in the same manner as the test piece of the laminated structure. In addition, when the force when the bonded state between the semiconductor chip of the comparative test piece and the copper substrate is broken is set as the comparative shear strength (N) of the comparative laminated structure,
The value of [shear strength of the laminated structure] / [comparative shear strength of the comparative laminated structure] is defined as the shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
Test specimens having a width of 5 mm and a length of 20 mm of all layers constituting the laminated structure were prepared, and all the test specimens were increased from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min. A heating / cooling test is performed in which the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min, and the expansion amount Eμm of the test piece when the temperature is increased from 23 ° C. to 150 ° C. The amount of expansion / shrinkage ES μm, which is the total amount of the shrinkage amount Sμm of the test piece when the temperature is lowered to 65 ° C., is obtained, and further, [expansion / shrinkage amount ES of the test piece] × [thickness of the test piece] The expansion / contraction parameter P μm ² which is the value of
Subsequently, an expansion / contraction parameter difference ΔP1 μm ² which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate] is obtained,
Next, an expansion / contraction standard parameter difference which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate, the first protective film, and the second protective film]. When obtaining ΔP0 μm ² ,
The value of ΔP1 / ΔP0 is used as a risk factor for fracture of the laminated structure.

  ADVANTAGE OF THE INVENTION According to this invention, the semiconductor device with which the joining with respect to the board | substrate of the semiconductor chip provided with the protective film was maintained stably also on the conditions where a temperature change is severe, and its manufacturing method are provided.

It is sectional drawing which shows typically one Embodiment of the laminated structure produced with the manufacturing method of this invention. It is sectional drawing which shows typically an example of the laminated structure for a comparison used when employ | adopting the manufacturing method of this invention. It is sectional drawing which shows typically other embodiment of the laminated structure produced with the manufacturing method of this invention. It is sectional drawing which shows typically other embodiment of the laminated structure produced with the manufacturing method of this invention. It is sectional drawing which shows typically an example of the sheet | seat for 1st protective film formation used with the manufacturing method of this invention. It is sectional drawing which shows typically the other example of the 1st sheet | seat for protective film formation used with the manufacturing method of this invention.

Semiconductor Device Manufacturing Method A semiconductor device manufacturing method according to an embodiment of the present invention includes at least a first protective film on a first surface having bumps of a semiconductor chip, or the first surface of a semiconductor chip. A step of manufacturing a semiconductor chip with a protective film, which is provided with a second protective film on the second surface on the opposite side to (abbreviated as “semiconductor chip with protective film manufacturing step” in this specification); A step of producing a laminated structure in which the semiconductor chip with a protective film is bonded to a substrate via a bump (in this specification, it may be abbreviated as a “laminated structure producing step”), In the manufacture of the semiconductor chip with a protective film, when the semiconductor chip with a protective film includes the first protective film, the upper part of the bump protrudes through the first protective film. Formed to The first protective film or the second protective film has a shear strength ratio of 1.05 to 2 when the shear strength ratio and fracture risk factor of the laminated structure are measured, and the fracture risk factor is − It is a protective film having a characteristic of 0.9 to 0.9.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate (that is, the upper surface of the copper substrate when the copper substrate is placed on a flat surface), and the semiconductor chip with the protective film and the copper substrate are joined. For comparison of the same structure as the laminated structure except that the force when the state is destroyed is the shear strength (N) of the laminated structure and the first protective film and the second protective film are not provided. A laminated structure (also referred to as a comparative test piece) is prepared, and a force is applied in the same manner as the laminated test piece, and the bonding state between the semiconductor chip and the copper substrate of the comparative test piece is destroyed. Force is the comparative shear strength (N) of the comparative laminated structure Occasionally, the value of the shear strength of the laminate structure] / [comparative shear strength of the comparative laminate structures, and shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
When all the layers constituting the laminated structure are viewed from above and viewed in plan, test pieces having a width of 5 mm and a length of 20 mm are produced. All the test pieces are heated from −70 ° C. The above-mentioned test piece when a heating / cooling test is performed in which the temperature is increased from 200 ° C. to 200 ° C. at a rate of 5 ° C./min, and the temperature is decreased to −70 ° C. at a rate of temperature decrease of 5 ° C./min. The expansion / shrinkage amount ESμm, which is the total amount of the expansion amount Eμm of the test piece and the shrinkage amount Sμm of the test piece when the temperature is lowered from 23 ° C. to −65 ° C., is further calculated. ] × [thickness of the test piece] is obtained as an expansion / contraction parameter P μm ² , and then [expansion / contraction parameter P of the test piece of the substrate] − [expansion / contraction parameter P of all the test pieces other than the substrate] With the value of “Total value” The expansion and contraction parameter difference DerutaP1myuemu ² determined that, then, [the expansion contraction parameter P of the substrate of the test piece] - [substrate, the total value of the expansion and contraction parameters P of all the specimens other than the first protective film and second protective film The value of ΔP1 / ΔP0 when the expansion / shrinkage reference parameter difference ΔP0 μm ² that is the value of] is obtained is taken as the risk of fracture of the laminated structure.

  In the method for manufacturing a semiconductor device according to the present invention, as the first protective film or the second protective film constituting the semiconductor chip with a protective film, the stacked structure satisfies both the above-described shear strength ratio and breakage risk factor conditions. By selecting the protective film having the above characteristics, it is possible to obtain a semiconductor device in which the bonding of the semiconductor chip with the protective film to the substrate is maintained in a stable state even under a severe temperature change condition.

  The semiconductor device obtained by the manufacturing method of the present invention is not particularly limited as long as it includes the laminated structure.

-Semiconductor chip with a protective film The semiconductor chip with a protective film produced in the process of producing the semiconductor chip with a protective film in the manufacturing method includes one or both of the first protective film and the second protective film. That is, the semiconductor chip with a protective film includes a first protective film and may not include a second protective film, or may include a second protective film and may not include a first protective film. Both the first protective film and the second protective film may be provided.

The first protective film is a film formed on the first surface (in other words, the circuit surface or bump forming surface of the semiconductor chip) having the bumps of the semiconductor chip, and is a resin film (a curable resin layer described later). . The first protective film protects the bumps and the first surface of the semiconductor chip.
On the other hand, the second protective film is a film formed on the second surface opposite to the first surface of the semiconductor chip (in other words, the back surface of the semiconductor chip), and is a resin film (a curable resin layer described later). is there. The second protective film is used when the semiconductor wafer having the bump formed on the circuit surface is diced to produce the semiconductor chip described above or until the semiconductor chip obtained by dicing is packaged to manufacture the semiconductor device. In the meantime, the generation of cracks in the semiconductor chip is prevented.
Hereinafter, the laminated structure produced by the manufacturing method will be described first.

Stacked Structure FIG. 1 is a cross-sectional view schematically showing one embodiment of the stacked structure manufactured by the manufacturing method. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The laminated structure 1 shown here includes a semiconductor chip 10 with a protective film and a substrate 14.
The semiconductor chip 10 with a protective film includes a first protective film 12 on the first surface 11 a of the semiconductor chip 11 and a second protective film 13 on the second surface 11 b of the semiconductor chip 11.
The semiconductor chip 11 has a plurality of aligned bumps 111 on its first surface 11a.
The first protective film 12 covers the first surface 11a of the semiconductor chip 11 and the region of the surface 111a of the bump 111 on the side close to the first surface 11a of the semiconductor chip 11, and covers these covered regions. Protect.
The upper portion 1110 of the bump 111, that is, the top portion of the bump 111 far from the first surface 11 a of the semiconductor chip 11 and the vicinity thereof penetrate the first protective film 12 and the surface (exposed surface) of the first protective film 12. ). Then, the surface 14a of the substrate 14 facing the semiconductor chip 10 with the protective film (which may be referred to as “first surface” of the substrate in this specification) 14a, and the above-described protruding portion of the bump 111 (for example, the top portion) ) Are in contact with each other, and the substrate 14 and the semiconductor chip 10 with the protective film are electrically connected.
As described above, the laminated structure 1 is configured by bonding the semiconductor chip 10 with the protective film to the substrate 14 via the bumps 111.

Next, the shear strength ratio of the laminated structure 1 will be described.
In the manufacturing method of the semiconductor device provided with the laminated structure 1, the shear strength of the laminated structure 1 when the substrate 14 is a copper substrate means that the substrate 14 is fixed and the substrate is fixed to the semiconductor chip 10 with the protective film. A force is applied in a direction parallel to the surface of the substrate 14 (that is, the upper surface of the substrate when the substrate is placed on a flat surface, for example, the first surface 14a), and the semiconductor chip 10 with a protective film and the substrate 14 are This means the force applied to the semiconductor chip 10 with the protective film when the bonded state is broken.
When the force is applied to the semiconductor chip 10 with the protective film, the semiconductor chip 11 is preferably included in a region to which the force is applied, for example, the force is applied only to the semiconductor chip 11.

In the manufacturing method, the laminated structure except that the first protective film 12 and the second protective film 13 are not provided as a comparative laminated structure corresponding to the laminated structure 1 for obtaining the shear strength ratio. 1 is used. An example of such a comparative laminated structure is shown in FIG. FIG. 2 is a cross-sectional view schematically showing an example of a comparative laminated structure according to the manufacturing method. In FIG. 2, reference numeral 9 is attached to indicate a comparative laminated structure.
2 and the subsequent drawings, the same components as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted.

  In the manufacturing method, the comparative shear strength (N) of the comparative multilayer structure 9 is the same as that of the multilayer structure 1, that is, the substrate 14 is fixed and the substrate 14 is fixed to the semiconductor chip 11. A force (N) is applied in a direction parallel to the surface of the substrate (that is, the upper surface of the substrate when the substrate is placed on a flat surface, for example, the first surface 14a), and the semiconductor chip 11 and the substrate 14 are joined. It means the force (N) applied to the semiconductor chip 11 when the state is destroyed.

  In the method of manufacturing a semiconductor device including the laminated structure 1, the laminated structure is a value of [shear strength (N) of the laminated structure 1] / [comparative shear strength (N) of the comparative laminated structure 9]. The shear strength ratio of the body 1 is 1.05-2.

Next, the fracture risk factor of the laminated structure 1 will be described.
In order to calculate the fracture risk factor of the laminated structure 1, first, all the layers constituting the laminated structure 1, that is, the semiconductor chip 11, the first protective film 12, the second protective film 13, and the substrate 14. A test piece having a width of 5 mm and a length of 20 mm when viewed from above and viewed in plan is prepared. The thickness of the test piece of each layer is the same as the thickness of each layer in the laminated structure 1.

  Next, for all these test pieces, a heating / cooling test is performed in which the temperature is increased from −70 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min, and the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min The amount of expansion E μm (E> 0) of the test piece when the temperature was raised from 23 ° C. to 150 ° C., and the amount of shrinkage S μm (S> 0) of the test piece when the temperature was lowered from 23 ° C. to −65 ° C. And measure. Then, an expansion / contraction amount ES μm, which is a total amount of the expansion amount E and the contraction amount S, is obtained for each test piece.

Further, an expansion / contraction parameter P μm ² which is a value of [expansion / shrinkage amount ES (μm) of test piece] × [thickness of test piece (μm)] is obtained for each test piece.

Next, an expansion / contraction parameter difference which is a value of [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − [total value of the expansion / contraction parameters P of all the test pieces other than the substrate 14 (μm ² )]. ΔP1 μm ² is obtained.
More specifically, in the case of the laminated structure 1, the expansion / contraction parameter difference ΔP 1 μm ² is expressed as [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − ([expansion / contraction parameter of the test piece of the semiconductor chip 11]. is calculated by P (μm ^2)] + [expansion contraction parameter P of the specimen of the first protective film 12 (μm ^2)] + [expansion contraction parameter P of the test piece of the second protective layer 13 (μm ^2)]) .

Next, [Expansion / shrinkage parameter P (μm ² ) of test piece of substrate 14] − [Total value of expansion / shrinkage parameter P of all test pieces other than substrate, first protective film and second protective film (μm ² )] An expansion / contraction reference parameter difference ΔP0, which is a value of
More specifically, in the case of the laminated structure 1, the expansion / contraction reference parameter difference ΔP 0 μm ² is expressed as [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − [expansion / contraction parameter of the test piece of the semiconductor chip 11]. P (μm ² )].

  In the method for manufacturing a semiconductor device including the laminated structure 1, the risk of rupture of the laminated structure 1, which is a value of ΔP1 / ΔP0, is −0.9 to 0.9.

FIG. 3 is a cross-sectional view schematically showing another embodiment of the laminated structure produced by the manufacturing method.
The laminated structure 2 shown here is the same as the laminated structure 1 shown in FIG. 1 except that the second protective film 13 is not provided.
The laminated structure 2 is configured by bonding a semiconductor chip 20 with a protective film to a substrate 14 through bumps 111 thereof.

  In the method of manufacturing a semiconductor device including the laminated structure 2, the laminated structure is a value of [shear strength (N) of the laminated structure 2] / [comparative shear strength (N) of the comparative laminated structure 9]. The shear strength ratio of the body 2 is 1.05-2.

In the method of manufacturing a semiconductor device provided with the laminated structure 2, the fracture risk factor of the laminated structure 2 that is a value of ΔP1 / ΔP0 is −0.9 to 0.9.
In the case of the laminated structure 2, the expansion / contraction parameter difference ΔP1 μm ² is [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − ([expansion / contraction parameter P (μm ² ) of the test piece of the semiconductor chip 11]]. + [Expansion / contraction parameter P (μm ² ) of the test piece of the first protective film 12])
On the other hand, in the case of the laminated structure 2, the expansion / contraction reference parameter difference ΔP 0 μm ² is the same as in the case of the laminated structure 1 [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − [semiconductor chip 11 It is calculated from the expansion / contraction parameter P (μm ² )] of the test piece.

FIG. 4 is a cross-sectional view schematically showing still another embodiment of the laminated structure manufactured by the manufacturing method.
The laminated structure 3 shown here is the same as the laminated structure 1 shown in FIG. 1 except that the first protective film 12 is not provided.
The laminated structure 3 is configured by bonding a semiconductor chip 30 with a protective film to the substrate 14 via the bumps 111.

  In the method of manufacturing a semiconductor device provided with the laminated structure 3, the laminated structure is a value of [shear strength (N) of the laminated structure 3] / [comparative shear strength (N) of the laminated structure 9 for comparison]. The shear strength ratio of the body 3 is 1.05-2.

In the method of manufacturing a semiconductor device provided with the laminated structure 3, the risk of fracture of the laminated structure 3, which is a value of ΔP1 / ΔP0, is −0.9 to 0.9.
In the case of the laminated structure 3, the expansion / contraction parameter difference ΔP1 μm ² is [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − ([expansion / contraction parameter P (μm ² ) of the test piece of the semiconductor chip 11]]. + [Expansion / shrinkage parameter P (μm ² ) of the test piece of the second protective film 13])).
On the other hand, in the case of the laminated structure 3, the expansion / contraction reference parameter difference ΔP 0 μm ² is the same as in the case of the laminated structure 1, [expansion / contraction parameter P (μm ² ) of the test piece of the substrate 14] − [semiconductor chip 11 It is calculated from the expansion / contraction parameter P (μm ² )] of the test piece.

The laminated structure produced by the manufacturing method is not limited to that shown in FIG. 1 and FIGS. The configuration of the part may be changed, deleted, or added.
For example, the laminated structure may include a layer other than the semiconductor chip 11, the first protective film 12, the second protective film 13, and the substrate 14.

  The other layers are not particularly limited and can be arbitrarily selected according to the purpose. Preferred examples of the other layers include intermediate layers (first intermediate layer and second intermediate layer) described later.

The other layer may be composed of one layer (single layer), or may be composed of two or more layers. When the other layer is composed of a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, not only the case of the other layers, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers. May be different, and only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent material and thickness of each layer is different from each other ” "Means.

  The laminated structure may include the other layer on any of a semiconductor chip with a protective film (for example, the semiconductor chip with protective film 10, 20, or 30) and a substrate (for example, the substrate 14). However, in terms of easier adjustment of the above-described shear strength ratio and fracture risk factor, it is preferable that the other layer is provided in direct contact with any part of the semiconductor chip with a protective film. .

  In the case of the laminated structure including the other layers, when obtaining ΔP1, the test pieces of the other layers are handled as “all test pieces other than the substrate”. Similarly, when obtaining ΔP0, the test pieces of the other layers are handled as “all test pieces other than the substrate, the first protective film, and the second protective film”.

  In the said manufacturing method, the shear strength ratio of the said laminated structure is 1.05-2, it is preferable that it is 1.1-1.65, and it is more preferable that it is 1.15-1.3. Since the shear strength ratio is equal to or higher than the lower limit value, the laminated structure in the semiconductor device is maintained in a stable bonding state with respect to the substrate of the semiconductor chip with a protective film even under conditions where the temperature change is severe. Becomes higher. On the other hand, since the shear strength ratio is less than or equal to the upper limit value, it is avoided that the bonding force of the semiconductor chip with a protective film to the substrate is excessively strong, for example, the reliability of the semiconductor device is further improved, Fabrication of the semiconductor device (the laminated structure) is easier.

  The shear strength ratio of the laminated structure can be adjusted by adjusting the shear strength of the laminated structure. The shear strength of the laminated structure can be adjusted, for example, by adjusting the hardness (curing degree) of the first protective film or the second protective film, and the hardness of the first protective film or the second protective film is It can be adjusted by these constituent materials, thicknesses, and the like. For example, by improving the hardness of the first protective film or the second protective film, the force (shearing force) applied to the semiconductor chip with the protective film is better dispersed in these protective films, and as a result, It is presumed that the shear strength of the laminated structure is improved.

In the manufacturing method, the risk of fracture of the laminated structure is -0.9 to 0.9, -0.8 to 0.8, and -0.5 to 0.5. Also good. When the fracture risk factor is within such a range, even in a condition where the temperature change is severe, in the stacked structure in the semiconductor device, the bonding of the semiconductor chip with a protective film to the substrate is maintained in a stable state. Increases effectiveness. In particular, when the risk factor for breakage is −0.9 or more, the bump has a portion on the first surface side (root portion) of the semiconductor chip and a top portion on the opposite side of the first surface side and the vicinity thereof. Damage is further suppressed.
Normally, in the laminated structure, the semiconductor chip is less likely to expand and contract than the substrate when the temperature changes (the substrate is more likely to expand and contract than the semiconductor chip). On the other hand, since the first protective film and the second protective film are usually more easily expanded and contracted than the semiconductor chip, the semiconductor chip with the protective film is more likely to expand and contract the substrate when the temperature changes than the single semiconductor chip. Easy to follow. Therefore, the effect of this invention is acquired because a fracture risk factor exists in the said range.

The said board | substrate is not specifically limited, According to the objective, it can select arbitrarily.
For example, examples of the constituent material of the substrate include metals such as copper, gold, and aluminum; resins such as polyimide and epoxy resin; ceramics such as aluminum oxide and glass.
The constituent material of the substrate may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. For example, the substrate having two or more constituent materials includes a substrate made of a polymer alloy using two or more resins in combination, a substrate made of a material using a resin component such as a glass epoxy resin and a non-resin component in combination, and the like. It is done. However, these are examples.

  Although the thickness of a board | substrate is not specifically limited, It is preferable that it is 10-3000 micrometers, It is more preferable that it is 100-2000 micrometers, It is especially preferable that it is 500-1000 micrometers. The effect of this invention becomes higher because the thickness of a board | substrate is in such a range.

  The thickness of the first protective film is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the first protective film is equal to or greater than the lower limit, the first surface of the semiconductor chip, the surface having the bumps of the semiconductor wafer (circuit surface or bump forming surface), and the bumps of the semiconductor chip and the semiconductor wafer, The protective ability of the first protective film becomes higher. Moreover, when the thickness of the first protective film is equal to or less than the upper limit value, an excessive thickness is suppressed.

  In the present specification, for the “semiconductor wafer having bumps on the surface”, the surface having the bumps (circuit surface or bump forming surface of the semiconductor wafer) is the first as in the case of the semiconductor chip having bumps on the surface. The surface opposite to the first surface (in other words, the back surface of the semiconductor wafer) may be referred to as the second surface.

  The thickness of the second protective film is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the second protective film is equal to or more than the lower limit value, the protective ability of the second protective film for the semiconductor chip is further increased. Moreover, when the thickness of the second protective film is equal to or less than the upper limit value, an excessive thickness is suppressed.

Although the thickness of a semiconductor chip is not specifically limited, It is preferable that it is 20-1000 micrometers, It is more preferable that it is 40-500 micrometers, For example, 100-300 micrometers etc. may be sufficient. The effect of this invention becomes higher because the thickness of a semiconductor chip is in such a range.
In this specification, “the thickness of the semiconductor chip” means “the thickness of the portion excluding the bumps of the semiconductor chip” unless otherwise specified. That is, the thickness of the semiconductor chip does not include the height of bumps described later.

The kind and arrangement | positioning form of the bump in a semiconductor chip can be selected arbitrarily according to the objective, and are not specifically limited.
For example, the height of the bump is not particularly limited, but is preferably 120 to 300 μm, more preferably 150 to 270 μm, and particularly preferably 180 to 240 μm. When the bump height is equal to or higher than the lower limit, the function of the bump can be further improved. Moreover, when the height of the bump is not more than the above upper limit value, the curable resin film on the upper part of the bump when the curable resin film for forming the first protective film is attached to the first surface of the semiconductor wafer. The effect of suppressing the remaining is further increased.
In the present specification, the “bump height” means the height of the bump at the highest position from the first surface of the semiconductor wafer or semiconductor chip.

The width of the bump is not particularly limited, but is preferably 170 to 350 μm, more preferably 200 to 320 μm, and particularly preferably 230 to 290 μm. When the bump width is equal to or greater than the lower limit, the function of the bump can be further improved. In addition, when the width of the bump is equal to or less than the upper limit value, when the curable resin film for forming the first protective film is attached to the first surface of the semiconductor wafer, The effect of suppressing the remaining becomes higher.
In the present specification, the “bump width” refers to a distance between two different points on the bump surface when the bump is viewed from a direction perpendicular to the first surface of the semiconductor wafer or semiconductor chip. It means the maximum value of the line segment obtained by connecting with a straight line.

The distance between adjacent bumps is not particularly limited, but is preferably 250 to 800 μm, more preferably 300 to 600 μm, and particularly preferably 350 to 500 μm. When the distance is not less than the lower limit value, the function of the bump can be further improved. Moreover, when the distance is not more than the upper limit, when the curable resin film for forming the first protective film is attached to the first surface of the semiconductor wafer, the curable resin film remains on the bumps. The effect which suppresses becomes higher.
In the present specification, “distance between adjacent bumps” means the minimum distance between the surfaces of adjacent bumps.
Next, the manufacturing method will be described more specifically.

-The semiconductor chip manufacturing process with a protective film The semiconductor chip manufacturing process with a protective film is, for example, for forming a first protective film in a semiconductor chip with a protective film having a first protective film on the first surface of the semiconductor chip. After the curable resin film is attached to the first surface (bump forming surface, circuit surface) of the semiconductor wafer, the curable resin film is cured to form the first protective film, and then the first protective film is formed by dicing. The semiconductor wafer is solidified (divided) together with the protective film, or the semiconductor wafer is solidified (divided) together with the curable resin film by dicing, and then the curable resin film is cured to be first. It can be manufactured by forming a protective film.

A semiconductor chip with a protective film provided with a second protective film on the second surface of the semiconductor chip is also a semiconductor chip with a protective film provided with the first protective film on the first surface, except that the formation part of the protective film is different. Can be produced by the same method.
For example, after a curable resin film for forming the second protective film is attached to the second surface of the semiconductor wafer, the curable resin film is cured to form a second protective film, and then dicing is performed. The semiconductor wafer is solidified (divided) together with the second protective film, or the semiconductor wafer is solidified (divided) together with the curable resin film by dicing, and then the curable resin film is cured. By forming the second protective film, a semiconductor chip with a protective film having the second protective film on the second surface can be manufactured.

When a semiconductor chip with a protective film including both the first protective film and the second protective film is manufactured, the order of forming these protective films is not particularly limited. For example, the second protective film may be formed after forming the first protective film, the first protective film may be formed after forming the second protective film, or the first protective film and the first protective film Two protective films may be formed simultaneously.
More specifically, for example, one of the sticking of the curable resin film for forming the first protective film to the semiconductor wafer and the sticking of the curable resin film for forming the second protective film to the semiconductor wafer are either May be performed first and the other may be performed later or simultaneously.
Further, the formation of the first protective film by curing of the curable resin film and the formation of the second protective film by curing of the curable resin film may be performed first, and the other may be performed later. You may do it at the same time.

  The first protective film is formed using, for example, a first protective film-forming sheet that includes a first support sheet and includes a curable resin film for forming the first protective film on the first support sheet. ,It can be carried out. In the present specification, the “curable resin film” may be referred to as a “curable resin layer”.

When the first protective film-forming sheet is used, the first protective film-forming sheet is attached to the semiconductor wafer first through the curable resin layer (curable resin film) constituting the first protective film-forming sheet. Affix to one side. And by heating the curable resin layer after pasting, its fluidity is increased, it is spread between the bumps so as to cover the bumps, and is in close contact with the first surface of the semiconductor wafer. The bump is embedded in the curable resin layer so as to cover the surface in the vicinity of the first surface of the semiconductor wafer. Thereby, the formation of the curable resin layer on the first surface of the semiconductor wafer is completed. The curable resin layer formed on the first surface of the semiconductor wafer or the semiconductor chip is cured by heating or irradiation with energy rays at a target timing, thereby forming a first protective film. The first protective film protects the first surface of the semiconductor wafer or semiconductor chip and the bumps in close contact with them.
The first support sheet in the first protective film forming sheet may be removed at a suitable timing before and after curing of the curable resin layer.

  The formation of the second protective film is, for example, a second protective film having a second support sheet and a curable resin film (curable resin layer) for forming a second protective film provided on the second support sheet. This can be done using a forming sheet.

When the second protective film forming sheet is used, the second protective film forming sheet is attached to the second surface of the semiconductor wafer via the curable resin layer (curable resin film) constituting the second protective film forming sheet. Affix to Thereby, the formation of the curable resin layer on the second surface of the semiconductor wafer is completed. The second protective film is formed by curing the curable resin layer formed on the second surface of the semiconductor wafer or the semiconductor chip by heating or irradiation with energy rays at a target timing. The second protective film protects the second surface of the semiconductor wafer or the semiconductor chip while being in close contact with the second surface.
The second support sheet in the second protective film forming sheet may be removed at a suitable timing before and after the curing of the curable resin layer. Moreover, a 2nd support sheet can also be used as a dicing sheet when dicing the semiconductor wafer provided with the 2nd protective film which is a curable resin layer or its hardened | cured material.

In the present specification, even when the curable resin layer is cured to become the first protective film, the laminate is used as long as the laminated structure of the first support sheet and the first protective film is maintained. 1 referred to as a protective film forming sheet. Similarly, when the curable resin layer is cured to become the second protective film, the laminate is used for forming the second protective film as long as the laminated structure of the second support sheet and the second protective film is maintained. This is called a sheet.
Hereinafter, the configuration of the first protective film forming sheet will be described.

◇ First protective film forming sheet ◎ First support sheet The first support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When a support sheet consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

As a preferable first support sheet, for example, a first substrate is provided, and a first pressure-sensitive adhesive layer is laminated on the first substrate; a first substrate is provided, and the first substrate is provided on the first substrate. Examples include those in which a first intermediate layer is laminated and a first pressure-sensitive adhesive layer is laminated on the first intermediate layer; those consisting only of a first substrate; those consisting only of a release film.
Moreover, the 1st sheet | seat for protective film formation may be replaced with the 1st adhesive layer, and may be equipped with the energy-beam hardened | cured material of the energy-beam curable 1st adhesive layer mentioned later.

-1st base material The said 1st base material is a sheet form or a film form, As a constituent material, various resin is mentioned, for example.
Examples of the resin include polyethylene such as low density polyethylene (may be abbreviated as LDPE), linear low density polyethylene (may be abbreviated as LLDPE), and high density polyethylene (sometimes abbreviated as HDPE); polypropylene, Polyolefins other than polyethylene such as polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- Ethylene copolymers such as norbornene copolymers (ie, copolymers obtained using ethylene as a monomer); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (ie, vinyl chloride as a monomer) Resin obtained using Polycycloolefins; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, wholly aromatic polyesters in which all structural units have aromatic cyclic groups; Poly (meth) acrylic ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; It is done.
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

  In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid. For example, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”, and “(meth) acryloyl group” Is a concept including both an “acryloyl group” and a “methacryloyl group”.

  Only 1 type may be sufficient as resin which comprises a 1st base material, and when it is 2 or more types and they are 2 or more types, those combinations and ratios can be selected arbitrarily.

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

The thickness of the first base material is preferably 5 to 1000 μm.
Here, the “thickness of the first base material” means the thickness of the entire first base material. For example, the thickness of the first base material composed of a plurality of layers means all of the first base material. Means the total thickness of the layers.

  The first base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin. You may do it.

  In order to improve the adhesion between the first substrate and the layer provided in contact with the first substrate such as the first pressure-sensitive adhesive layer, the first substrate has an anchor coat layer on the surface thereof. The surface may be modified.

  The first substrate can be manufactured by a known method. For example, the 1st base material containing resin can be manufactured by shape | molding the resin composition containing the said resin.

○ Release Film The release film may be a known film in this field.
As the preferable release film, for example, at least one surface of a resin film such as polyethylene terephthalate is release-treated by silicone treatment or the like; at least one surface of the film is a release surface composed of polyolefin. And the like.
The thickness of the release film is preferably the same as the thickness of the first substrate.

-1st adhesive layer The said 1st adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, and polycarbonate, and acrylic resin is preferable.

  In the present invention, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has an adhesive property, Also included are resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.

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

The thickness of the first pressure-sensitive adhesive layer is preferably 1 to 1000 μm.
Here, the “thickness of the first pressure-sensitive adhesive layer” means the thickness of the entire first pressure-sensitive adhesive layer. For example, the thickness of the first pressure-sensitive adhesive layer composed of a plurality of layers means the first pressure-sensitive adhesive layer. Means the total thickness of all the layers that make up.

The first pressure-sensitive adhesive layer may be formed from an energy ray-curable pressure-sensitive adhesive, or may be formed from a non-energy ray-curable pressure-sensitive adhesive. The first pressure-sensitive adhesive layer formed from the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
In the present specification, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In this specification, “energy ray curable” means a property that cures when irradiated with energy rays, and “non-energy ray curable” means a property that does not cure even when irradiated with energy rays. To do.

<< 1st adhesive composition >>
The first pressure-sensitive adhesive layer can be formed from a first pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, a 1st adhesive layer can be formed in the target site | part by applying a 1st adhesive composition to the formation object surface of a 1st adhesive layer, and making it dry as needed.

  The first pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.

  Although the drying conditions of a 1st adhesive composition are not specifically limited, It is preferable to heat-dry the 1st adhesive composition containing the solvent mentioned later. It is preferable to dry the 1st adhesive composition containing a solvent on the conditions for 10 second-5 minutes at 70-130 degreeC, for example.

  When the first pressure-sensitive adhesive layer is energy ray-curable, the first pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable first pressure-sensitive adhesive composition is, for example, non-energy A first pressure-sensitive adhesive composition containing a linear curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound. (I-1); energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter referred to as “adhesiveness”) A first pressure-sensitive adhesive composition (I-2) containing the resin (I-2a) ”; the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable low molecular weight compound; The 1st adhesive composition (I-3) etc. to contain are mentioned.

Examples of the first pressure-sensitive adhesive composition include a non-energy ray-curable pressure-sensitive adhesive composition in addition to the energy beam-curable pressure-sensitive adhesive composition.
Examples of the non-energy ray curable first pressure-sensitive adhesive composition include non-energy materials such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. The 1st adhesive composition (I-4) containing a linear curable adhesive resin (I-1a) is mentioned, What contains acrylic resin is preferable.

<< Method for Producing First Adhesive Composition >>
The first pressure-sensitive adhesive compositions such as the first pressure-sensitive adhesive compositions (I-1) to (I-4) are the first pressure-sensitive adhesive, such as components other than the pressure-sensitive adhesive and, if necessary, the pressure-sensitive adhesive. It is obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

-1st intermediate | middle layer The said 1st intermediate | middle layer is a sheet form or a film form, What is necessary is just to select the constituent material suitably according to the objective, and it is not specifically limited.

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

The thickness of the first intermediate layer may be appropriately selected according to the purpose and is not particularly limited.
Here, the “thickness of the first intermediate layer” means the thickness of the entire first intermediate layer. For example, the thickness of the first intermediate layer composed of a plurality of layers means all of the first intermediate layer. Means the total thickness of the layers.

<< first intermediate layer forming composition >>
A 1st intermediate | middle layer can be formed from the composition for 1st intermediate | middle layer formation containing the constituent material.
For example, the first intermediate layer-forming composition is applied to the surface of the first intermediate layer and dried as necessary, or cured by irradiation with energy rays, so that the first intermediate layer is formed on the target site. Layers can be formed.

<< Method for Producing First Intermediate Layer Forming Composition >>
The composition for forming the first intermediate layer is obtained by the same method as in the case of the first pressure-sensitive adhesive composition except that the blending components are different.

◎ Curable resin layer The curable resin layer may be either a thermosetting resin layer (also referred to as a thermosetting resin film) or an energy ray curable resin layer (also referred to as an energy ray curable resin film). .
The curable resin layer forms a first protective film by curing.

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

○ Thermosetting resin layer The thermosetting resin layer preferably contains, for example, a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger. In the present invention, the polymerization reaction includes a polycondensation reaction.

The thickness of the thermosetting resin layer is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the thermosetting resin layer is equal to or more than the lower limit value, it is possible to form a first protective film with higher protection ability. Moreover, when the thickness of the thermosetting resin layer is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, “the thickness of the thermosetting resin layer” means the thickness of the entire thermosetting resin layer. For example, the thickness of the thermosetting resin layer composed of a plurality of layers means the thermosetting resin layer. Means the total thickness of all the layers that make up.

The thermosetting resin layer is affixed to the first surface of the semiconductor wafer and cured to form the first protective film. The curing condition is such that the first protective film exhibits its function sufficiently. As long as it is, it is not particularly limited, and may be appropriately selected according to the type of the thermosetting resin layer.
For example, the heating temperature during curing of the thermosetting resin layer is preferably 100 to 200 ° C, more preferably 110 to 180 ° C, and particularly preferably 120 to 170 ° C. The heating time during the curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3.5 hours, and particularly preferably 1 to 2.5 hours.

<< Composition for forming thermosetting resin layer >>
A thermosetting resin layer can be formed from the composition for thermosetting resin layer formation containing the constituent material. For example, a thermosetting resin layer can be formed at a target site by applying a thermosetting resin layer forming composition to the surface on which the thermosetting resin layer is to be formed and drying it as necessary.

The thermosetting resin layer-forming composition may be applied by a known method, for example, by the same method as that for the first pressure-sensitive adhesive composition described above.
Moreover, the drying conditions of the composition for thermosetting resin layer formation are not specifically limited, For example, it may be the same as the case of the above-mentioned 1st adhesive composition.

<Resin layer forming composition (III)>
As the thermosetting resin layer forming composition, for example, a thermosetting resin layer forming composition (III) containing a polymer component (A) and a thermosetting component (B) (in this specification, And may be simply abbreviated as “resin layer forming composition (III)”).

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like to the thermosetting resin layer.
The polymer component (A) contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one type, two or more types, and when two or more types are combined, The ratio can be arbitrarily selected.

  Examples of the polymer component (A) include polyvinyl acetal, acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, thermosetting polyimide, and the like. An acrylic resin is preferred.

As said polyvinyl acetal in a polymer component (A), a well-known thing is mentioned.
Especially, as a preferable polyvinyl acetal, polyvinyl formal, polyvinyl butyral, etc. are mentioned, for example, Polyvinyl butyral is more preferable.
As polyvinyl butyral, what has a structural unit represented by following formula (i) -1, (i) -2, and (i) -3 is mentioned.

（式中、ｌ、ｍ及びｎは、それぞれ独立に１以上の整数である。）

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

The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5,000 to 200,000, and more preferably 8,000 to 100,000. When the weight average molecular weight of the polyvinyl acetal is in such a range, when the thermosetting resin layer is pasted on the first surface, the thermosetting at the upper part of the bump (the top part of the bump and the vicinity thereof). The effect of suppressing the remaining resin layer is further increased.
In the present specification, the “weight average molecular weight” is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

  The glass transition temperature (Tg) of polyvinyl acetal is preferably 40 to 80 ° C, and more preferably 50 to 70 ° C. When the Tg of the polyvinyl acetal is within such a range, the effect of suppressing the remaining of the thermosetting resin layer on the upper part of the bump is higher when the thermosetting resin layer is attached to the first surface. Become.

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

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. When the weight average molecular weight of the acrylic resin is not less than the lower limit, the shape stability of the thermosetting resin layer (time stability during storage) is improved. Further, since the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the thermosetting resin layer easily follows the uneven surface of the adherend, and between the adherend and the thermosetting resin layer. Generation of voids and the like is further suppressed.

  The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. When Tg of the acrylic resin is equal to or more than the lower limit value, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved. Moreover, adhesive force with the to-be-adhered body of a thermosetting resin layer and a 1st protective film improves because Tg of acrylic resin is below the said upper limit.

  Examples of acrylic resins include polymers of one or more (meth) acrylic acid esters; in addition to (meth) acrylic acid esters, (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and Examples thereof include a copolymer obtained by copolymerizing one or more monomers selected from N-methylolacrylamide and the like.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid (Also known as uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (also known as palmityl (meth) acrylate) The alkyl group constituting the alkyl ester such as heptadecyl (meth) acrylate and octadecyl (meth) acrylate (also referred to as stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms. (Meth) acrylic acid alkyl ester;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) 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 esters such as (meth) acrylic acid N-methylaminoethyl. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

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

The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the first protective film forming sheet tends to be improved.
As one aspect, the acrylic resin is an acrylic resin obtained by copolymerizing at least one monomer selected from the group consisting of butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate. Is preferred.

  In the present invention, for example, as the polymer component (A), a thermoplastic resin other than polyvinyl acetal and acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used as polyvinyl acetal and acrylic resin. You may use independently, without using, and may use together with polyvinyl acetal or an acrylic resin. By using the thermoplastic resin, the peelability of the first protective film from the first support sheet is improved, and the thermosetting resin layer can easily follow the uneven surface of the adherend. Generation of voids and the like may be further suppressed between the curable resin layer.

  The thermoplastic resin preferably has a weight average molecular weight of 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, and more preferably -20 to 120 ° C.

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

  The thermoplastic resin contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof are as follows: Can be arbitrarily selected.

  The content of the polymer component (A) is based on the total mass of all components other than the solvent constituting the resin layer forming composition (III) regardless of the type of the polymer component (A) (that is, 5 to 85% by weight, more preferably 5 to 80% by weight, for example, 5 to 70% by weight, 5 to 60% by weight, based on the total weight of the thermosetting resin layer) Any of 5-50 mass%, 5-40 mass%, and 5-30 mass% may be sufficient. However, these contents in composition (III) for resin layer formation are examples.

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

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing the thermosetting resin layer to form a hard first protective film.
The thermosetting component (B) contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one type, two or more types, or a combination thereof when two or more types are used. The ratio can be arbitrarily selected.

  Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and epoxy thermosetting resins are preferable.

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy-based thermosetting resin contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one type, two or more types, and in the case of two or more types, combinations thereof and The ratio can be arbitrarily selected.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

  As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the 1st sheet | seat for protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meth) acrylamide groups and the like, and an acryloyl group is preferred.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000 from the viewpoints of curability of the thermosetting resin layer and strength and heat resistance of the first protective film after curing. 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
In the present specification, the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 130 to 800 g / eq.
In the present specification, the “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

  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, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. 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 has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. .
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (sometimes abbreviated as “DICY” in this specification).

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

  In the case of using a phenolic curing agent as the thermosetting agent (B2), the thermosetting agent (B2) has a softening point or a glass transition temperature from the viewpoint of improving the peelability of the first protective film from the first support sheet. A high one is preferred.

Among the thermosetting agents (B2), for example, the number average molecular weight of the resin component such as polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin is preferably 300 to 30000. 400 to 10,000 is more preferable, and 500 to 3000 is particularly preferable.
Among the thermosetting agents (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

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

  In the resin layer forming composition (III) and the thermosetting resin layer, the content of the thermosetting agent (B2) is 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). It is preferable that it is 1-200 mass parts, for example, 1-100 mass parts, 1-80 mass parts, and 1-60 mass parts may be sufficient. When the content of the thermosetting agent (B2) is equal to or more than the lower limit, curing of the thermosetting resin layer is more likely to proceed. Moreover, the moisture absorption rate of a thermosetting resin layer is reduced because the said content of a thermosetting agent (B2) is below the said upper limit, The package obtained using the sheet | seat for 1st protective film formation Reliability is further improved.

  In the resin layer forming composition (III) and the thermosetting resin layer, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is heavy. It is preferably 50 to 1000 parts by mass, more preferably 60 to 950 parts by mass, and particularly preferably 70 to 900 parts by mass with respect to 100 parts by mass of the combined component (A). When the content of the thermosetting component (B) is within such a range, the adhesive force between the first protective film and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

[Curing accelerator (C)]
The resin layer forming composition (III) and the thermosetting resin layer may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the resin layer forming composition (III).
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (that is, one or more hydrogen atoms are hydrogenated). Imidazoles substituted with groups other than atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (ie, phosphines in which one or more hydrogen atoms are replaced with organic groups); tetraphenylphosphonium tetra La tetraphenylborate, tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.

  The curing accelerator (C) contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one type, two or more types, and when two or more types are combined, The ratio can be arbitrarily selected.

  When the curing accelerator (C) is used, in the resin layer forming composition (III) and the thermosetting resin layer, the content of the curing accelerator (C) is 100 masses of the thermosetting component (B). It is preferable that it is 0.01-10 mass parts with respect to a part, and it is more preferable that it is 0.1-5 mass parts. The effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit. Further, since the content of the curing accelerator (C) is not more than the above upper limit value, for example, the highly polar curing accelerator (C) is deposited in the thermosetting resin layer under high temperature and high humidity conditions. The effect of suppressing segregation by moving toward the adhesion interface with the body is enhanced, and the reliability of the package obtained using the first protective film forming sheet is further improved.

[Filler (D)]
The resin layer forming composition (III) and the thermosetting resin layer may contain a filler (D). When the thermosetting resin layer contains the filler (D), the first protective film obtained by curing the thermosetting resin layer can easily adjust the thermal expansion coefficient. And the reliability of the package obtained using the sheet | seat for 1st protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation object of a 1st protective film. Moreover, when the thermosetting resin layer contains the filler (D), the moisture absorption rate of the first protective film can be reduced or the heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

  The resin layer forming composition (III) and the filler (D) contained in the thermosetting resin layer may be only one kind, two or more kinds, and when two or more kinds are used, combinations and ratios thereof. Can be chosen arbitrarily.

The average particle diameter of the filler (D) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. . When the average particle diameter of the filler (D) is in such a range, it is possible to suppress a decrease in the light transmittance of the first protective film while maintaining the adhesion to the formation target of the first protective film.
In the present specification, “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. .

  When the filler (D) is used, the content of the filler (D) (that is, the content of the filler (D) of the thermosetting resin layer) is other than the solvent of the resin layer forming composition (III). It is preferably 3 to 60% by mass, more preferably 3 to 55% by mass, based on the total mass of all components (that is, relative to the total mass of the thermosetting resin layer). Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range. Moreover, the infrared transmittance of a curable resin layer and a 1st protective film improves more because content of a filler (D) is below the said upper limit.

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

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.
Preferred examples of the silane coupling agent include 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-mercaptopropi Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.

  The composition for forming the resin layer (III) and the coupling agent (E) contained in the thermosetting resin layer may be only one kind, two or more kinds, and in the case of two or more kinds, a combination thereof and The ratio can be arbitrarily selected.

  When the coupling agent (E) is used, the content of the coupling agent (E) in the resin layer forming composition (III) and the thermosetting resin layer is such that the polymer component (A) and the thermosetting component ( It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of B), It is more preferable that it is 0.05-10 mass parts, It is 0.1-5 mass parts Is particularly preferred. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) in the resin and the adhesion of the thermosetting resin layer to the adherend are improved. The effect by using a coupling agent (E) etc. is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]
As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the resin layer forming composition (III) and the thermosetting resin layer may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the functional group in the polymer component (A) with another compound to cross-link, and by this cross-linking, initial adhesion of the thermosetting resin layer Force and cohesion can be adjusted.

  Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.

  Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

  More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Like lysine diisocyanate and the like; the compound or two or more are added.

  Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

  When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a cross-linked structure is formed on the thermosetting resin layer by a reaction between the crosslinking agent (F) and the polymer component (A). Easy to introduce.

  The composition for forming the resin layer (III) and the crosslinking agent (F) contained in the thermosetting resin layer may be only one kind, two or more kinds, and in the case of two or more kinds, combinations and ratios thereof. Can be chosen arbitrarily.

  When the crosslinking agent (F) is used, in the resin layer forming composition (III), the content of the crosslinking agent (F) is 0.01 to 100 parts by mass of the polymer component (A). It is preferably 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. The effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit. Moreover, the excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

[Energy ray curable resin (G)]
The resin layer forming composition (III) and the thermosetting resin layer may contain an energy ray curable resin (G). Since the thermosetting resin layer contains the energy ray curable resin (G), the characteristics can be changed by irradiation with energy rays.

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

  Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; Rigoesuteru (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

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

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

  The energy ray curable resin (G) contained in the resin layer forming composition (III) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

  When the energy beam curable resin (G) is used, the content of the energy beam curable resin (G) is based on the total mass of all components other than the solvent of the resin layer forming composition (III) (that is, 1 to 95% by mass, based on the total mass of the thermosetting resin layer), preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.

[Photopolymerization initiator (H)]
When the resin layer forming composition (III) and the thermosetting resin layer contain an energy ray curable resin (G), photopolymerization is performed in order to efficiently advance the polymerization reaction of the energy ray curable resin (G). An initiator (H) may be contained.

Examples of the photopolymerization initiator (H) in the resin layer forming composition (III) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl, and benzoin. Benzoin compounds such as dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethyl Sulfide compounds such as uranium monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthate and 2,4-diethylthioxanthone Peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone ;; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; Anthraquinone etc. are mentioned.
As the photopolymerization initiator (H), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

  The photopolymerization initiator (H) contained in the resin layer forming composition (III) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrarily selected. it can.

  When using a photoinitiator (H), in composition (III) for resin layer formation, content of a photoinitiator (H) is 100 mass parts of content of energy-beam curable resin (G). It is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

[Colorant (I)]
The resin layer forming composition (III) and the thermosetting resin layer may contain a colorant (I). The colorant (I) is a component for imparting appropriate light transmittance to, for example, the thermosetting resin layer and the first protective film.
The colorant (I) may be a known one, for example, any of a dye and a pigment.
For example, the dye may be any of an acid dye, a reactive dye, a direct dye, a disperse dye, a cationic dye, and the like.

  The colorant (I) contained in the resin layer forming composition (III) and the thermosetting resin layer may be only one type, or two or more types, and in the case of two or more types, combinations and ratios thereof. Can be chosen arbitrarily.

  The content of the colorant (I) in the resin layer forming composition (III) may be appropriately adjusted so that the visible light transmittance and the infrared transmittance of the thermosetting resin layer have desired values, and are particularly limited. Not. For example, the content of the colorant (I) depends on the type of the colorant (I) or a combination of these colorants (I) when two or more colorants (I) are used in combination. It may be adjusted as appropriate.

  When the colorant (I) is used, the content of the colorant (I) (that is, the content of the colorant (I) in the thermosetting resin layer) is a solvent constituting the resin layer forming composition (III). It is preferable that it is 0.01-10 mass% with respect to the total content of all the components other than.

[General-purpose additive (J)]
The resin layer forming composition (III) and the thermosetting resin layer may contain a general-purpose additive (J) as long as the effects of the present invention are not impaired.
The general-purpose additive (J) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Is mentioned.

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

[solvent]
The resin layer forming composition (III) preferably further contains a solvent. The resin layer forming composition (III) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. An ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; an amide (a compound having an amide bond) such as dimethylformamide or N-methylpyrrolidone;
The solvent contained in the resin layer forming composition (III) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

  The solvent contained in the resin layer forming composition (III) is preferably methyl ethyl ketone from the viewpoint that the components contained in the resin layer forming composition (III) can be more uniformly mixed.

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

<< Method for producing composition for forming thermosetting resin layer >>
The thermosetting resin layer forming composition such as the resin layer forming composition (III) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

-Energy ray curable resin layer As a preferable energy ray curable resin layer, what contains an energy ray curable component (a) is mentioned, for example.
The energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky. Here, “energy beam” and “energy beam curability” are as described above.

The thickness of the energy ray curable resin layer is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the energy ray curable resin layer is equal to or more than the lower limit, a first protective film with higher protective ability can be formed. Moreover, it will be suppressed that it becomes excessive thickness because the thickness of an energy-beam curable resin layer is below the said upper limit.
Here, “the thickness of the energy ray curable resin layer” means the thickness of the entire energy ray curable resin layer. For example, the thickness of the energy ray curable resin layer composed of a plurality of layers means the energy ray. It means the total thickness of all layers constituting the curable resin layer.

The energy ray curable resin layer is applied to the first surface of the semiconductor wafer and cured to form the first protective film. The curing condition is such that the first protective film exhibits its function sufficiently. The degree is not particularly limited as long as it is a degree, and may be appropriately selected according to the type of the energy ray curable resin layer.
For example, the illuminance of the energy rays at the time of curing the energy ray curable resin layer is preferably 180 to 280 mW / cm ² . And it is preferable that the light quantity of an energy ray at the time of the said hardening is 450-1000mJ / cm < ² >.

<< Energy ray-curable resin layer forming composition >>
The energy ray curable resin layer can be formed from an energy ray curable resin layer forming composition containing the constituent material. For example, an energy ray curable resin layer is formed on a target site by applying a composition for forming an energy ray curable resin layer on the surface on which the energy ray curable resin layer is to be formed, and drying as necessary. it can.

The application of the energy ray curable resin layer forming composition may be performed by a known method, for example, by the same method as in the case of applying the first pressure-sensitive adhesive composition described above.
Moreover, the drying conditions of the composition for forming an energy ray curable resin layer are not particularly limited, and may be the same as, for example, the case of the first pressure-sensitive adhesive composition described above.

<Resin layer forming composition (IV)>
Examples of the energy ray curable resin layer forming composition include, for example, the energy ray curable resin layer forming composition (IV) containing the energy ray curable component (a) (in the present specification, simply “resin”). Layer forming composition (IV) ”and the like.

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film forming property, flexibility, and the like to the energy ray-curable resin layer.
Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray curable group and a molecular weight of 100 to 80000. A compound (a2) is mentioned. The polymer (a1) may be crosslinked at least partly with a crosslinking agent or may not be crosslinked.

Examples of the polymer (a1) include an acrylic polymer having a functional group capable of reacting with a group possessed by another compound, a group that reacts with the functional group, and energy such as an energy ray-curable double bond. Examples thereof include an acrylic resin formed by a reaction of an energy ray curable compound having a linear curable group.
Examples of the functional group capable of reacting with the group possessed by the other 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 a hydrogen atom). Group), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
Among these, the functional group is preferably a hydroxyl group.
The polymer (a1) contained in the resin layer forming composition (IV) and the energy ray curable resin layer may be only one kind, two kinds or more, and a combination thereof when they are two kinds or more. The ratio can be arbitrarily selected.

The energy ray curable group having an energy ray curable group and having a molecular weight of 100 to 80,000 (a2) includes a group containing an energy ray curable double bond, and (meth) is preferable. An acryloyl group, a vinyl group, etc. are mentioned. Preferably, it is a low molecular weight compound having a (meth) acryloyl group as an energy ray curable group.
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. A phenol resin etc. are mentioned.
Among the compounds (a2), examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
The compound (a2) contained in the resin layer forming composition (IV) and the energy ray curable resin layer may be only one kind, two kinds or more, and in the case of two kinds or more, a combination thereof and The ratio can be arbitrarily selected.

[Polymer (b) having no energy ray curable group]
When the composition for resin layer formation (IV) and the energy ray curable resin layer contain the compound (a2) as the energy ray curable component (a), the polymer having no energy ray curable group ( It is also preferable to contain b).
The polymer (b) may be crosslinked at least partially by a crosslinking agent, or may not be crosslinked.

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

  The resin layer forming composition (IV) is not an energy ray curable component (a), and is not a heat ray curable component (a) or polymer (b), depending on the purpose. You may contain 1 type, or 2 or more types selected from the group which consists of a sclerosing | hardenable component, a photoinitiator, a coloring agent, a filler, a coupling agent, a crosslinking agent, and a general purpose additive. For example, by using the resin layer forming composition (IV) containing the energy ray curable component and the thermosetting component, the formed energy ray curable resin layer has an adhesive force to an adherend by heating. And the strength of the first protective film formed from this energy beam curable resin layer is also improved.

  As the thermosetting component, photopolymerization initiator, colorant, filler, coupling agent, crosslinking agent and general-purpose additive in the resin layer forming composition (IV), the resin layer forming composition (III ), A thermosetting component (B), a photopolymerization initiator (H), a colorant (I), a filler (D), a coupling agent (E), a crosslinking agent (F), and a general-purpose additive (J). The same can be mentioned.

In the resin layer forming composition (IV), each of the thermosetting component, the photopolymerization initiator, the colorant, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive may be used alone. Two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily selected.
If the content of the thermosetting component, photopolymerization initiator, colorant, filler, coupling agent, crosslinking agent and general-purpose additive in the resin layer forming composition (IV) is appropriately adjusted according to the purpose. Well, not particularly limited.

The resin layer forming composition (IV) preferably further contains a solvent since its handleability is improved by dilution.
Examples of the solvent contained in the resin layer forming composition (IV) include the same solvents as those in the resin layer forming composition (III).
The solvent contained in the resin layer forming composition (IV) may be only one kind or two or more kinds.
As one aspect, the resin layer forming composition (IV) comprises an energy ray curable component (a), and optionally a polymer (b) having no energy ray curable group, a thermosetting component, and photopolymerization. It includes at least one component selected from the group consisting of an initiator, a colorant, a filler, a coupling agent, a crosslinking agent, a general-purpose additive, and a solvent.

<< Method for Manufacturing Composition for Forming Energy Ray Curable Resin Layer >>
The composition for forming an energy ray curable resin layer such as the resin layer forming composition (IV) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

An example of the first protective film forming sheet will be described with reference to the drawings.
FIG. 5 is a cross-sectional view schematically showing an example of the first protective film-forming sheet.
The 1st sheet | seat 801 for protective film formation shown here uses the 1st adhesive layer laminated | stacked on a 1st base material as a 1st support sheet. That is, the first protective film forming sheet 801 includes a first base material 811, a first pressure-sensitive adhesive layer 812 on the first base material 811, and a curable resin layer (cured) on the first pressure-sensitive adhesive layer 812. A functional resin film) 82. As another aspect, the first support sheet includes a first substrate 811, a first adhesive layer 812 laminated on the first substrate 811, and a curable resin laminated on the first adhesive layer 812. Layer (curable resin film) 82.
The first support sheet 810 is a laminate of the first base material 811 and the first pressure-sensitive adhesive layer 812, and is on the one surface 810 a of the first support sheet 810, that is, the first pressure-sensitive adhesive layer 812 in the first support sheet 810. A curable resin layer 82 is provided on the surface 812a on the side where the layers are stacked.

FIG. 6 is a cross-sectional view schematically showing another example of the first protective film forming sheet.
The sheet | seat 802 for 1st protective film formation shown here uses what consists only of peeling films as a 1st support sheet. That is, the first protective film forming sheet 802 includes a curable resin layer (curable resin film) 82 on the release film 821. As another aspect, the first protective film forming sheet 802 includes a release film 821 and a curable resin layer (curable resin film) 82 laminated on the release film 821.
The first support sheet 820 is a release film 821, on one surface 820 a of the first support sheet 820, that is, one surface of the release film 821 (in this specification, it may be referred to as “first surface”). A curable resin layer 82 is provided on 821a.
The first surface 821a of the release film 821 is preferably subjected to a release treatment (a release treatment surface).

  In addition, the 1st support film formation sheet | seat in which a 1st support sheet consists only of a 1st base material also becomes a structure similar to what is shown in FIG. That is, in the first protective film forming sheet 802 shown in FIG. 6, what is denoted by reference numeral 821 is not the release film but the first base material is also suitable as the first protective film forming sheet.

In any case described above, the first protective film-forming sheet is the outermost layer (for example, a curable resin layer) on the side opposite to the side on which the first support sheet is provided in the first protective film-forming sheet. Further, a release film may be further provided on the surface. Thus, the 1st protective film formation sheet provided with the peeling film is easy to store and handle.
The release film in this case may be removed when the first protective film forming sheet is used. When the first support sheet is composed only of the release film as described above, the release film as the first support sheet and the release film provided on the outermost layer on the side opposite to the first support sheet are mutually They may be the same or different.

◇ Method for Producing First Protective Film Forming Sheet The first protective film forming sheet can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.

  For example, a first protective film-forming sheet (first film shown in FIG. 5) in which a first base material, a first pressure-sensitive adhesive layer, and a curable resin layer (curable resin film) are laminated in this order in the thickness direction. 1 sheet for protective film formation etc.) can be manufactured by the method shown below. That is, a 1st adhesive layer is laminated | stacked by applying the above-mentioned 1st adhesive composition on a 1st base material, and making it dry as needed. Moreover, the above-mentioned curable resin layer forming composition is applied onto the release-treated surface of the release film, and dried as necessary, thereby laminating the curable resin layer. And the 1st substrate, the 1st adhesive layer, the curable resin layer, and the release film are in this order by pasting together the curable resin layer on this release film with the 1st adhesive layer on the 1st substrate. Thus, a first protective film forming sheet laminated in the thickness direction is obtained. The release film may be removed when the first protective film forming sheet is used.

  The above-mentioned first protective film forming sheet can also be produced by the following method. That is, a 1st adhesive layer is laminated | stacked by applying a 1st adhesive composition on the peeling process surface of a peeling film, and making it dry as needed. Separately, a curable resin layer is laminated on the release treatment surface of the release film by the same method as described above. And after sticking the 1st adhesive layer on a release film with the 1st substrate, removing the release film on the 1st adhesive layer, the surface where the release film of the 1st adhesive layer was further laminated By bonding the (exposed surface) and the curable resin layer on the release film obtained above, the first base material, the first pressure-sensitive adhesive layer, the curable resin layer, and the release film are in this order. To obtain a first protective film-forming sheet laminated in the thickness direction.

The first protective film-forming sheet provided with a layer other than each of the above-described layers is the above-described manufacturing method, and the stacking process of the other layer is performed so that the stacking position of the other layer is an appropriate position. It can manufacture by adding suitably and performing.
For example, when the first support sheet is formed by laminating the first base material, the first intermediate layer, and the first pressure-sensitive adhesive layer in this order in the thickness direction, the first protective film forming sheet is the above-mentioned In a manufacturing method, it can manufacture by adding and laminating | stacking a 1st intermediate | middle layer so that a 1st intermediate | middle layer may be arrange | positioned between a 1st base material and a 1st adhesive layer.

Moreover, the 1st protective film formation sheet | seat which is not provided with any arbitrary layers among each above-mentioned layers can be manufactured by abbreviate | omitting the lamination | stacking process of the said arbitrary layers in the above-mentioned manufacturing method.
For example, the first protective film-forming sheet in the case where the first support sheet is composed only of the first base material can be manufactured by omitting the step of laminating the first pressure-sensitive adhesive layer in the above-described manufacturing method.

◇ Second protective film forming sheet and method for producing the same As the second protective film forming sheet, for example, the same sheet as the first protective film forming sheet described above may be used. However, the second protective film forming sheet is not necessarily the same as the first protective film forming sheet because the required function is different from that of the first protective film forming sheet.
In particular, the curable resin layer in the second protective film forming sheet can be composed of the same components as in the case of the curable resin layer in the first protective film forming sheet, but the content of each component of the curable resin layer is The second protective film is preferably adjusted as appropriate so that the intended function can be sufficiently exhibited.

  In the present specification, the first base material, the first intermediate layer, and the first pressure-sensitive adhesive layer in the first protective film-forming sheet are respectively the second base material, It is called a second intermediate layer and a second pressure-sensitive adhesive layer.

  The 2nd protective film formation sheet can be manufactured by the same method as the case of the above-mentioned 1st protective film formation sheet.

-Laminated structure manufacturing process In the said laminated structure manufacturing process, the said laminated structure is produced by joining the said semiconductor chip with a protective film to a board | substrate via the bump which this chip has.
The laminated structure is a novel one.

  In the laminated structure manufacturing step, for example, a flux agent is applied to the upper surface of the bump of the semiconductor chip with a protective film, the upper portion of the bump is brought into contact with the substrate, and the bump and the substrate are heated in this state. As a result, the bumps and the substrate are joined together to produce a laminated structure. Although the heating conditions in this case are not specifically limited, For example, it is preferable to heat at 220-320 degreeC for 0.5 to 10 minutes.

After the laminated structure manufacturing step, a semiconductor device can be manufactured by the same method as the conventional method using the obtained laminated structure.
For example, the laminated structure is sealed with a resin to form a semiconductor package, and a target semiconductor device can be manufactured using the semiconductor package.

-Semiconductor device The semiconductor device obtained by the above-mentioned manufacturing method is equipped with the laminated structure and is a novel one.
That is, a semiconductor device according to an embodiment of the present invention is a semiconductor device including a stacked structure in which a semiconductor chip with a protective film having a bump is bonded to a substrate through the bump, and the semiconductor with a protective film The chip has at least a first protective film on the first surface having bumps of the semiconductor chip, or has a second protective film on the second surface opposite to the first surface of the semiconductor chip, In the case where the semiconductor chip with a protective film includes the first protective film, in the first protective film, an upper portion of the bump protrudes through the first protective film, and the first protective film or The second protective film has a shear strength ratio of 1.05 to 2 and a fracture risk factor of −0.9 to 0 when the shear strength ratio and fracture risk factor of the laminated structure are measured by the following method. .9 with characteristics As a protective film.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state between the semiconductor chip with a protective film and the copper substrate is broken is applied to the shear strength (N )age,
Except that the first protective film and the second protective film are not provided, a comparative laminated structure (comparative test piece) having the same structure as the test piece of the laminated structure is produced and is the same as the laminated structure. When a force is applied by the method, and the force when the bonding state between the semiconductor chip of the comparative test piece and the copper substrate is broken is used as the comparative shear strength (N) of the comparative laminated structure,
The value of [shear strength of the laminated structure] / [comparative shear strength of the comparative laminated structure] is defined as the shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
Test specimens having a width of 5 mm and a length of 20 mm of all layers constituting the laminated structure were prepared, and all the test specimens were increased from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min. A heating / cooling test is performed in which the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min, and the expansion amount Eμm of the test piece when the temperature is increased from 23 ° C. to 150 ° C. The amount of expansion / shrinkage ES μm, which is the total amount of the shrinkage amount Sμm of the test piece when the temperature is lowered to 65 ° C., is obtained, and further, [expansion / shrinkage amount ES of the test piece] × [thickness of the test piece] The expansion / contraction parameter P μm ² which is the value of
Subsequently, an expansion / contraction parameter difference ΔP1 μm ² which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate] is obtained,
Next, an expansion / contraction standard parameter difference which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate, the first protective film, and the second protective film]. When obtaining ΔP0 μm ² ,
The value of ΔP1 / ΔP0 is used as a risk factor for fracture of the laminated structure.

  The semiconductor device of the present invention can have the same configuration as a conventional semiconductor device except that the semiconductor device includes the laminated structure.

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

The components used for the production of the protective film-forming composition are shown below.
[Polymer component (A)]
(A) -1: Polyvinyl butyral having structural units represented by the following formulas (i) -1, (i) -2, and (i) -3 (“ESREC BL-10” manufactured by Sekisui Chemical Co., Ltd., weight average) (Molecular weight 25000, glass transition temperature 59 ° C.).
(A) -2: copolymerized n-butyl acrylate (1 part by mass), methyl methacrylate (79 parts by mass), glycidyl methacrylate (5 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). An acrylic resin (weight average molecular weight 370000, glass transition temperature 7 ° C.).

（式中、ｌ_１は約２８であり、ｍ_１は１〜３であり、ｎ_１は６８〜７４の整数である。）

(Wherein l ₁ is about 28, m ₁ is 1 to 3, and n ₁ is an integer of 68 to 74)

[Thermosetting component (B)]
・ Epoxy resin (B1)
(B1) -1: Liquid epoxy resin (epoxy resin having a flexible skeleton introduced, “EXA 4850-150” manufactured by DIC, molecular weight 900)
(B1) -2: polyfunctional aromatic epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.)
(B1) -3: Dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent of 274 to 286 g / eq)
(B1) -4: Bisphenol A type epoxy resin (“BPA328” manufactured by Nippon Shokubai Co., Ltd.) / Thermosetting agent (B2)
(B2) -1: Novolac type phenolic resin ("BRG-556" manufactured by Showa Denko KK)
(B2) -2: Dicyandiamide (solid dispersion type latent curing agent, “ADEKA HARDNER EH-3636AS” manufactured by ADEKA, active hydrogen content 21 g / eq) [curing accelerator (C)]
(C) -1: 2-phenyl-4,5-dihydroxymethylimidazole (“Cureazole 2PHZ-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
[Filler (D)]
(D) -1: Fused quartz filler (spherical silica ("SV-10" manufactured by Tatsumori Co., Ltd.) physically crushed, average particle size 8 μm)
[Coupling agent (E)]
(E) -1: Silane coupling agent (an oligomer type silane coupling agent containing an epoxy group, a methyl group and a methoxy group, “X-41-1056” manufactured by Shin-Etsu Silicone Co., epoxy equivalent 280 g / eq)
(E) -2: 3-glycidoxypropyltriethoxysilane (silane coupling agent, “KBE-403” manufactured by Shin-Etsu Silicone Co., Ltd., methoxy equivalent 8.1 mmol / g, molecular weight 278.4)
(E) -3: 3-Glycidoxypropyltrimethoxysilane (silane coupling agent, “KBM-403” manufactured by Shin-Etsu Silicone, methoxy equivalent 12.7 mmol / g, molecular weight 236.3)
[Colorant (I)]
(I) -1: Carbon black (“MA600” manufactured by Mitsubishi Chemical Corporation, average particle size 20 nm)

[Example 1]
<Manufacture of laminated structure>
(Manufacture of a composition for forming a thermosetting resin layer (1))
Polymer component (A) -1, epoxy resin (B1) -1, epoxy resin (B1) -2, epoxy resin (B1) -3, thermosetting agent (B2) -1, and curing accelerator (C)- 1 is dissolved or dispersed in methyl ethyl ketone so that the ratio of these contents is the value shown in Table 1, and stirred at 23 ° C., so that the solid content concentration is as a composition for forming a thermosetting resin layer. A resin layer forming composition (III) -1 having a content of 55% by mass was obtained. In addition, description of "-" of the column of the containing component in Table 1 means that the composition for thermosetting resin layer formation does not contain the component. Moreover, all content of each component shown in Table 1 is solid content.

(Production of adhesive resin (I-2a))
An acrylic polymer (molecular weight of about 700,000) obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (20 parts by mass), 2-Methacryloyloxyethyl isocyanate (hereinafter abbreviated as “MOI”) (the total number of isocyanate groups in 2-methacryloyloxyethyl isocyanate relative to the total number of HEA-derived hydroxyl groups in the acrylic polymer) Is added at an amount of 0.8 times) and allowed to react at room temperature for 1 day, and an ultraviolet curable adhesive resin (I-2a), which is an acrylic copolymer having a methacryloyloxy group in the side chain, is obtained. Obtained.

(Production of first pressure-sensitive adhesive composition (I-2))
For the adhesive resin (I-2a) (100 parts by mass) obtained above, an isocyanate-based crosslinking agent (“Coronate L” manufactured by Nippon Polyurethane Co., Ltd., a tolylene diisocyanate trimer adduct of trimethylolpropane) (2 0.0 parts by mass), a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone) (0.1 parts by mass) and 0.1 g by mass, are UV curable. A first pressure-sensitive adhesive composition (I-2) was obtained.

(Manufacture of first support sheet)
A first pressure-sensitive adhesive composition (I -2) was applied and dried by heating at 100 ° C. for 1 minute to form a first pressure-sensitive adhesive layer having a thickness of 10 μm.
Next, the first pressure-sensitive adhesive layer on the release film and the first base material (thickness 400 μm) made of a polyurethane acrylate film are bonded together, and the first base material and the first pressure-sensitive adhesive layer are laminated, The 1st support sheet provided with the peeling film on the 1st adhesive layer was obtained.

(Manufacture of sheet for forming first protective film)
On the release-treated surface of a release film ("SP-PET 381031" manufactured by Lintec Co., Ltd., thickness 38 μm) from which one side of a polyethylene terephthalate film was released by silicone treatment, the resin layer forming composition (III ) -1 was applied and dried by heating at 120 ° C. for 2 minutes to form a thermosetting resin film having a thickness of 30 μm.
Next, the release film is removed from the first support sheet, and the exposed first pressure-sensitive adhesive layer and the thermosetting resin film on the release film obtained above are bonded together to form the first base material, the first The 1st sheet | seat for protective film formation which has the structure shown in FIG. 5 by which an adhesive layer, a thermosetting resin film, and a peeling film are laminated | stacked in these thickness directions in this order was obtained.

(Production of composition for forming thermosetting resin layer (2))
Polymer component (A) -2, epoxy resin (B1) -3, epoxy resin (B1) -4, thermosetting agent (B2) -2, curing accelerator (C) -1, filler (D) -1 , Coupling agent (E) -1, Coupling agent (E) -2, Coupling agent (E) -3, and Colorant (I) -1, the values of these contents are shown in Table 1. By dissolving or dispersing in methyl ethyl ketone so as to be and stirring at 23 ° C., a resin layer forming composition (III) − having a solid content concentration of 55% by mass as a thermosetting resin layer forming composition 2 was obtained.

(Manufacture of second support sheet)
The first pressure-sensitive adhesive composition (I-2) described above is applied to the release-treated surface of a release film ("SP-PET 381031" manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. The first pressure-sensitive adhesive layer was formed by coating and drying by heating.
Next, the first pressure-sensitive adhesive layer on the release film and the second base material (thickness 100 μm) made of a polyolefin film are bonded together, and the second base material, the first pressure-sensitive adhesive layer and the release film are in this order, A laminate formed by laminating these in the thickness direction was produced.
Next, the second pressure-sensitive adhesive is obtained by irradiating the first pressure-sensitive adhesive layer from the release film side of the obtained laminate with ultraviolet rays under the conditions of an illuminance of 230 mW / cm ² and a light amount of 120 mJ / cm ² and curing the ultraviolet rays. As a layer, an ultraviolet cured product of a first pressure-sensitive adhesive layer having a thickness of 10 μm was laminated on the second base material, and a second support sheet provided with a release film on the second pressure-sensitive adhesive layer was obtained.

(Manufacture of second protective film forming sheet)
A resin layer-forming composition (III ) -2 was applied and dried by heating at 120 ° C. for 2 minutes to form a thermosetting resin film having a thickness of 25 μm.
Next, the release film is removed from the second support sheet, the exposed second pressure-sensitive adhesive layer and the thermosetting resin film on the release film obtained above are bonded together, and the second base material, the second The 2nd protective film formation sheet which has the structure shown in FIG. 5 by which an adhesive layer, a thermosetting resin film, and a peeling film are laminated | stacked in this thickness direction in this order was obtained.

(Manufacture of laminated structures)
As a semiconductor wafer, a silicon wafer having a large number of bumps having a shape similar to that shown in FIG. 200 mm, thickness 250 μm) was prepared.
And a peeling film is removed from the sheet | seat for 1st protective film formation obtained above, The newly produced exposed surface (1st adhesion) of this thermosetting resin film is heated at 70 degreeC. The surface opposite to the side provided with the agent layer) was affixed to the first surface (bump forming surface) of the above-mentioned silicon wafer, and the thermosetting resin film was brought into close contact with the circuit surface and the bump surface.
Next, the first support sheet was removed from the thermosetting resin film.

  On the other hand, the release film was removed from the second protective film-forming sheet obtained above, and the newly exposed exposed surface (second adhesive) of the thermosetting resin film was heated while heating the thermosetting resin film at 70 ° C. The surface opposite to the side provided with the agent layer) was affixed to the second surface (back surface) of the silicon wafer described above.

As described above, a laminate in which the second base material, the second pressure-sensitive adhesive layer, the curable resin film, the semiconductor wafer, and the curable resin film were laminated in this order was obtained.
Next, the two-layered thermosetting resin film was heat-cured by heat treatment at 130 ° C. for 2 hours to form a first protective film and a second protective film.
Next, the semiconductor wafer provided with the first protective film and the second protective film is diced into individual pieces by using a dicing blade, and the size is 6 cm × 6 cm. A semiconductor chip with a protective film comprising a film and having a second protective film on the second surface was obtained.
Subsequently, this semiconductor chip with a protective film was picked up by being separated from a laminated sheet (corresponding to a dicing sheet) of the second base material and the second pressure-sensitive adhesive layer.

  Next, a flux agent is applied to the surface of the bump upper portion protruding through the first protective film of the semiconductor chip with the protective film, and an organic substrate (thickness) made of glass epoxy resin is formed on the upper portion of the bump. In this state, the bump and the organic substrate are heated on a heater at 300 ° C. for 1 minute to bond the semiconductor chip with a protective film to the organic substrate via the bump, thereby forming the laminated structure. Obtained. After heating, the obtained laminated structure was washed to remove the fluxing agent. In the laminated structure obtained here, a semiconductor chip with a protective film having a first protective film on the first surface and a second protective film on the second surface was bonded to the organic substrate via the bumps. Is.

<Evaluation of laminated structure>
(Calculation of shear strength ratio)
A semiconductor chip with a protective film was obtained by the same method as above.
Next, a flux agent is applied to the surface of the upper part of the bump protruding through the first protective film of the semiconductor chip with the protective film, and a copper substrate (thickness: 930 μm) is placed on the upper part of the bump. In this state, the bump and the copper substrate were heated on a heater at 300 ° C. for 1 minute, whereby the semiconductor chip with a protective film was bonded to the copper substrate via the bump to obtain a laminated structure. After heating, the obtained laminated structure was washed to remove the fluxing agent. The laminated structure obtained here is the same as the laminated structure including the organic substrate described above except that a copper substrate is provided instead of the organic substrate. Four such laminated structures were manufactured.

Next, by using a bonding strength test apparatus (“DAGE 4000 Die Shear Tester” manufactured by Nordson), the laminated structure provided with the copper substrate obtained above is subjected to a Die Shear test, thereby providing a semiconductor chip with a protective film. The bonding strength between the copper substrate and the copper substrate, that is, the shear strength was measured.
More specifically, the shear strength was measured by the following method. That is, the laminated structure is set on the bonding strength test equipment, the copper substrate in the laminated structure is fixed, and the direction parallel to the surface of the copper substrate with respect to the semiconductor chip with the protective film in the laminated structure Added power. At this time, as a tool for applying force to the semiconductor chip with a protective film, a model number “SHR-250-9000” is used, a load cell is model number “DS100”, a share speed is 100 μm / sec, and a share height is 5 μm. Power was applied under the conditions of And the force applied when the joining state of the semiconductor chip with a protective film and a copper substrate was destroyed was read, and the value was made into the shear strength (N) of a laminated structure. For the four laminated structures, the shear strength was measured in this way, and the average value of the measured values at this time was adopted as the shear strength (N) of the laminated structure.

Separately, four comparative laminated structures having the same structure as the laminated structure provided with the copper substrate described above were produced except that the first protective film and the second protective film were not provided.
Next, a force is applied to this comparative laminated structure in the same manner as in the above laminated structure, and the force applied when the bonding state between the semiconductor chip and the copper substrate is broken is read. The value was taken as the comparative shear strength (N) of the comparative laminated structure. For the four comparative laminated structures, the comparative shear strength was measured in this way, and the average value of the measured values at this time was adopted as the comparative shear strength (N) of the comparative laminated structure.

  Using these measured values of shear strength (N), the value of [shear strength of laminated structure (N)] / [comparative shear strength of comparative laminate structure (N)] is calculated, and this value is laminated. The shear strength ratio of the structure was used. The results are shown in Table 2.

(Calculation of fracture risk factors for laminated structures)
Test layers of all the layers constituting the laminated structure including the organic substrate described above, that is, the substrate (organic substrate), the first protective film, the semiconductor chip, and the second protective film were prepared. These test pieces have the same width as that of each layer constituting the laminated structure except that the width is 5 mm and the length is 20 mm, and thus the sizes (width and length) are different (that is, The thickness of each test piece is the same as the thickness of each layer constituting the laminated structure). Four test pieces were prepared for each type.
Subsequently, using a thermomechanical analyzer (“TMA4000SA” manufactured by NETCH), all the test pieces were heated from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min, and from 200 ° C. to a cooling rate of 5 A heating / cooling test in which the temperature is lowered to -70 ° C at a rate of ° C / min, the expansion amount E μm of the test piece when the temperature is raised from 23 ° C to 150 ° C, and the test piece when the temperature is lowered from 23 ° C to -65 ° C The amount of shrinkage Sμm was measured.
Then, for each test piece, an expansion / shrinkage amount ES μm, which is the total amount of these measured values (sum of absolute values), is obtained, and further, [expansion / shrinkage amount ES (μm) of test piece] × [thickness of test piece ( It calculates the value of [mu] m)], and the expansion and contraction parameters Pμm ^2. For the four test pieces, the expansion / contraction parameter Pμm ² was determined in this way, and the average value was adopted as the expansion / contraction parameter Pμm ² of the test piece.

Then, [expansion and contraction parameters of the substrate of the test piece P (μm ^2)] - [sum of expansion and contraction parameters P of all the specimens other than the substrate (μm ^2)] which is a value expansion contraction parameter difference DerutaP1myuemu ² Asked. Here, “all test pieces other than the substrate” are test pieces of the semiconductor chip, the first protective film, and the second protective film.

Next, [expansion / shrinkage parameter P of substrate test piece P (μm ² )] − [total value of expansion / shrinkage parameter P of all test pieces other than substrate, first protective film and second protective film (μm ² )] The expansion / contraction standard parameter difference ΔP0 μm ² as a value was obtained. Here, “all the test pieces other than the substrate, the first protective film, and the second protective film” are test pieces of the semiconductor chip.

  Next, a value of ΔP1 / ΔP0 was calculated, and this value was used as a risk factor for fracture of the laminated structure. The results are shown in Table 2.

(Reliability evaluation)
About the laminated structure provided with the above-mentioned organic substrate, in accordance with JEDEC STANDERD 22-A104E, the temperature cycle test (may be abbreviated as TCT) depending on the condition C (−65 ° C. to 150 ° C., exposure time 10 minutes) The number of cycles (times) until the bonded state between the semiconductor chip with a protective film and the organic substrate was destroyed was confirmed. This temperature cycle test was performed on four laminated structures, the average value of the number of cycles was determined, and the value was used as an index of reliability of the laminated structure. The results are shown in Table 2.

<Manufacture and evaluation of laminated structure>
[Example 2]
A laminated structure was obtained in the same manner as in Example 1 except that the second protective film was not formed. In the laminated structure obtained here, a semiconductor chip with a protective film having a first protective film on the first surface and no second protective film on the second surface was bonded to the substrate via the bumps. Is.
And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 2.

[Example 3]
As a semiconductor wafer, a silicon wafer having a thickness of 500 μm instead of 250 μm and the same as that used in Example 2 was prepared. And the laminated structure was manufactured by the same method as the case of Example 2 except the point which used this silicon wafer, and was evaluated. The results are shown in Table 2.

[Example 4]
As a semiconductor wafer, a silicon wafer having a thickness of 500 μm instead of 250 μm and the other points being the same as those used in Example 1 was prepared.
Moreover, as shown in Table 1, except that the filler (D) -1 (230 parts by mass) was newly used, the same method as in the case of the above-described resin layer forming composition (III) -1, As the thermosetting resin layer forming composition, a resin layer forming composition (III) -3 having a solid content concentration of 69% by mass was obtained.
And the laminated structure was manufactured and evaluated by the same method as the case of Example 2 except the point which used these silicon wafers and composition (III) -3 for resin layer formation. The results are shown in Table 2.

[Example 5]
A laminated structure was obtained in the same manner as in Example 1 except that the thickness of the second protective film was changed to 43 μm instead of 25 μm and the first protective film was not formed. The laminated structure obtained here has a second protective film on the second surface and a semiconductor chip with a protective film that does not have the first protective film on the first surface is bonded to the substrate via the bumps. Is.
And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 3.

[Comparative Example 1]
Except that the curing accelerator (C) -1 was not used, the resin layer forming composition (IX) -1 was obtained as the thermosetting resin layer forming composition in the same manner as in Example 1. It was.
Then, in place of the resin layer forming composition (III) -1, this laminated layer structure was prepared in the same manner as in Example 2 except that this resin layer forming composition (IX) -1 was used. Manufactured and evaluated. The results are shown in Table 3.

[Comparative Example 2]
As a semiconductor wafer, a silicon wafer having a thickness of 500 μm instead of 250 μm and the other points being the same as those used in Example 1 was prepared.
A laminated structure was obtained in the same manner as in Example 1 except that this silicon wafer was used and the first protective film was not formed. The laminated structure obtained here has a second protective film on the second surface and a semiconductor chip with a protective film that does not have the first protective film on the first surface is bonded to the substrate via the bumps. Is.
And the obtained laminated structure was evaluated by the same method as the case of Example 1. The results are shown in Table 3.

<Manufacture and evaluation of laminated structure for comparison>
[Experimental Example 1]
The same semiconductor wafer as that used in Example 1 (that is, an 8-inch silicon wafer) was used as a semiconductor wafer, and a dicing sheet was attached to the second surface (back surface).
Next, in the same manner as in the first embodiment, the semiconductor wafer that is not provided with both the first protective film and the second protective film is diced into individual pieces to obtain semiconductor chips, and the semiconductor chips are picked up. did.
Next, in place of the above-described semiconductor chip with a protective film, a laminated structure is formed in the same manner as in Example 1 except that a semiconductor chip that does not include both the first protective film and the second protective film is used. A body (a laminated structure for comparison) was obtained. The comparative laminated structure obtained here is a semiconductor chip alone and bonded to the substrate via its bumps, and is different from the comparative laminated structure including the copper substrate described above. .
Next, reliability evaluation was performed on this comparative laminated structure by the same method as in Example 1. The results are shown in Table 3.

  As apparent from the above results, in Examples 1 to 5, the shear strength ratio of the laminated structure is 1.15 to 2.00, and the fracture risk factor is 0.83 to 0.90. The number of cycles until the bonding state between the semiconductor chip with the protective film and the organic substrate is broken is 300 times or more, and the bonding of the semiconductor chip with the protective film to the substrate can be performed over a long period of time even under a temperature change condition. It was stable.

On the other hand, in Comparative Example 1, the shear strength ratio of the laminated structure is less than 1.05, and the fracture risk factor is greater than 0.9, so that the bonded state between the semiconductor chip with a protective film and the organic substrate The bonding of the semiconductor chip with a protective film to the substrate was unstable under the condition that the number of cycles until the breakage was small and the temperature change was severe.
In Comparative Example 2, the number of cycles until the bonded state between the semiconductor chip with a protective film and the organic substrate is destroyed due to the shear strength ratio of the laminated structure being greater than 2 and the fracture risk factor being greater than 0.9. The bonding of the semiconductor chip with the protective film to the substrate was unstable under the condition that the temperature was small and the temperature change was severe.

  INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing a semiconductor chip or the like having bumps in connection pad portions used in a flip chip mounting method.

1, 2, 3 ... Laminated structure 10, 20, 30 ... Semiconductor chip with protective film 11 ... Semiconductor chip 11a ... First surface of semiconductor chip 11b ... Second surface of semiconductor chip DESCRIPTION OF SYMBOLS 111 ... Bump 111a ... Upper part of bump 12 ... 1st protective film 13 ... 2nd protective film 14 ... Substrate 14a ... 1st surface of a board | substrate 9 ... Laminated structure for a comparison body

Claims (2)

A method for manufacturing a semiconductor device, comprising:
At least a first protective film is provided on the first surface of the semiconductor chip having bumps, or a second protective film is provided on the second surface of the semiconductor chip opposite to the first surface. Producing a semiconductor chip;
Producing a laminated structure in which the semiconductor chip with a protective film is bonded to a substrate via bumps;
In the fabrication of the semiconductor chip with a protective film, the first protective film is formed such that an upper portion of the bump protrudes through the first protective film;
The first protective film or the second protective film has a shear strength ratio of 1.05 to 2 when the shear strength ratio and fracture risk factor of the laminated structure are measured by the following method, and the fracture risk factor is A protective film having a characteristic of -0.9 to 0.9;
A method for manufacturing a semiconductor device.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state between the semiconductor chip with a protective film and the copper substrate is broken is applied to the shear strength (N )age,
Except that the first protective film and the second protective film are not provided, a comparative test piece having the same structure as the test piece of the laminated structure is produced, and the force is applied in the same manner as the test piece of the laminated structure. In addition, when the force when the bonded state between the semiconductor chip of the comparative test piece and the copper substrate is broken is set as the comparative shear strength (N) of the comparative laminated structure,
The value of [shear strength of the laminated structure] / [comparative shear strength of the comparative laminated structure] is defined as the shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
Test specimens having a width of 5 mm and a length of 20 mm of all layers constituting the laminated structure were prepared, and all the test specimens were increased from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min. A heating / cooling test is performed in which the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min, and the expansion amount Eμm of the test piece when the temperature is increased from 23 ° C. to 150 ° C. The amount of expansion / shrinkage ES μm, which is the total amount of the shrinkage amount Sμm of the test piece when the temperature is lowered to 65 ° C., is obtained, and further, [expansion / shrinkage amount ES of the test piece] × [thickness of the test piece] The expansion / contraction parameter P μm ² which is the value of
Subsequently, an expansion / contraction parameter difference ΔP1 μm ² which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate] is obtained,
Next, an expansion / contraction standard parameter difference which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate, the first protective film, and the second protective film]. When obtaining ΔP0 μm ² ,
The value of ΔP1 / ΔP0 is used as a risk factor for fracture of the laminated structure. A semiconductor device with a protective film having a bump is a semiconductor device including a laminated structure bonded to a substrate through the bump,
The semiconductor chip with a protective film includes at least a first protective film on a first surface having bumps in the semiconductor chip, or a second protection on a second surface opposite to the first surface in the semiconductor chip. With a membrane,
In the first protective film, the upper part of the bump protrudes through the first protective film,
The first protective film or the second protective film has a shear strength ratio of 1.05 to 2 when the shear strength ratio and fracture risk factor of the laminated structure are measured by the following method, and the fracture risk factor is A semiconductor device which is a protective film having a characteristic of −0.9 to 0.9.
<Shear strength ratio of laminated structure>
A test piece of the multilayer structure in which the substrate is a copper substrate is manufactured, the copper substrate in the test piece of the multilayer structure is fixed, and a semiconductor chip with a protective film in the test piece of the multilayer structure Then, a force is applied in a direction parallel to the surface of the copper substrate, and the force when the bonding state between the semiconductor chip with a protective film and the copper substrate is broken is applied to the shear strength (N )age,
Except that the first protective film and the second protective film are not provided, a comparative test piece having the same structure as the test piece of the laminated structure is produced, and the force is applied in the same manner as the test piece of the laminated structure. In addition, when the force when the bonded state between the semiconductor chip of the comparative test piece and the copper substrate is broken is set as the comparative shear strength (N) of the comparative laminated structure,
The value of [shear strength of the laminated structure] / [comparative shear strength of the comparative laminated structure] is defined as the shear strength ratio of the laminated structure.
<Risk risk factor of laminated structure>
Test specimens having a width of 5 mm and a length of 20 mm of all layers constituting the laminated structure were prepared, and all the test specimens were increased from −70 ° C. to 200 ° C. at a heating rate of 5 ° C./min. A heating / cooling test is performed in which the temperature is decreased from 200 ° C. to −70 ° C. at a temperature decrease rate of 5 ° C./min, and the expansion amount Eμm of the test piece when the temperature is increased from 23 ° C. to 150 ° C. The amount of expansion / shrinkage ES μm, which is the total amount of the shrinkage amount Sμm of the test piece when the temperature is lowered to 65 ° C., is obtained, and further, [expansion / shrinkage amount ES of the test piece] × [thickness of the test piece] The expansion / contraction parameter P μm ² which is the value of
Subsequently, an expansion / contraction parameter difference ΔP1 μm ² which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate] is obtained,
Next, an expansion / contraction standard parameter difference which is a value of [expansion / contraction parameter P of substrate test piece] − [total value of expansion / contraction parameters P of all test pieces other than the substrate, the first protective film, and the second protective film]. When obtaining ΔP0 μm ² ,
The value of ΔP1 / ΔP0 is used as a risk factor for fracture of the laminated structure.

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