TW202241713A - Method for manufacturing support sheet, composite sheet for forming resin film, kit, and wafer with resin film wherein the support sheet is used for heating workpieces or wafers obtained by dividing workpieces - Google Patents

Abstract

The present invention relates to a support sheet (10) which is used for heating workpieces or wafers obtained by dividing workpieces. Moreover, when the support sheet (10) with a sample size of 20 mm in length and 5 mm in width is subjected to the thermomechanical analysis (TMA) in either the traveling direction (MD) or the vertical direction (CD) tensile mode, the displacement (A 130) at 130 DEG C is 500 [mu]m or less, and the average displacement per 1 DEG C when the temperature rises from 23 DEG C to 130 DEG C (A 23 → 130) is less than the absolute value of the average displacement per 1 DEG C when slowly cooling from 130 DEG C to 50 DEG C (|B 130 → 50|).

Description

Method for manufacturing support sheet, composite sheet for forming resin film, kit, and wafer with resin film

The present invention relates to a method for manufacturing a support sheet, a composite sheet for forming a resin film and a kit including the support sheet and a resin film forming layer, and a wafer with a resin film. This application claims priority based on Japanese Patent Application No. 2021-062255 filed in Japan on March 31, 2021, and the contents of the application are incorporated herein.

Among workpieces such as semiconductor wafers, insulator wafers, and semiconductor device panels, there are workpieces in which a circuit is formed on one side (circuit surface) of the workpiece, and protruding electrodes such as bumps are further formed on the surface (circuit surface) . A laminate may be obtained by attaching the aforementioned workpiece to a support sheet (for example, a dicing sheet). The laminated body is heated and then cooled in a state where the peripheral portion of the support sheet is attached to a fixing jig such as a ring frame. Wafers are obtained by dividing the workpiece attached to the support sheet. Then, the wafer is picked up from the support sheet (see Patent Document 1).

In the manufacturing process of semiconductor devices using the so-called face-down packaging method, in order to protect the inner surface of the wafer formed by dicing the aforementioned workpiece, a protective film is used to form a film, and the protective film is used to form a A composite sheet for forming a protective film, which is a combination of a film and a support sheet. Furthermore, in order to bond the inner surface of the chip to a lead frame or an organic substrate, etc., a film-like adhesive is used. When dicing the above-mentioned workpiece, a dicing bond chip that combines a film-like adhesive and a support sheet is also used. The protective film forming film and the film-like adhesive are used by sticking to the inner surface of the aforementioned workpiece.

Hereinafter, in this specification, a protective film-forming film or a film-like adhesive is called a resin film-forming layer, and a composite sheet for protective film formation or a dicing bond wafer is called a composite sheet for resin film formation. A protective film formed of a protective film forming film or a bonding film formed of a film-like adhesive is called a resin film.

In the manufacturing process of a wafer with a resin film, a resin film forming layer for forming a protective film or a bonding film is attached to the inner surface of a workpiece. The resin film-forming layer may be attached to the inner surface of the workpiece in a state where the aforementioned resin film-forming composite sheet for resin film formation is laminated on the support sheet. The resin film forming layer may be attached to the inner surface of the workpiece without being laminated on the support sheet, and then attached to the support sheet.

The resin film forming layer attached to the inner surface of the workpiece is thermally cured on the support sheet as necessary to form a resin film. When the resin film-forming layer attached to the inner surface of the workpiece is thermally cured on the support sheet, the first laminate may be formed by laminating the support sheet, the resin film-forming layer, and the workpiece sequentially in the thickness direction. The composite sheet is heated in a state where the periphery of the sheet is attached to the ring frame, and then cooled. Then, the workpiece is divided by the cutting step on the support sheet, the resin film is cut off, and it is picked up in the form of a wafer with the resin film (refer to Patent Document 2).

Or, regarding the resin film forming layer attached to the inner surface of the workpiece, the workpiece is divided by the cutting step on the support sheet, the resin film is cut off, and after the wafer with the resin film forming layer is made, the resin film is formed on the support sheet. The formation layer is thermally cured to produce a wafer with a resin film. When the resin film-forming layer attached to the inner surface of the wafer is thermally cured on the support sheet, the fourth laminated composite sheet is formed by laminating the support sheet, the resin film-forming layer, and the wafer sequentially in the thickness direction of these The sheet was heated in a state where the periphery of the sheet was attached to the ring frame, and then cooled. Then, pick up the wafer with the resin film. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2015/190230. [Patent Document 2] International Publication No. 2015/178346.

[Problem to be Solved by the Invention]

For example, the semiconductor wafers described in Patent Document 1 and Patent Document 2 have a diameter of 8 inches, a thickness of 100 μm, and a mass of about 7.4 g. It is described that the aforementioned semiconductor wafer is diced into wafers having a wafer size of 9 mm×9 mm to form wafers.

In the manufacture and processing of wafers with resin films, semiconductor wafers with larger diameters are used, and the number and size of protruding electrodes on the semiconductor wafers increase, so the load on the support piece supported by the ring frame at the peripheral part There is a tendency to become larger, and the chip size tends to become smaller.

In the case of using the previous composite sheet or support sheet for forming a resin film, the above-mentioned manufacturing process is carried out in a state where the peripheral edge of the sheet for manufacturing and processing such as the first laminated composite sheet or the fourth laminated composite sheet is attached to the ring frame. When the processing sheet is heated, the load of workpieces such as semiconductor wafers or the load of multiple chips may cause the aforementioned manufacturing processing sheet to loosen, and the position of the wafer with the resin film may be displaced. In addition, in the dicing step after heating the sheet for manufacturing and processing, the position of the wafer with the resin film may be shifted. As a result, when the size of the wafer is smaller, the problem of poor recognition of the wafer with the resin film at the time of picking up may arise.

The object of the present invention is to provide a support sheet capable of eliminating the influence of the slack of the manufacturing processing sheet caused by heating and cooling and improving the visibility of the wafer in the pick-up device, and a resin film forming layer comprising the support sheet and a resin film forming layer. A method for manufacturing composite sheets and kits, and wafers with resin films. [Means to solve the problem]

The present invention provides the following support sheet, composite sheet and kit for forming a resin film, and a method for manufacturing a wafer with a resin film.

[1] A support sheet used for heating a workpiece or a wafer obtained by dividing a workpiece; When conducting thermomechanical analysis (TMA) in tensile mode, the displacement (A ₁₃₀ ) at 130°C is less than 500μm; the average displacement per 1°C (A _23→130 ) when the temperature rises from 23°C to 130°C is less than that of The absolute value of the average displacement per 1°C when slowly cooling from 130°C to 50°C (|B _130→50 |).

[Conditions of thermomechanical analysis (TMA)] Sample size: length 20mm, width 5mm; chuck interval: 15mm; with a load of 0.8g and a heating rate of 10°C/min, the temperature is raised from 23°C to 130°C and kept for 30 minutes. Then, it cooled from 130°C to 50°C with a load of 0.8 g and a cooling rate of 1°C/min. The amount of displacement [μm] during this period was measured.

[2] The support sheet as described in [1], wherein the above-mentioned support sheet is subjected to thermomechanical analysis (TMA) in the tensile mode in the direction of travel (MD) and in the tensile mode in the vertical direction (CD) under the aforementioned conditions. ), the displacement (A ₁₃₀ ) at 130°C is less than 500μm; the average displacement (A _23→130 ) per 1°C when the temperature rises from 23°C to 130°C is less than that of slow cooling from 130°C to 50°C The absolute value of the average displacement per 1°C up to °C (|B _130→50 |).

[3] The support sheet as described in [1] or [2], wherein the thermomechanical analysis is performed on the support sheet under the aforementioned conditions by stretching in any one of the traveling direction (MD) or the vertical direction (CD) (TMA), the average displacement (A _23→130 ) per 1°C when the temperature rises from 23°C to 130°C is a positive value. [4] The support sheet as described in [3], wherein the above-mentioned support sheet is subjected to thermomechanical analysis (TMA) in the tensile mode in the direction of travel (MD) and in the tensile mode in the vertical direction (CD) under the aforementioned conditions. ), the average displacement per 1°C (A _23→130 ) when the temperature rises from 23°C to 130°C is positive.

[5] The supporting sheet as described in [3] or [4], wherein thermomechanical analysis is performed on the supporting sheet under the aforementioned conditions by stretching in any one of the traveling direction (MD) or the vertical direction (CD) (TMA), the average displacement per 1°C (A _60→130 ) from 60°C to 130°C is relative to the average displacement per 1°C when the temperature is raised from 23°C to 130°C (A _{23 →130} ) ratio does not reach 1. [6] The support sheet as described in [5], wherein the above-mentioned support sheet is subjected to thermomechanical analysis (TMA) in the tensile mode in the direction of travel (MD) and in the tensile mode in the vertical direction (CD) under the aforementioned conditions. ), the average displacement per 1°C (A _60→130 ) from 60°C to 130°C is relative to the average displacement per 1°C from 23°C to 130°C (A _23→130 ) ratio did not reach 1.

[7] The support sheet according to any one of [1] to [6], wherein the support sheet is composed of a base material, or has a base material and an adhesive layer provided on one side of the base material, Moreover, the constituent material of the said base material contains polyolefin resin. [8] The support sheet according to any one of [1] to [7], wherein the support sheet is composed of only the base material, or has a base material and an adhesive layer provided on one side of the base material, In addition, the aforementioned base material is a stretched film. [9] The support sheet according to any one of [1] to [8], wherein the support sheet is in a roll shape.

[10] A composite sheet for forming a resin film, comprising the support sheet according to any one of [1] to [8], and a resin film forming layer provided on one side of the support sheet. [11] The composite sheet for forming a resin film according to [10], wherein the resin film forming layer is a protective film forming film. [12] The composite sheet for forming a resin film according to [10] or [11], wherein the composite sheet for forming a resin film is in a roll shape.

[13] A kit comprising: a first laminate formed by sequentially laminating a first release film, a resin film forming layer, and a second release film; and as described in any one of [1] to [9] The support sheet described is used for supporting a work to be attached to the resin film forming layer and the resin film forming layer. [14] The kit according to [13], wherein the resin film forming layer is a protective film forming film. [15] The kit according to [13] or [14], wherein the first laminate is in the shape of a roll.

[16] A method of manufacturing a wafer with a resin film, wherein the wafer with a resin film comprises a wafer and a resin film provided on an inner surface of the wafer; and, the method of manufacturing a wafer with a resin film has the following steps: Step: attaching the resin film forming layer in the resin film forming composite sheet as described in any one of [10] to [12] on the inner surface of the workpiece, or attaching the resin film forming layer as described in [13] to the inner surface of the workpiece. The resin film-forming layer in the kit described in any one of [15] is to produce a first laminated film formed by laminating the aforementioned resin film-forming layer and the workpiece in the thickness direction of these, and further in the aforementioned first laminated film The step of attaching the above-mentioned resin film-forming layer to the support sheet in the above-mentioned kit, thereby making the first laminated composite sheet formed on the above-mentioned support sheet so that the above-mentioned resin film-forming layer and the above-mentioned workpiece are sequentially laminated in the thickness direction of these; In the state where the peripheral portion of the first laminated composite sheet is attached to a jig for fixing, the first laminated composite sheet is heated to harden the resin film forming layer to form the resin film, thereby forming the above-mentioned supporting sheet so that the The second laminated composite sheet formed by laminating the resin film and the aforementioned workpieces sequentially in the thickness direction; cooling the aforementioned second laminated composite sheet, and then placing the aforementioned workpieces in the aforementioned second laminated composite sheet on the aforementioned support sheet Dividing, the step of cutting the aforementioned resin film, thereby manufacturing a third laminated composite sheet in which a plurality of wafers with resin films are fixed on the aforementioned supporting sheet; The step of picking up the aforementioned wafer with the resin film by tearing it off from the aforementioned supporting sheet.

[17] A method of manufacturing a wafer with a resin film, wherein the wafer with a resin film comprises a wafer and a resin film provided on an inner surface of the wafer; and, the method of manufacturing a wafer with a resin film comprises the following steps: Step: attaching the resin film forming layer in the resin film forming composite sheet as described in any one of [10] to [12] on the inner surface of the workpiece, or attaching the resin film forming layer as described in [13] to the inner surface of the workpiece. The resin film-forming layer in the kit described in any one of [15] is to produce a first laminated film formed by laminating the aforementioned resin film-forming layer and the workpiece in the thickness direction of these, and further in the aforementioned first laminated film The step of attaching the above-mentioned resin film-forming layer to the support sheet in the above-mentioned kit, thereby making the first laminated composite sheet formed on the above-mentioned support sheet so that the above-mentioned resin film-forming layer and the above-mentioned workpiece are sequentially laminated in the thickness direction of these; On the aforementioned support sheet, the aforementioned workpiece in the aforementioned first laminated composite sheet is divided, and the aforementioned resin film forming layer is cut, thereby manufacturing a fourth wafer having a plurality of wafers having resin film forming layers fixed on the aforementioned supporting sheet. The step of the laminated composite sheet: heating and cooling the fourth laminated composite sheet in a state where the periphery of the fourth laminated composite sheet is attached to the jig for fixing, so that the resin film in the fourth laminated composite sheet is formed Layer hardening to form the aforementioned resin film, thereby making a third laminated composite sheet in which a plurality of wafers with resin films are fixed on the aforementioned supporting sheet; The aforementioned supporting sheet is torn off, whereby the step of picking up the aforementioned wafer with the resin film. [Efficacy of the invention]

According to the present invention, there are provided a support sheet capable of eliminating the influence of the slack of the manufacturing processing sheet caused by heating and cooling and eliminating the recognition failure of the wafer in the pick-up device, and a resin film forming resin film comprising the above support sheet and a resin film forming layer. A method for manufacturing a composite sheet, a package, and a chip with a resin film.

[Support sheet] The support sheet of the embodiment of the present invention is used for heating the workpiece or the wafers obtained by dividing the workpiece; ) in any one of the tensile modes for thermomechanical analysis (TMA), the displacement (A ₁₃₀ ) at 130°C is less than 500μm; the average displacement per 1°C when the temperature rises from 23°C to 130°C (A _23→130 ) is smaller than the absolute value of the average displacement per 1°C (|B _130→50 |) when slowly cooling from 130°C to 50°C.

[Conditions of thermomechanical analysis (TMA)] Sample size: length 20mm, width 5mm; chuck interval: 15mm; with a load of 0.8g and a heating rate of 10°C/min, the temperature is raised from 23°C to 130°C and kept for 30 minutes. Thereafter, it was cooled from 130°C to 50°C with a load of 0.8 g and a cooling rate of 1°C/min. The amount of displacement [μm] during this period was measured.

When the displacement in the aforementioned thermomechanical analysis (TMA) is a positive value, it means that the supporting sheet is elongated, and when the displacement is negative, it means that the supporting sheet is shrinking.

The displacement amount (A ₁₃₀ ) of the supporting sheet of this embodiment at 130°C is 500 μm or less. Here, the displacement amount (A ₁₃₀ ) at 130°C was measured at the time point when the temperature reached 130°C after the temperature was raised from 23°C to 130°C. When the displacement (A ₁₃₀ ) at 130°C is 500 μm or less, the slack of the support sheet during heating can be reduced. The displacement amount (A ₁₃₀ ) at 130°C is preferably at most 450 μm, more preferably at most 400 μm, and still more preferably at most 360 μm. The displacement at 130°C (A ₁₃₀ ) is preferably greater than -50 μm, more preferably greater than 0 μm, further preferably greater than 21 μm, still more preferably greater than 43 μm, and most preferably greater than 64 μm.

For example, in the case of the support sheet having a negative value of displacement (A ₁₃₀ ) and a large shrinkage property, the adhesive force with the fixing jig such as the adhesive layer for the jig becomes weak at high temperature, so The weight of the workpiece and the risk of the support piece peeling off from the fixing jig. However, when the temperature is lowered, the adhesive force of the jig adhesive layer and the like to the fixing jig recovers, so the absolute value of the average displacement per 1°C when slowly cooling from 130°C to 50°C (｜B _{130→ 50} |) can also be large. Therefore, it is preferable that the average displacement per 1°C (A _{23 → 130} ) from 23°C to 130°C is smaller than the absolute value of the average displacement per 1°C when slowly cooling from 130°C to 50°C (|B _130→50 |).

Here, the average displacement per 1°C (A _23→130 ) when the temperature is raised from 23°C to 130°C can be obtained by the following formula. A _{23 → 130} = (A ₁₃₀ - A ₂₃ )/107 = A ₁₃₀ /107 [μm/°C].

Displacement (A ₂₃ ) at 23°C = 0 μm; displacement at 130°C (A ₁₃₀ ) [μm].

Here, the average displacement per 1°C (B _130→50 ) when slowly cooling from 130°C to 50°C can be obtained from the following formula. B _130→50 = (B ₅₀ -B ₁₃₀ )/80 [μm/°C]. Furthermore, it is not assumed that the support sheet is elongated during slow cooling, so usually B _130→50 is a negative value.

Here, the absolute value of the average displacement per 1°C (|B _130→50 |) when slowly cooling from 130°C to 50°C can be obtained by the following formula. |B _{130 → 50} |=|B ₅₀ -B ₁₃₀ |/80 [μm/°C].

Displacement (B ₁₃₀ ) [μm] after holding at 130°C for 30 minutes; displacement (B ₅₀ ) [μm] at 50°C after slow cooling.

Since the above-mentioned average displacement (A _23→130 ) is smaller than the absolute value of the above-mentioned average displacement (|B _130→50 |), the position change of the wafer on the support sheet caused by heating and cooling can be reduced, and pick-up can be eliminated. The device does not recognize the chip properly.

When performing thermomechanical analysis (TMA) on the aforementioned supporting sheet under the following conditions by tensile mode in either the traveling direction (MD) or the vertical direction (CD), subtract from the aforementioned average displacement (A _23→130 ) The value [(A _23→130 )－｜B _{130 →50 ｜) obtained from the absolute value of the aforementioned average displacement (｜B 130→50} ｜) is a negative value, preferably -0.10μm/℃ to -5μm/℃ , more preferably -0.40 μm/°C to -4 μm/°C, further preferably -0.75 μm/°C to -3 μm/°C.

Compared with when the temperature rises to 130°C and remains in a state where there is no temperature change, the slow elongation of the support sheet caused by applying the same load (the load of the workpiece) to the base material of the support sheet for a long time is due to the temperature rise and slow cooling And the value obtained by subtracting the absolute value of the above-mentioned average displacement (｜B _130→50 ｜) from the above-mentioned average displacement (A _23→130 ) when the temperature changes [(A _23→130 )－｜B _130→50 ｜ ]more important. The reason is that when the first laminated composite sheet or the fourth laminated composite sheet is actually kept at 130°C, the resin film forming layer, the adhesive layer, and the adhesive layer for jigs in the first laminated composite sheet or the fourth laminated composite sheet It is viscous at high temperature, so the phenomenon of slow elongation of the support sheet eases the stress in the first laminated composite sheet or the fourth laminated composite sheet as a whole, and is not easy to affect relaxation.

Here, subtract the [(A _{23 →130 )} -| The absolute value of the value obtained by B _{130 → 50} |]" is used as the "balance evaluation value of MD and CD". The balance evaluation value of MD and CD is preferably at most 3.0, more preferably at most 2.5, still more preferably at most 2.0, and most preferably at most 1.8. When the balance evaluation value of MD and CD is greater than the above-mentioned upper limit, under the condition that the shrinkage behavior of the support sheet is restricted by the fixing fixture such as the ring frame, after heating and cooling, the support sheet will only appear in the Excessive contraction force in any one direction of MD or CD will easily form wrinkles (the undulating shape of the support sheet) on the support sheet near the fixing jig. When the aforementioned wrinkles are to be formed, since a force is generated in the direction in which the supporting sheet or the resin film forming composite sheet is peeled from the fixing jig (that is, the direction perpendicular to the plane of the fixing jig such as a ring frame), it is supported. The sheet or the composite sheet for resin film formation peels from the jig for fixation, and there exists a high possibility that it will fall off from this as a starting point. However, it is considered that this possibility can be further reduced by making the balance evaluation value of MD and CD below the said upper limit.

When thermomechanical analysis (TMA) is performed on the aforementioned supporting sheet under the aforementioned conditions by stretching mode in either the traveling direction (MD) or the vertical direction (CD), it is only necessary to fully satisfy the aforementioned requirements.

When the support sheet is subjected to thermomechanical analysis (TMA) under the aforementioned conditions in the tensile mode in the traveling direction (MD) and in the tensile mode in the vertical direction (CD), it is preferable that all of the above requirements are fully satisfied.

That is, it is preferable that the displacement (A ₁₃₀ ) at 130°C is 500 μm or less when the support sheet is subjected to thermomechanical analysis (TMA) in the tensile mode in the traveling direction (MD) under the aforementioned conditions, and, When performing thermomechanical analysis (TMA) in the tensile mode in the vertical direction (CD), the displacement (A ₁₃₀ ) at 130°C is 500 μm or less. Preferably, when the above-mentioned supporting sheet is subjected to thermomechanical analysis (TMA) by the tensile mode of the traveling direction (MD) under the above-mentioned conditions, the above-mentioned average displacement (A _{23 → 130} ) is smaller than the absolute value of the above-mentioned average displacement ( |B _130→50 |), and, when thermomechanical analysis (TMA) is carried out by tensile mode in the vertical direction (CD), the above-mentioned average displacement (A _23→130 ) is smaller than the absolute value of the above-mentioned average displacement ( |B _130→50 |).

Usually, the traveling direction (MD) of the support sheet refers to the traveling direction of the resin when the support sheet is formed. The so-called vertical direction (CD) of the supporting sheet refers to the direction perpendicular to the traveling direction (MD) of the supporting sheet. When the support sheet is in the shape of a roll, regardless of whether the support sheet is extended or not, the long direction of the support sheet is the traveling direction (MD), and the width direction of the support sheet is the vertical direction (CD). Even when the support sheet is in a single sheet shape, the traveling directions of the resins can be distinguished from each other by optical analysis such as analysis of X-ray two-dimensional diffraction images, for example.

When the supporting sheet has a substrate and an adhesive layer, the displacement of the supporting sheet during thermomechanical analysis (TMA) is greatly affected by the characteristics of the substrate, so the traveling direction (MD) of the supporting sheet is set as The traveling direction (MD) of the substrate, the vertical direction (CD) of the support sheet is the vertical direction (CD) of the substrate.

The support sheet of this embodiment is preferably: when the above-mentioned support sheet is subjected to thermomechanical analysis (TMA) in the tensile mode of either the traveling direction (MD) or the vertical direction (CD) under the aforementioned conditions, from 23°C The average displacement per 1°C (A _{23 → 130} ) when the temperature rises to 130°C is a positive value. The adhesion to the fixing fixture is weak at high temperature. If the average displacement (A _23→130 ) is a negative value, the support sheet may shrink, and the support sheet may peel off from the fixing jig due to the weight of the workpiece or wafer at high temperature. Since the average displacement amount (A _23→130 ) is a positive value, it is possible to eliminate the possibility that the support sheet will peel off from the fixing jig.

Here, the average displacement per 1°C (A _23→130 ) when the temperature is raised from 23°C to 130°C can be obtained from the above formula (A _23→130 =A ₁₃ /107 [μm/°C]).

The aforementioned average displacement (A _23→130 ) is more preferably at least 0.20 μm/°C, still more preferably at least 0.40 μm/°C, and most preferably at least 0.60 μm/°C.

When thermal mechanical analysis (TMA) is carried out on the aforementioned supporting sheet under the aforementioned conditions by stretching in either the traveling direction (MD) or the vertical direction (CD), as long as the aforementioned average displacement (A _23→130 ) is positive value.

Preferably, when the above-mentioned supporting sheet is subjected to thermomechanical analysis (TMA) through the tensile mode of the traveling direction (MD) and the tensile mode of the vertical direction (CD) under the aforementioned conditions, the aforementioned average displacement (A _{23→ 130} ) are all positive values.

When the above-mentioned supporting sheet is subjected to thermomechanical analysis (TMA) under the above-mentioned conditions through the tensile mode in the traveling direction (MD) and the tensile mode in the vertical direction (CD), the above-mentioned average displacement (A _23→130 ) is More preferably, it is at least 0.20 μm/°C, still more preferably at least 0.40 μm/°C, and most preferably at least 0.60 μm/°C.

Preferably, when the above-mentioned support sheet is subjected to thermomechanical analysis (TMA) under the above-mentioned conditions by stretching mode in either the traveling direction (MD) or the vertical direction (CD), when the temperature is raised from 60°C to 130°C The ratio of the average displacement per 1°C (A _60→130 ) to the average displacement per 1°C (A _23→130 ) from 23°C to 130°C was less than 1. After 60°C during heating, the support sheet tends to become soft as a material. Since the ratio of the above-mentioned average displacement (A _60→130 ) to the above-mentioned average displacement (A _23→130 ) is less than 1, the elongation behavior of the supporting sheet is suppressed after 60°C during heating, thereby Easy to suppress relaxation after final cooling.

The average displacement per 1°C (A _{23 → 130} ) when the temperature is raised from 23°C to 130°C can be obtained by the following formula. A _{23 → 130} = (A ₁₃₀ - A ₂₃ )/107 = A ₁₃₀ /107 [μm/°C].

Displacement (A ₂₃ ) at 23°C = 0 μm; displacement at 130°C (A ₁₃₀ ) [μm].

Here, the average displacement per 1°C (A _60→130 ) when the temperature is raised from 60°C to 130°C can be obtained by the following formula. A _60→130 ＝(A ₁₃₀ －A ₆₀ )/70[μm/℃]

Displacement (A ₆₀ ) [μm] at 60°C; displacement (A ₁₃₀ ) [μm] at 130°C.

Therefore, the average displacement per 1°C (A _60→130 ) when the temperature is raised from 60°C to 130°C is relative to the average displacement per 1°C (A _23→130 ) when the temperature is raised from 23°C to 130°C The ratio [(A _60→130 )/(A _23→130 )] can be obtained from these formulas.

The ratio [(A _60→130 )/(A _23→130 )] of the aforementioned average displacement (A _60→130 ) to the aforementioned average displacement (A ₂₃ →130 )] is preferably less than 1, more preferably 0.99 or less, more preferably 0.98 or less. The ratio [(A _60→130 )/(A _23→130 )] of the above average displacement (A _60→130 ) to the above average displacement (A ₂₃ →130 )] is preferably 0.10 or more, more preferably 0.20 or more , more preferably not less than 0.30, especially preferably not less than 0.90.

Compared with the state where there is no temperature change after the temperature rises to 130°C, the slow elongation of the support sheet caused by applying the same load (the load of the workpiece) to the base material of the support sheet for a long time is caused by the temperature rise and slow cooling. The ratio [(A _60→130 )/(A _23→130 )] of the above average displacement (A _60→130 ) to the above average displacement (A _23→130 ) at the time of temperature change is more important. The reason is that when the first laminated composite sheet or the fourth laminated composite sheet is actually held at 130°C, the resin film forming layer, the adhesive layer, and the adhesive layer for jigs in the first laminated composite sheet or the fourth laminated composite sheet It is viscous at high temperature, so the phenomenon of slow elongation of the support sheet eases the stress in the first laminated composite sheet or the fourth laminated composite sheet as a whole, and is not easy to affect relaxation.

Preferably, when the above-mentioned supporting sheet is subjected to thermomechanical analysis (TMA) through the tensile mode of the traveling direction (MD) and the tensile mode of the vertical direction (CD) under the aforementioned conditions, the aforementioned average displacement (A _{60→ 130} ) to the aforementioned average displacement (A _23→130 ) did not reach 1.

When the above-mentioned supporting sheet is subjected to thermomechanical analysis (TMA) under the above-mentioned conditions through the tensile mode in the traveling direction (MD) and the tensile mode in the vertical direction (CD), the above-mentioned average displacement (A _60→130 ) is relatively The above average displacement (A _23→130 ) ratio [(A _60→130 )/(A _23→130 )] is preferably less than 1, more preferably 0.99 or less, and even more preferably 0.98 the following. The ratio [(A _60→130 )/(A _23→130 )] of the above average displacement (A _60→130 ) to the above average displacement (A ₂₃ →130 )] is preferably 0.10 or more, more preferably All are at least 0.20, and more preferably all are at least 0.30.

The support sheet of this embodiment can be suitably used in the following method of manufacturing a wafer with a resin film: attaching a resin film forming layer to the inner surface of a workpiece, and making the aforementioned resin film forming layer and the aforementioned workpiece sequentially on the support sheet The first laminated composite sheet formed by laminating these layers in the thickness direction is formed on the support sheet by heating the first laminated composite sheet in a state where the peripheral portion of the first laminated composite sheet is attached to a jig for fixing. The second laminated composite sheet formed by laminating the resin film and the aforementioned workpiece sequentially in the thickness direction thereof, cooling the aforementioned second laminated composite sheet, and then dividing the aforementioned workpiece on the aforementioned support sheet, cutting the aforementioned resin film, and forming in A third laminated composite sheet on which a plurality of chips with resin films are fixed on the support sheet, picks up the aforementioned wafers with resin films in the third laminated composite sheet. The support sheet according to the embodiment of the present invention has the above-mentioned structure, so even if the peripheral portion of the first laminated composite sheet is attached to the jig for fixing, the first laminated composite sheet is heated and then the second laminated composite sheet is cooled. , It is also possible to eliminate the influence of the slack of the third laminated composite sheet and improve the recognition of the chip of the pick-up device.

Furthermore, the support sheet of this embodiment can be suitably used in a method of manufacturing a wafer with a resin film as follows: affixing a resin film-forming layer to the inner surface of a work, placing the resin film-forming layer and the work on the support sheet The above-mentioned work in the first laminated composite sheet formed by sequentially laminating these layers in the thickness direction is divided, the above-mentioned resin film-forming layer is cut off, and a fourth wafer in which a plurality of wafers with resin film-forming layers are fixed on the above-mentioned supporting sheet is formed. As for the laminated composite sheet, for the aforementioned fourth laminated composite sheet, in a state where the periphery of the aforementioned fourth laminated composite sheet is attached to a jig for fixing, the aforementioned fourth laminated composite sheet is heated to form a plurality of For the third laminated composite sheet of wafers with resin film, the aforementioned third laminated composite sheet is cooled, and then the aforementioned wafer with resin film in the aforementioned third laminated composite sheet is picked up. The support sheet according to the embodiment of the present invention has the above-mentioned structure, so even if the fourth laminated composite sheet is heated with the peripheral portion of the fourth laminated composite sheet attached to the jig for fixing, and then the third laminated composite sheet is cooled, Also, the influence of the slack of the third laminated composite sheet can be eliminated, and the visibility of the chip of the pick-up device can be improved.

The support sheet according to the embodiment of the present invention has the above structure, so even when the mass of the workpiece is 20g or more, the visibility of the wafer of the pick-up device can be improved, and when the mass of the workpiece is 30g or more, it can also be improved. The discriminability of the pick-up device can also improve the discriminability of the pick-up device when the mass of the workpiece is 40 g or more.

In this specification, the so-called "workpiece" refers to a wafer or a semiconductor device panel. Examples of "wafers" include: semiconductor wafers made of elemental semiconductors such as silicon, germanium, and selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; , lithium tantalate and other insulators composed of insulator wafers. The so-called "semiconductor device panel" refers to an aggregate in which a plurality of semiconductor devices are arranged in a planar manner and at least one electronic component is sealed with a sealing resin layer. A circuit is formed on one surface of these works, and in this specification, the surface of the work on which the circuit is formed in this way is called a "circuit surface". In addition, the surface on the opposite side to the circuit surface in the workpiece is referred to as an "inner surface". The workpiece is divided into wafers by means of dicing or the like. In this specification, as in the case of the workpiece, the surface of the wafer on which the circuit is formed is referred to as a "circuit surface", and the surface of the wafer opposite to the circuit surface is referred to as an "inner surface". Protruding electrodes such as bumps and pillars are arranged on the circuit surface of the workpiece and the circuit surface of the chip. The protruding electrodes are preferably made of solder.

The above-mentioned supporting sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the supporting sheet is composed of multiple layers, the constituent materials and thicknesses of these layers may be the same or different, and the combination of these layers is not particularly limited as long as it does not impair the effect of the present invention.

The support sheet is preferably transparent, and may be colored according to the purpose. When the resin film forming layer has energy ray curability, it is preferable that the support sheet allows energy ray to pass through.

As a support sheet, the support sheet which has a base material and the adhesive layer provided on one side of the said base material, the support sheet which consists only of a base material, etc. are mentioned, for example. When the support sheet has an adhesive layer, the adhesive layer is arranged between the base material and the resin film forming layer in the composite sheet for resin film formation.

When using the support sheet provided with a base material and an adhesive layer, in the composite sheet for resin film formation, the adhesiveness and peelability between a support sheet and a resin film formation layer can be adjusted easily. When using the support sheet which consists only of a base material, the composite sheet for resin film formation can be manufactured at low cost.

Hereinafter, an example of the supporting sheet of this embodiment will be described with reference to the drawings.

Fig. 1 is a cross-sectional view schematically showing an example of a support sheet according to this embodiment. In addition, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention, the main parts may be enlarged and shown for convenience, and the dimensional ratio of each component may not necessarily be the same as the actual one.

The support sheet 10 shown in FIG. 1 is provided with an adhesive layer 12 on one side 11 a of the substrate 11 (in this specification, sometimes referred to as “the first side 11 a ”).

Next, each layer constituting the support sheet 10 will be described in more detail.

○Substrate The above-mentioned base material is in the form of a sheet or a film, and examples of the constituent material of the base material include various resins. Examples of the aforementioned resins include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, poly Polyolefins other than polyethylene such as methylpentene and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornene Vinyl copolymers such as ethylene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene ; Polycycloolefin; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Polyethylene isophthalate, Polyethylene 2,6-naphthalate Esters, polyesters such as wholly aromatic polyesters having aromatic ring groups in all their constituent units; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyacrylamines Acrylic acid ester; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide;

The constituent material of the aforementioned base material preferably contains polyolefin resin, and among these, polyolefin other than polyethylene is preferable, and polypropylene is more preferable.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than this polyester, are also mentioned, for example. In the polymer alloy of the aforementioned polyester and a resin other than the polyester, it is preferable that the amount of the resin other than the polyester is relatively small. Furthermore, examples of the above-mentioned resins include: cross-linked resins obtained by cross-linking one or two or more of the above-mentioned resins exemplified so far; Modified resins such as polymers.

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

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

The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. When the thickness of the base material is in such a range, the flexibility of the support sheet and the composite sheet for forming a resin film, and the sticking suitability to workpieces are further improved. Here, the "thickness of the substrate" refers to the thickness of the entire substrate, for example, the thickness of a substrate composed of multiple layers refers to the total thickness of all the layers constituting the substrate. In this specification, unless otherwise specified, "thickness" means the average value of the thickness measured at 5 randomly selected places in the object, which can be measured using constant pressure thickness in accordance with JIS K7130 (Japanese Industrial Standards; Japanese Industrial Standards) device to obtain.

The base material may further contain various well-known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the aforementioned resins.

The base material is preferably transparent, but it may be colored according to the purpose, and another layer may be vapor-deposited.

For the base material, in order to adjust the adhesion with the adhesive layer or resin film forming layer provided on the base material, the following treatments may be performed on the surface: roughening treatment by sandblasting, solvent treatment, etc.; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; lipophilic treatment; hydrophilic treatment, etc. Moreover, the surface of the substrate may also be treated with a primer.

The substrate can also have adhesiveness on at least one side by containing a specific range of components (such as resin, etc.).

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

The aforementioned substrate is preferably a stretched film. The extending direction of the substrate can be only the traveling direction (MD) of the substrate, or only the vertical direction (CD) of the substrate, more preferably biaxial extension of the traveling direction (MD) and the vertical direction (CD).

Since the base material is a stretched film, the residual stress of the stretched film can reduce the aforementioned average displacement (A _23→130 ) and the aforementioned average displacement (A _60→130 ) of the supporting sheet. In particular, the residual stress of the stretched film has a great effect on reducing the average displacement (A _60→130 ), so it can reduce the displacement (A ₁₃₀ ) at 130°C and the ratio [(A _60→130 )/(A _{23 → 130} )].

The stretching of the substrate is preferably under heating. The heating temperature conditions are adjusted according to the constituent materials of the substrate. For example, when the constituent material of the substrate is polypropylene, the heating temperature condition is preferably from 100°C to 140°C, more preferably from 105°C to 135°C, and still more preferably from 110°C to 130°C.

The heating time condition is preferably from 15s to 120s, more preferably from 30s to 100s, and still more preferably from 45s to 80s.

The stretching tension is preferably from 1.0N/m to 6.0N/m, more preferably from 1.3N/m to 5.0N/m, and still more preferably from 1.6N/m to 4.0N/m.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or a film, and contains an adhesive resin. Examples of the adhesive resin include acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonate, and ester-based resins. Among them, an acrylic resin is preferable from the viewpoint of adjusting the adhesiveness with respect to the resin film forming layer and the resin film.

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

The thickness of the adhesive layer is not particularly limited, but it is preferably from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, and still more preferably from 1 μm to 30 μm, more preferably 1 μm to 15 μm, especially preferably 1 μm to 9 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all the layers constituting the adhesive layer.

The adhesive layer is preferably transparent, and may be colored according to purposes. When the resin film forming layer has energy ray curability, it is preferable that the pressure-sensitive adhesive layer transmits energy ray.

The adhesive layer may be either energy ray curable or non-energy ray curable. The energy ray hardening adhesive layer can adjust the physical properties before and after hardening. For example, by hardening the energy ray curable adhesive layer before picking up the wafer with a resin film mentioned later, it becomes possible to pick up the wafer with a resin film more easily.

In this specification, the term "energy ray" refers to those having energy quanta in electromagnetic waves or charged particle beams. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode, Light Emitting Diode) lamp as an ultraviolet source. Regarding electron beams, those generated by an electron beam accelerator or the like can be irradiated. In this specification, "energy ray curability" means the property of being cured by irradiation of energy ray, and "non-energy ray curability" means the property of not being cured even when irradiated with energy ray. In addition, "non-curable" means the property of not being cured by any means such as heating or irradiation of energy rays.

In the case where the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include the following adhesive composition, etc.: Adhesive composition (I-1) contains Non-energy ray-curable and adhesive acrylic resin (I-1a) (hereinafter, sometimes simply referred to as "adhesive resin (I-1a)"), and an energy ray-curable compound; adhesive composition ( I-2), the energy-ray-curable adhesive resin (I-2a) (hereinafter, sometimes referred to as is "adhesive resin (I-2a)"); and an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound.

When the adhesive layer is non-energy ray-curable, the non-energy ray-curable adhesive composition includes, for example, an adhesive composition containing the aforementioned non-energy ray-curable adhesive resin (I-1a) Object (I-4) and so on.

[Non-energy ray-curable adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is an adhesive acrylic resin having functional groups such as hydroxyl groups. As said acrylic resin, the acrylic polymer which has a structural unit derived from a hydroxyl group-containing monomer, and a structural unit derived from an alkyl (meth)acrylate is mentioned, for example. Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the aforementioned alkyl group is preferably linear or branched. shape.

The said acrylic resin is resin containing the structural unit derived from the (meth)acrylate which is a monomer. The so-called "derived from" mentioned here means that the aforementioned monomers are subjected to structural changes necessary for polymerization. In addition, in this specification, "(meth)acrylic acid" is taken as the concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

The above-mentioned acrylic polymer may have structural units derived from functional group-containing monomers other than hydroxyl-containing monomers in addition to structural units derived from hydroxyl-containing monomers and alkyl (meth)acrylates. . Examples of the functional group-containing monomer include: starting point of crosslinking by reacting the functional group with a cross-linking agent described later, or an isocyanate group and glycidyl group in an unsaturated group-containing compound described below with the functional group A monomer that introduces unsaturated groups into the side chains of acrylic polymers by reacting functional groups such as groups.

As said functional group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example other than a hydroxyl group containing monomer.

The said acrylic polymer may have the structural unit derived from another monomer other than the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group containing monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like. Examples of the other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

In the aforementioned adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3) and adhesive composition (I-4) (hereinafter, these adhesive compositions are included In the abbreviated as "adhesive composition (I-1) to adhesive composition (I-4)"), the constituent units of the aforementioned acrylic resin such as the aforementioned acrylic polymer may be only one type or two types. In the case of two or more of the above, combinations and ratios of these constituent units can be selected arbitrarily.

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

Adhesive resin (I-1a) contained in adhesive composition (I-1) or adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds , the combination and ratio of these adhesive resins (I-1a) can be selected arbitrarily.

In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-4), relative to the total mass of the aforementioned adhesive layer, the content of the adhesive resin (I-1a) is The ratio is preferably 5% by mass to 99% by mass, and may be, for example, any of 25% by mass to 98% by mass, 45% by mass to 97% by mass, and 65% by mass to 96% by mass.

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

The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy ray polymerizable unsaturated group, a compound capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). base compound. As said energy ray polymerizable unsaturated group, a (meth)acryl group, vinyl (ethenyl), allyl (2-propenyl) etc. are mentioned, for example, Preferably it is a (meth)acryl group. Examples of groups capable of bonding to functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding to hydroxyl groups or amine groups, and carboxyl groups or epoxy groups capable of bonding Hydroxyl and amino groups, etc.

As said unsaturated group containing compound, (meth)acryloxyethyl isocyanate, (meth)acryl isocyanate, glycidyl (meth)acrylate, etc. are mentioned, for example.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) or adhesive composition (I-3) may be only one kind, or two or more kinds, and in the case of two or more kinds , the combination and ratio of these adhesive resins (I-2a) can be selected arbitrarily.

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

[Energy Beam Curing Compound] Examples of the energy ray-curable compound contained in the adhesive composition (I-1) or adhesive composition (I-3) include energy ray polymerizable unsaturated groups that can be cured by energy ray irradiation. Hardened monomer or oligomer.

Among the energy ray-curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. base) acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid aminomethyl Ester; Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc. In the energy ray-curable compound, examples of the oligomer include oligomers that are polymers of the monomers exemplified above, and the like.

The aforementioned energy ray-curing compound contained in the adhesive composition (I-1) or adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, these Combinations and ratios of energy ray-curing compounds can be selected arbitrarily.

In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-3), the ratio of the content of the energy ray-curable compound to the total mass of the adhesive layer is relatively Preferably, it is 1 mass % to 95 mass %.

[Crosslinking agent] It is preferable that the adhesive composition (I-1) to adhesive agent composition (I-4) further contain an isocyanate type crosslinking agent.

The crosslinking agent reacts with the hydroxyl group to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a) together.

In the aforementioned adhesive composition (I-1) to adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a) to 50 parts by mass, for example, any one of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass may be used. As a crosslinking agent, the thing similar to "(crosslinking agent)" mentioned in the composition (III-1) for protective film formation mentioned later is mentioned, for example.

[Photopolymerization Initiator] Adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) (hereinafter including these adhesive compositions are referred to simply as "adhesive composition (I-1) Adhesive composition (I-3)") may further contain a photopolymerization initiator. Adhesive composition (I-1) to adhesive composition (I-3) containing a photopolymerization initiator fully progressed the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

As said photoinitiator, the photoinitiator similar to "(photoinitiator)" mentioned in the composition (III-1) for protective film formation mentioned later is mentioned, for example.

The photopolymerization initiator contained in adhesive composition (I-1) to adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, these photopolymerization initiators The combination and ratio of the polymerization initiators can be selected arbitrarily.

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

[Other additives] Adhesive composition (I-1) to adhesive composition (I-4) may also contain other additives that do not correspond to any of the above-mentioned components within the range that does not impair the efficacy of the present invention. Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Reaction delay agent, crosslinking accelerator (catalyst) and other known additives. Furthermore, the so-called reaction delaying agent is, for example, the adhesive composition (I-4) that suppresses the effect of the catalyst mixed in the adhesive composition (I-1) to the adhesive composition (I-4) during preservation. -1) A component that undergoes an unintended cross-linking reaction in the adhesive composition (I-4). As a reaction retarder, for example, a compound that forms a chelate complex by chelating a catalyst, more specifically, a compound having two or more carbonyl groups (-C(=O) in one molecule can be mentioned. -) compounds.

Adhesive composition (I-1) to adhesive composition (I-4) may contain only one kind of other additives, or two or more kinds. In the case of two or more kinds, the combination of these other additives And the ratio can be chosen arbitrarily.

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

[solvent] Adhesive composition (I-1) to adhesive composition (I-4) may also contain a solvent. Adhesive composition (I-1) to adhesive composition (I-4) improve the applicability to the surface to be coated by containing a solvent.

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

The solvents contained in adhesive composition (I-1) to adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these solvents Can be selected arbitrarily.

The content of the solvent in the adhesive composition (I-1) to adhesive composition (I-4) is not particularly limited, as long as it is properly adjusted.

○Manufacturing method of adhesive composition Adhesive compositions such as adhesive composition (I-1) to adhesive composition (I-4) are made by using the above-mentioned adhesive resin and, if necessary, components other than the above-mentioned adhesive resin. It is obtained by blending the components of the composition. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. The method of mixing the ingredients is not particularly limited, as long as it is properly selected from known methods such as the following methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; A method of mixing by applying ultrasonic waves. The temperature and time for adding and mixing the ingredients are not particularly limited as long as the ingredients are not deteriorated, as long as they are properly adjusted, the temperature is preferably 15°C to 30°C.

○Adhesive layer manufacturing method The aforementioned adhesive layer can be formed using an adhesive composition containing an adhesive resin. For example, the adhesive layer can be formed on the target site by applying an adhesive composition to the surface to be formed of the adhesive layer and drying it as necessary. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In the adhesive layer, the ratio of the total content of one or two or more of the following components in the adhesive layer to the total mass of the adhesive layer does not exceed 100% by mass. Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the following components of the adhesive composition to the total mass of the adhesive composition does not exceed 100% by mass.

The application of the adhesive composition may be performed by a known method, for example, use of an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife Coater, curtain coater, die coater, knife coater, screen coater, Meyer rod coater, kiss coater and other coating methods.

The drying conditions of the adhesive composition are not particularly limited. However, when the adhesive composition contains a solvent, it is preferable to heat and dry it. In addition, the adhesive composition containing a solvent, for example, is preferably heated and dried at 70° C. to 130° C. for 10 seconds to 5 minutes.

◇Manufacturing method of support sheet When providing an adhesive layer on a base material, for example, it is only necessary to apply an adhesive composition on a base material, and to dry it as needed. In addition, for example, an adhesive composition may be applied on a release film and dried as necessary to form an adhesive layer on the release film in advance, and the exposed surface of the adhesive layer may be bonded to one surface of the substrate. In this way, an adhesive layer is laminated on the base material. The release film in this case may be removed at any timing during the production process or use process of the composite sheet for resin film formation.

The support sheet 10 is preferably in the shape of a roll. When the support sheet 10 is in the shape of a roll, regardless of whether the support sheet 10 is extended or not, the longitudinal direction of the support sheet 10 is the traveling direction (MD), and the width direction of the support sheet 10 is the vertical direction (CD).

[Composite sheet for resin film formation] The composite sheet for resin film formation of embodiment of this invention is equipped with the support sheet 10 of embodiment of this invention mentioned above, and the resin film formation layer provided on one surface of the said support sheet 10. Hereinafter, an example of the composite sheet for resin film formation of this embodiment is demonstrated, referring drawings.

Fig. 2 is a cross-sectional view schematically showing an example of the composite sheet for forming a resin film according to the present embodiment. In addition, in the figures after FIG. 2, the same code|symbol as the case of the figure which was demonstrated is attached|subjected to the component element shown in the figure which was already explained, and detailed description is abbreviate|omitted.

The resin film-forming composite sheet 101 shown here includes a support sheet 10 and a resin film-forming layer 13 provided on one side (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10 And constitute. The support sheet 10 is constituted by including a base material 11 and an adhesive layer 12 provided on one surface (first surface) 11 a of the base material 11 . In the composite sheet 101 for resin film formation, the adhesive layer 12 is arrange|positioned between the base material 11 and the resin film formation layer 13.

That is, the composite sheet 101 for resin film formation is comprised by laminating|stacking the base material 11, the adhesive agent layer 12, and the resin film formation layer 13 sequentially in the thickness direction of these. The first surface 10a of the support sheet 10 is the same as the surface (in this specification, sometimes referred to as “first surface”) 12a on the side opposite to the substrate 11 side in the adhesive layer 12 .

The composite sheet 101 for resin film formation is further equipped with the adhesive agent layer 16 for clips, and the peeling film 15 on the resin film formation layer 13. In the resin film forming composite sheet 101, the resin film forming layer 13 is laminated on the entire or substantially entire surface of the first surface 12a of the adhesive layer 12, and the side of the resin film forming layer 13 opposite to the adhesive layer 12 is A part of the side surface (in this specification, sometimes referred to as "first surface") 13a, that is, a region near the peripheral portion, is laminated with an adhesive layer 16 for jigs. Furthermore, in the first surface 13a of the resin film forming layer 13, the area where the adhesive layer 16 for jigs is not laminated, and the surface of the adhesive layer 16 for jigs that is on the opposite side to the side of the resin film forming layer 13 (in this paper) In the specification, sometimes referred to as "the first surface") 16a, the release film 15 is laminated. The support sheet 10 is provided on a surface (in this specification, sometimes referred to as a "second surface") 13b of the resin film forming layer 13 on the opposite side to the first surface 13a.

It is not limited to the composite sheet 101 for forming a resin film. In the composite sheet for forming a resin film of this embodiment, the release film may have any configuration. The composite sheet for forming a resin film of this embodiment may or may not have a release film. .

The adhesive layer 16 for jigs is for fixing the composite sheet 101 for resin film formation to the jig 18 for fixation, such as a ring frame. The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure comprising a sheet as a core material and adhesive components provided on both sides of the aforementioned sheet. Floor.

As the adhesive constituting the adhesive layer 16 for the jig, it is preferable to have the required adhesive force and re-peelability. For example, acrylic adhesives, rubber adhesives, polysiloxane adhesives, and urethane adhesives can be used. Ester-based adhesives, polyester-based adhesives, polyvinyl ether-based adhesives, etc. Among these, an acrylic adhesive having high adhesiveness to the fixing jig 18 such as a ring frame and capable of effectively suppressing peeling of the fixing jig 18 such as a ring frame from the composite sheet for forming a protective film in a cutting step or the like is preferable. In addition, the base material which is a core material may be inserted in the middle of the thickness direction of the adhesive agent layer for jigs.

The adhesive layer for the jig can be formed using an adhesive composition for the jig containing an adhesive resin. For example, the adhesive layer for the jig can be formed on the target site by applying the adhesive composition for the jig on the surface to be formed of the adhesive layer for the jig and drying it. Examples of the adhesive composition for jigs include the same compositions as the aforementioned adhesive composition (I-1) to adhesive composition (I-4). The content ratio of the components that do not vaporize at room temperature in the adhesive composition for jigs is usually the same as the content ratio of the above-mentioned components in the adhesive layer for jigs.

On the other hand, from the viewpoint of adhesiveness to the fixing jig 18 such as a ring frame, the thickness of the adhesive layer for the jig is preferably 5 μm to 200 μm, particularly preferably 10 μm to 100 μm.

The composite sheet 101 for forming a resin film is attached to the inner surface of the workpiece on the first surface 13a of the resin film forming layer 13 with the peeling film 15 removed, and then the first surface 16a of the adhesive layer 16 for the jig is attached to the ring. Use the jig 18 for fixing a frame or the like.

Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a resin film according to this embodiment. In the resin film forming composite sheet 102 shown here, the shape and size of the resin film forming layer are different, and the adhesive for jigs is laminated on the first surface of the adhesive layer instead of the first surface of the resin film forming layer. Other than that, it is the same as the composite sheet 101 for resin film formation shown in FIG. 2 .

More specifically, in the composite sheet 102 for forming a resin film, the resin film forming layer 23 is laminated on a part of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12 (in FIG. The area on the central side of the left-right direction). Furthermore, on the first surface 12a of the adhesive layer 12, the adhesive layer 16 for the jig is laminated so as to surround the resin film forming layer 23 from the outside in the width direction in a non-contact manner in a region where the resin film forming layer 23 is not laminated. . In addition, on the side opposite to the side of the adhesive layer 12 of the resin film forming layer 23 (in this specification, sometimes referred to as "the first side") 23a, and the first side 16a of the adhesive layer 16 for jigs A release film 15 is laminated. The support sheet 10 is provided on the surface (in this specification, it may be called a "2nd surface") 23b on the opposite side to the 1st surface 23a of the resin film formation layer 23. As shown in FIG.

Fig. 4 is a cross-sectional view schematically showing still another example of the composite sheet for forming a resin film according to the present embodiment. The composite sheet 103 for resin film formation shown here is the same as the composite sheet 102 for resin film formation shown in FIG. 3 except the point which does not have the adhesive agent layer 16 for jigs.

Fig. 5 is a cross-sectional view schematically showing still another example of the composite sheet for forming a resin film according to the present embodiment. The composite sheet 104 for resin film formation shown here is the same as the composite sheet 101 for resin film formation shown in FIG. 2 except the point comprised with the support sheet 20 instead of the support sheet 10.

The supporting sheet 20 is only composed of the base material 11 . That is, the composite sheet 104 for resin film formation is comprised by laminating|stacking the base material 11 and the resin film formation layer 13 in the thickness direction of these. The surface (first surface) 20 a of the support sheet 20 on the side of the resin film forming layer 13 is the same as the first surface 11 a of the base material 11 . The substrate 11 has adhesiveness at least in the first surface 11a.

The composite sheet for forming a resin film in this embodiment is not limited to those shown in FIGS. 2 to 5 , and the composite sheet for forming a resin film shown in FIGS. Some configurations may be changed or deleted, or other configurations may be further added to the composite sheet for resin film formation described so far.

○Resin film forming layer The aforementioned resin film-forming layer is used by being attached to the inner surface of a workpiece in a method of manufacturing a wafer with a resin film. The resin film forming layer is preferably a protective film forming film for protecting the inner surface of a wafer obtained by dividing the workpiece or the workpiece.

By using the above-mentioned resin film-forming composite sheet or the above-mentioned set provided with the above-mentioned supporting sheet and the above-mentioned resin film forming layer, it is possible to manufacture a chip having a chip and an inner chip provided on the chip by the method of manufacturing a chip with a resin film described later. Wafer with resin film on the surface of the resin film.

When the aforementioned resin film-forming layer is a protective film-forming film, by using the aforementioned protective-film-forming composite sheet or the aforementioned set provided with the aforementioned support sheet and the aforementioned protective film-forming film, the wafer with the resin film described later can be formed. A manufacturing method for manufacturing a wafer with a protective film comprising a wafer and a protective film provided on the inner surface of the wafer.

Furthermore, by using the aforementioned wafer with a resin film, a substrate device can be manufactured. In this specification, the term "substrate device" refers to a device configured by flip-chip connection of a chip with a resin film on the protruding electrodes on the circuit surface of the chip to the connection pads on the circuit board. For example, when a semiconductor wafer is used as the wafer, a semiconductor device may be cited as the substrate device.

The aforementioned resin film forming layer is preferably thermosetting. The resin film-forming layer can be formed using a composition for forming a resin film. In particular, when the resin film-forming layer is a thermosetting protective film-forming film, the composition for forming a protective film described below can be used for the protective film-forming film. (III-1) and formed.

[Protective film forming composition (III-1)] Examples of the composition for forming a resin film include composition (III-1) for forming a protective film containing a polymer component (A) and a thermosetting component (B). Composition for film formation (III-1)") and the like.

[Polymer component (A)] The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to a thermosetting protective film-forming film. The polymer component (A) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, these The combination and ratio of the polymer component (A) can be selected arbitrarily.

A polymer component may also correspond to a hardening component. In this specification, when the protective film forming composition contains such components corresponding to both the polymer component and the curable component, it is considered that the protective film forming composition contains the polymer component and the curable component.

As the polymer component, acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like can be used. As the polymer component, an acrylic resin can be preferably used.

The weight average molecular weight (Mw) of the polymer component is preferably from 10,000 to 2 million, more preferably from 100,000 to 1.2 million. When the weight average molecular weight of a polymer component is more than the said lower limit, it exists in the tendency for the adhesiveness with respect to the support sheet 10 to fall easily, and the adhesiveness of a support sheet and a protective film can be reduced. The adhesiveness of a support sheet and a protective film forming film can be improved that the weight average molecular weight of a polymer component is below the said upper limit.

The glass transition temperature (Tg) of the polymer component is preferably in the range of -60°C to 50°C, more preferably in the range of -50°C to 40°C, particularly preferably in the range of -40 to 30°C. When the glass transition temperature of a polymer component is more than the said lower limit, the adhesiveness of a support sheet and a protective film can be reduced. When the glass transition temperature of the polymer component is below the above-mentioned upper limit, the adhesion between the support sheet and the protective film forming film can be improved, and the occurrence of cracks (cracks) when the protective film forming film is bent when it is formed into a roll body can be reduced. risk.

From the viewpoint of adhesiveness, adhesion and film-forming properties, the preferred content of the polymer component is 5 to 50 parts by mass, 10 to 45 parts by mass relative to 100 parts by mass of the total weight of the protective film forming film , 14 to 40 parts by mass, and 18 to 35 parts by mass.

The glass transition temperature (Tg) of the resin constituting the polymer component can be calculated using the Fox formula shown below. 1/Tg=(W1/Tg1)+(W2/Tg2)+...+(Wm/Tgm) (In the formula, Tg is the glass transition temperature of the resin that constitutes the polymer component, and Tg1, Tg2,...Tgm are the constituent polymers The glass transition temperature of the homopolymer of each monomer of the raw material of the resin, W1, W2, ... Wm is the mass fraction of each monomer. Among them, W1 + W2 + ... + Wm = 1). The glass transition temperature of the homopolymer of each monomer in the aforementioned Fox's formula can use the value described in Polymer Data-Handbook, Adhesive Handbook, or Polymer Handbook. For example, regarding the glass transition temperature of homopolymer, methyl acrylate is 10°C, methyl methacrylate is 105°C, n-butyl acrylate is -54°C, 2-ethylhexyl acrylate is -70°C, methyl Glycidyl acrylate is 41°C, and 2-hydroxyethyl acrylate is -15°C.

As a monomer which comprises the said acrylic resin, (meth)acrylate monomer or its derivative(s) are mentioned. For example, alkyl (meth)acrylates having an alkyl group having 1 to 18 carbon atoms, specifically methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate , Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. In addition, examples include (meth)acrylates having a cyclic skeleton, specifically cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, (meth) Dicyclopentyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imide (meth)acrylate, and the like. Furthermore, examples of functional group-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate having a hydroxyl group; Glycidyl (meth)acrylate having an epoxy group, etc. As for the acrylic resin, an acrylic polymer containing a structural unit having a hydroxyl group has good compatibility with a curable component described later, and is therefore preferable. Furthermore, the above-mentioned acrylic polymer may be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and the like.

[hardening ingredients] As the curable component, for example, a thermosetting component (B) can be used. Thereby, the protective film forming film can be made thermosetting.

By using a thermosetting protective film forming film, even if the protective film forming film is thickened, thermosetting can be easily performed, so that a protective film forming film having good protective performance can be thickened. In the heat hardening step, one-time hardening of multiple workpieces can be achieved.

As the thermosetting component, a thermosetting resin and a thermosetting agent can be used. As the thermosetting resin, for example, epoxy resin is preferable.

As the epoxy resin, previously known epoxy resins can be used. Specific examples of the epoxy resin include polyfunctional epoxy resins or biphenyl compounds, bisphenol A diglycidyl ether or hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. have more than two functional epoxy compounds in the molecule. These can be used alone or in combination of two or more.

The preferred content of the thermosetting component is preferably 1 to 75 parts by mass, more preferably 2 to 60 parts by mass, and still more preferably 3 to 50 parts by mass relative to 100 parts by mass of the total weight of the protective film forming film. Parts by mass may be, for example, 4 to 40 parts by mass, 5 to 35 parts by mass, or 6 to 30 parts by mass. If the content of the thermosetting resin is more than the above lower limit, the protective film can obtain sufficient adhesion with the workpiece, and the protective film can protect the workpiece excellently. If it is below the above upper limit, it can be stored in the form of a roll The storage stability is excellent.

The thermosetting agent functions as a curing agent for thermosetting resins, especially epoxy resins. As a preferable thermosetting agent, the compound which has two or more functional groups which can react with an epoxy group in one molecule is mentioned. As this functional group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride, etc. are mentioned. Among these, preferable examples include phenolic hydroxyl groups, amino groups, acid anhydrides, and the like, and more preferable examples include phenolic hydroxyl groups and amino groups.

Specific examples of the phenolic curing agent include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, Xyloc-type phenolic resins, and aralkylphenolic resins. As a specific example of the amine-based curing agent, DICY (Dicyandiamide; dicyandiamide) is mentioned. These may be used alone or in combination of two or more.

The content of the thermosetting agent is preferably from 0.1 to 500 parts by mass, more preferably from 1 to 200 parts by mass, relative to 100 parts by mass of the thermosetting resin. If the content of the thermosetting agent is more than the above lower limit, it will be sufficiently hardened to obtain adhesiveness, and if it is below the above upper limit, the moisture absorption rate of the protective film will be suppressed, and the adhesion reliability between the workpiece and the protective film will be improved.

The composition (III-1) for forming a protective film may contain an energy ray curable component. As the energy ray curable component, a low molecular weight compound (energy ray polymerizable compound) that contains an energy ray polymerizable group and is polymerized and hardened upon irradiation with energy rays such as ultraviolet rays and electron beams can be used. Specific examples of such energy ray-curing components include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, or 1,4- Butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy modified acrylate, Acrylate compounds such as polyether acrylate and itaconic acid oligomers. Such compounds have at least one polymerizable double bond in the molecule, and usually have a weight average molecular weight of 100 to 30,000, preferably about 300 to 10,000. The preferred content of the energy ray curable component is preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, based on 100 parts by mass of the total weight of the protective film forming film.

Furthermore, an energy ray-curable polymer in which energy ray-polymerizable groups are bonded to the main chain or side chain of the polymer component can also be used as the energy ray-curable component. Such an energy ray-curable polymer has both a function as a polymer component and a function as a curable component.

The main skeleton of the energy ray curable polymer is not particularly limited, and it may be an acrylic polymer commonly used as a polymer component, and may also be polyester, polyether, etc., in terms of ease of synthesis and control of physical properties , especially preferably acrylic polymer as the main skeleton.

The energy ray polymerizable group bonded to the main chain or side chain of the energy ray curable polymer is, for example, an energy ray polymerizable group containing a carbon-carbon double bond, specifically a (meth)acryl group and the like can be exemplified. The energy ray polymerizable group may also be bonded to the energy ray curable polymer via an alkylene group, an alkyleneoxy group, or a polyalkylene group.

The weight average molecular weight (Mw) of the energy ray curable polymer is preferably from 10,000 to 2 million, more preferably from 100,000 to 1.5 million. Moreover, the glass transition temperature (Tg) of the energy ray curable polymer is preferably in the range of -60°C to 50°C, more preferably in the range of -50°C to 40°C, and especially preferably in the range of -40°C to 30°C. ℃ range.

Energy ray-curable polymers are obtained, for example, by reacting acrylic resins containing functional groups such as hydroxyl groups, carboxyl groups, amino groups, substituted amino groups, and epoxy groups with polymerizable group-containing compounds. Each molecule has 1 to 5 substituents reactive with the functional group and energy ray polymerizable carbon-carbon double bonds. As a substituent which reacts with this functional group, an isocyanate group, a glycidyl group, a carboxyl group etc. are mentioned.

Examples of polymerizable group-containing compounds include: (meth)acryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryl isocyanate, alkene Propyl isocyanate, glycidyl (meth)acrylate; (meth)acrylic acid, etc.

The acrylic resin is preferably composed of (meth)acrylic monomers or their derivatives with functional groups such as hydroxyl, carboxyl, amino, substituted amino, and epoxy groups and other (meth)acrylic acid that can be copolymerized with it A copolymer composed of ester monomers or their derivatives.

Examples of (meth)acrylic monomers or derivatives thereof having functional groups such as hydroxyl groups, carboxyl groups, amino groups, substituted amino groups, and epoxy groups include 2-hydroxyethyl (meth)acrylates having hydroxyl groups. Esters, 2-hydroxypropyl (meth)acrylate; acrylic acid, methacrylic acid, and itaconic acid with carboxyl groups; glycidyl methacrylate and glycidyl acrylate with epoxy groups, etc.

Examples of other (meth)acrylate monomers or derivatives thereof that can be copolymerized with the above-mentioned monomers include: alkyl (meth)acrylates having an alkyl group having 1 to 18 carbon atoms, specifically, Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.; have a ring skeleton The (meth)acrylates specifically include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, acrylic acid Dicyclopentenyloxyethyl ester, imide acrylate, etc. Furthermore, vinyl acetate, acrylonitrile, styrene, etc. may be copolymerized with the said acrylic resin.

Even when an energy ray-curable polymer is used, the aforementioned energy ray polymerizable compound may be used in combination, and a polymer component may also be used in combination.

The protective film forming film may contain the following components in addition to the above-mentioned polymer component and curable component.

[Colorant] It is preferable that a protective film forming film contains a coloring agent. By mixing the coloring agent in the protective film forming film, it is possible to shield infrared rays and the like generated from surrounding devices when the semiconductor device is incorporated into equipment, and to prevent malfunction of the semiconductor device caused by these. In semiconductor devices or semiconductor wafers on which a protective film is formed, the product number and the like are usually printed on the surface of the protective film by a laser marking method, and the protective film can be sufficiently marked by laser light by containing a colorant in the protective film The contrast between the marked part and the unmarked part is poor, and the visibility is improved. As colorants, organic or inorganic pigments and dyes can be used. From the viewpoint of heat resistance and the like, a pigment is preferable. As the pigment, carbon black, iron oxide, manganese dioxide, nigrosine, activated carbon, etc. can be used, but not limited to these. Among them, carbon black is particularly preferable from the viewpoint of handleability and dispersibility. A coloring agent may be used individually by 1 type, and may use it in combination of 2 or more types.

The content of the coloring agent is preferably 0.05 to 35 parts by mass, more preferably 0.1 to 25 parts by mass, and most preferably 0.2 to 15 parts by mass relative to 100 parts by mass of the total solids constituting the protective film forming film share.

[hardening accelerator] The hardening accelerator is used to adjust the hardening speed of the protective film forming film. In particular, a curing accelerator can be preferably used when an epoxy resin and a thermosetting agent are used in combination for the thermosetting component (B).

As preferred hardening accelerators, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be enumerated; 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy Imidazoles such as methylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron such as tetraphenylphosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate salt etc. These may be used alone or in combination of two or more.

The curing accelerator is contained in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the curable component. By containing the hardening accelerator in the amount within the above range, it has excellent adhesive properties even when exposed to high temperature and high humidity, and high adhesive reliability can be achieved even when exposed to severe reflow conditions.

[Coupling agent] The coupling agent can also be used to improve the adhesion reliability of the protective film to the workpiece. Furthermore, by using a coupling agent, the water resistance of the protective film can be improved without impairing the heat resistance of the protective film obtained by curing the protective film forming film.

As the coupling agent, a compound having a group reactive with a functional group contained in a polymer component, a curable component, or the like can be preferably used. As the coupling agent, a silane coupling agent is preferable. Examples of such coupling agents include: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-amino Propyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetyloxysilane, imidazole silane, etc. These may be used alone or in combination of two or more.

With respect to the total of 100 parts by mass of the polymer component and the curable component, it is usually contained in a ratio of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass. mixture. If the content of the coupling agent is less than 0.1 parts by mass, the above effects may not be obtained, and if it exceeds 20 parts by mass, it may cause outgassing.

[Filler] The thermal expansion coefficient of the cured protective film can be adjusted by mixing the filler in the protective film forming film, and the thermal expansion coefficient of the cured protective film can be optimized with respect to the semiconductor wafer, and the workpiece and the protective film can be improved. Then reliability. As a filler, an inorganic filler is preferable. Moreover, the moisture absorption rate of the cured protective film can also be reduced.

Examples of preferable inorganic fillers include: powders of silicon dioxide, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheroidizing these; single crystal fiber and glass fiber etc. Among these, silica fillers and alumina fillers are preferable. These inorganic fillers may be used alone or in combination of two or more. The content of the inorganic filler may be 1 to 85 parts by mass, 5 to 80 parts by mass, or 10 parts by mass relative to 100 parts by mass of the total solids constituting the protective film forming film. Parts to 75 parts by mass, may also be set to 20 parts by mass to 70 parts by mass, or may be set to 30 parts by mass to 66 parts by mass. By setting the content of the inorganic filler below the above-mentioned upper limit, the risk of cracks (cracks) occurring when the protective film-forming film is deflected by forming a roll body can be reduced, and by setting it above the above-mentioned lower limit, And can improve the heat resistance of the protective film.

[Photopolymerization Initiator] When the protective film-forming film contains an energy ray-curable component, when the protective film is used to form a film, energy rays such as ultraviolet rays are irradiated to cure the energy ray-curable component. At this time, by including a photopolymerization initiator in the composition, it is possible to reduce the polymerization hardening time and the amount of light exposure.

Specific examples of such photopolymerization initiators include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin methyl benzoate. , benzoin dimethyl ketal, 2,4-diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyl Nitrile, benzoyl, dibenzoyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone , 2,4,6-trimethylbenzoyldiphenylphosphine oxide and β-chloroanthraquinone, etc. A photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types.

The compounding ratio of the photopolymerization initiator is preferably 0.1 to 10 parts by mass of the photopolymerization initiator, more preferably 1 to 5 parts by mass, with respect to 100 parts by mass of the energy ray curable component. The photopolymerization initiator. If it is more than the above lower limit, photopolymerization can be carried out to obtain satisfactory protective performance, and if it is below the above upper limit, the generation of residues that do not contribute to photopolymerization can be suppressed and the protective film can be formed into a film. Fully hardened.

[Crosslinking agent] In order to adjust the adhesion and cohesion of the protective film forming film relative to the workpiece, a crosslinking agent can also be added. As a crosslinking agent, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, etc. are mentioned.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polypolyisocyanate compounds, trimers of these organic polyisocyanate compounds, and combinations of these organic polyisocyanate compounds and polyol compounds. The terminal isocyanate urethane prepolymer obtained by reaction, etc.

Examples of organic polyvalent isocyanate compounds include: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4 ,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane- 4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethylolpropane adducted toluene diisocyanate and lysine isocyanate.

Examples of the above-mentioned organic polyimine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine Pyridyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate and N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene Melamine etc.

The amount of the crosslinking agent is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 parts by mass relative to 100 parts by mass of the total amount of the polymer component and the energy ray-curable polymer. Use at a ratio of up to 5 parts by mass.

[General Additives] In addition to the above-mentioned components, various additives may be mix|blended as needed in a protective film forming film. Examples of various additives include thickeners, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, getters, chain transfer agents, and the like.

[solvent] The protective film forming composition preferably further contains a solvent. The protective film-forming composition containing a solvent has better workability. The aforementioned solvents are not particularly limited, and as preferred solvents, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1- Alcohols such as butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) Wait. The solvent contained in the protective film forming composition may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio of these solvents can be selected arbitrarily.

The solvent contained in the protective film forming composition is preferably methyl ethyl ketone or the like at the point that the components contained in the composition can be more uniformly mixed.

The protective film-forming film obtained by applying the protective film-forming composition composed of the above-mentioned components and drying it has adhesiveness and curability, and is pressure-bonded to the workpiece in an uncured state. At the time of crimping, the protective film forming film may be heated. It can then be hardened to form a protective film with high impact resistance, excellent adhesiveness, and can maintain sufficient protection function under severe high temperature and high humidity conditions. In addition, the film for forming a protective film may have a single-layer structure, and may also have a multi-layer structure as long as it includes one or more layers containing the above-mentioned components.

The thickness of the protective film forming film is not particularly limited, and may be 3 μm to 300 μm, 3 μm to 200 μm, 5 μm to 100 μm, 7 μm to 80 μm, or 10 μm to 70 μm , can also be set to 12 μm to 60 μm, can also be set to 15 μm to 50 μm, can also be set to 18 μm to 40 μm, and can also be set to 20 μm to 30 μm. When the thickness of the protective film formation film is more than the said lower limit, the protective performance of a protective film can be made sufficient, and when it is below the said upper limit, cost can be reduced.

○Method for producing resin film-forming composition The composition for resin film formation, such as the composition for protective film formation (III-1), is obtained by preparing each component which comprises this composition. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. In the case of using a solvent, it may be used by mixing the solvent with any formulation component other than the solvent and then diluting the formulation component beforehand, or by diluting any formulation component other than the solvent in advance. These preparation components are mixed and used. The method of mixing the ingredients during preparation is not particularly limited, as long as it is appropriately selected from known methods such as the following methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; A method of mixing sound waves. The temperature and time during the addition and mixing of each component can be adjusted appropriately considering the conditions that the components are not easy to deteriorate. The temperature is preferably 15°C to 30°C.

◇Manufacturing method of composite sheet for resin film formation The above-mentioned composite sheet for forming a resin film can be produced by laminating the above-mentioned layers in a corresponding positional relationship, and adjusting the shape of some or all of the layers as necessary. The formation method of each layer is as described above.

The resin film-forming composition can be further coated on the adhesive layer that has been laminated on the base material to directly form the resin film-forming layer. In this way, a new layer (hereinafter referred to as "second layer") is formed on any layer that has been laminated on the substrate (hereinafter referred to as "first layer") to form a continuous two-layer laminated structure (in other words, In the case of the laminated structure of the first layer and the second layer), the following method can be applied: the composition for forming the second layer is applied on the first layer, and dried as necessary. However, the second layer is preferably formed in advance on the release film using a composition for forming the second layer, and the side opposite to the side contacting the release film in the formed second layer is exposed. The surface is attached to the exposed surface of the first layer, thereby forming a laminated structure of two consecutive layers. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. What is necessary is just to remove a peeling film as needed after forming a laminated structure. Here, the case where a resin film-forming layer is laminated on an adhesive layer is exemplified, but for example, when a layer (film) other than a resin film-forming layer is laminated on an adhesive layer, the target laminated structure can be selected arbitrarily. .

In this way, the layers other than the base material constituting the composite sheet for forming a resin film can be laminated by forming in advance on the release film and sticking to the surface of the target layer. What is necessary is just to manufacture the composite sheet for resin film formation.

In addition, the composite sheet for resin film formation is normally stored with the peeling film attached to the surface of the outermost layer (for example, resin film formation layer) of the composite sheet for resin film formation on the side opposite to a support sheet. Therefore, a resin film-forming composition is applied on the release film (preferably, the release-treated surface of the release film) and dried if necessary, thereby forming a resin film-forming layer on the release film in advance, and forming a resin film on the release film. On the exposed surface of the layer opposite to the side that is in contact with the release film, the remaining layers are laminated by any of the above methods, and the release film is not removed and kept in a bonded state, thereby obtaining a resin film with a release film. Use composite sheets.

When the said resin film forming layer is a protective film forming film, the said composite sheet for protective film formation provided with the said support sheet and the said protective film forming film can be obtained.

The aforementioned composite sheet for forming a resin film may be in the form of a single sheet, preferably in the form of a roll.

[kit] The kit according to the embodiment of the present invention is provided with: a first laminate formed by sequentially laminating a first release film, a resin film forming layer, and a second release film; The workpiece to which the layer is attached and the aforementioned resin film form a layer. Hereinafter, an example of the kit 1 of this embodiment will be described with reference to the drawings.

Fig. 6 is a cross-sectional view schematically showing an example of the kit 1 of this embodiment. The set 1 of this embodiment is provided with: a first laminated body 5, which is sequentially laminated by a first release film 151, a resin film forming layer 13, and a second release film 152; The work to which the film-forming layer 13 is attached, the resin film-forming layer 13, and the support sheet 10 are the above-mentioned support sheets in the embodiment of the present invention.

The resin film-forming layer 13 shown here has a first release film 151 on one side (in this specification, sometimes referred to as "first side") 13a, and on the other side opposite to the first side 13a ( In this specification, it may be referred to as "the second surface") 13b is equipped with the second release film 152 .

When the aforementioned resin film forming layer is a protective film forming film, by using the kit 1 provided with the aforementioned support sheet 10 and the aforementioned protective film forming film, a wafer having a wafer and A wafer with a protective film provided on the protective film on the inner surface of the aforementioned wafer.

Such a resin film forming layer 13 is preferably stored in a roll form, for example. That is, the aforementioned first laminate is preferably in the shape of a roll.

The resin film forming layer 13 can be formed using the composition for resin film formation mentioned above.

Both the first release film 151 and the second release film 152 can be known release films. The 1st peeling film 151 and the 2nd peeling film 152 may mutually be the same, for example, the peeling force required when peeling from the resin film formation layer 13 may differ from each other, etc. and may be mutually different.

In the resin film forming layer 13 shown in FIG. 6 , either one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the sticking surface to the inner surface of the workpiece (not shown). In addition, the remaining one of the first release film 151 and the second release film 152 is removed, and the resulting exposed surface becomes the sticking surface of the support sheet.

6 shows an example in which the release film is provided on both sides (first surface 13a, second surface 13b) of the resin film forming layer 13, but the release film may also be provided only on either side of the resin film forming layer 13, that is, only on the The first surface 13a is only provided on the second surface 13b.

The kit 1 of the present embodiment uses the resin film forming layer 13 and the support sheet 10 together, so that the attachment of the resin film forming layer to the workpiece and the subsequent attachment of the support sheet can be carried out in an in-line process. Here, the so-called "in-line process" refers to "a process performed in a device formed by connecting multiple (multiple) devices that will perform one or more steps, or in the same device, including multiple steps and will The step-by-step transfer is the process of transferring workpieces one by one between one step and the subsequent step.

[Manufacturing method of wafer with resin film] The support sheet according to the embodiment of the present invention described above, the composite sheet for forming a resin film provided with the support sheet, and the set 1 provided with the support sheet can be used in a method of manufacturing a wafer with a resin film comprising a wafer, And the resin film provided on the inner surface of the aforementioned wafer.

[manufacturing method 1] The manufacturing method of the first embodiment is a method of manufacturing a wafer with a resin film, wherein the wafer with a resin film includes a wafer and a resin film provided on the inner surface of the wafer; and the manufacturing of the wafer with a resin film The method has the following steps: affixing the resin film forming layer in the resin film forming composite sheet according to the embodiment of the present invention to the inner surface of the workpiece, thereby manufacturing the resin film forming layer and the workpiece on the supporting sheet. The step of laminating the first laminated composite sheet sequentially in the thickness direction of these sheets; heating the first laminated composite sheet in a state where the peripheral portion of the first laminated composite sheet is attached to the jig for fixing, so that the The resin film forming layer is hardened to form the aforementioned resin film, thereby manufacturing a second laminated composite sheet formed by laminating the aforementioned resin film and the aforementioned workpiece sequentially in the thickness direction on the aforementioned support sheet; forming the aforementioned second laminated composite sheet After cooling, the aforementioned workpiece in the aforementioned second laminated composite sheet is divided on the aforementioned supporting sheet, and the aforementioned resin film is cut off, thereby making a third laminated composite sheet in which a plurality of wafers with resin films are fixed on the aforementioned supporting sheet. steps; and, a step of tearing the aforementioned wafer with the resin film in the aforementioned third laminated composite sheet from the aforementioned support sheet, thereby picking up the aforementioned wafer with the resin film. Hereinafter, in this specification, the manufacturing method of 1st Embodiment may be called "manufacturing method 1."

7A to 7E are cross-sectional views for schematically illustrating the manufacturing method 1 . Here, the case where the composite sheet 101 for resin film formation of FIG. 2 provided with the support sheet 10 shown in FIG. 1 is used is taken as an example, and manufacturing method 1 is demonstrated.

In the step of producing the aforementioned first laminated composite sheet in the manufacturing method 1, as shown in FIG. On the supporting sheet 10, the resin film formation layer 13 and the workpiece|work 9 are laminated|stacked sequentially in the thickness direction of these and the 1st laminated composite sheet 501 which consists. The 1st surface 13a of the resin film formation layer 13 in the composite sheet 101 for resin film formation is stuck to the inner surface 9b of the work 9.

The resin film forming layer 13 in the resin film forming composite sheet 101 can be attached to the work 9 by a known method. For example, the resin film forming layer 13 may be attached to the workpiece 9 while heating.

Next, in the step of producing the aforementioned second laminated composite sheet in Manufacturing Method 1, the peripheral portion of the first laminated composite sheet 501 is attached to a fixing jig 18 such as a ring frame through the adhesive layer 16 for the jig. The first laminated composite sheet 501 is heated (FIG. 7B). In this way, the resin film forming layer 13 is hardened to form a resin film 13', and as shown in FIG. Two laminated composite sheet 502.

Reference numeral 13a' denotes a surface (in this specification, sometimes referred to as "the first surface") that is the first surface 13a of the resin film forming layer 13 in the resin film 13'. Reference numeral 13b' denotes a surface (in this specification, sometimes referred to as "the second surface") that is the second surface 13b of the resin film forming layer 13 in the resin film 13'.

The curing of the resin film forming layer 13 can be cured by heating the resin film forming layer 13 if the resin film forming layer 13 is thermosetting.

In the case where the resin film-forming layer 13 is a protective film-forming film, laser marking can be performed by irradiating the resin film-forming layer 13 shown in FIG. Laser marking can also be performed by irradiating the resin film 13' shown in FIG. 7C through the support sheet 10 (penetrating the support sheet 10).

Then, in the step of making the aforementioned third laminated composite sheet in Manufacturing Method 1, the second laminated composite sheet 502 is cooled, and then, as shown in FIG. 7D , the workpiece 9 in the second laminated composite sheet 502 is It is divided and the resin film 13' is cut. The workpiece 9 is divided into individual pieces to form a plurality of wafers 90 .

The division of the workpiece 9 and the cutting of the resin film 13' may be performed by known methods. For example, the division of the workpiece 9 and the separation of the resin film 13' can be continuously performed by blade cutting, laser cutting by laser irradiation, or water cutting by spraying water containing abrasives. cut off. The resin film 13' is cut along the outer periphery of the wafer 90 regardless of the cutting method.

In this way, by dividing the workpiece 9 and cutting the resin film 13', a cut resin film including the wafer 90 and the inner surface 90b of the wafer 90 (in this specification, sometimes simply referred to as "resin film") is obtained. 130' a plurality of wafers 901 with resin film. Reference numeral 130b' denotes a surface (in this specification, sometimes referred to as "the second surface") that is the second surface 13b' of the resin film 13' in the cut resin film 130'.

In the step of manufacturing the aforementioned third laminated composite sheet in Manufacturing Method 1, the third laminated composite sheet 503 in which the plurality of chips 901 with resin films are fixed on the support sheet 10 is manufactured through the above operations.

Then, in the aforementioned picking-up step of manufacturing method 1, as shown in FIG. 7E , the wafer 901 with the resin film in the third laminated composite sheet 503 is torn off from the supporting sheet 10, thereby picking up the wafer with the resin film 901.

Manufacturing method 1 according to the embodiment of the present invention, since the support sheet 10 has the above-mentioned structure, even if the peripheral portion of the first laminated composite sheet 501 is attached to the fixing jig and heated, and then the second laminated composite sheet 502 is cooled, Also, the influence of the slack of the third laminated composite sheet 503 can be eliminated, and the visibility of the chip of the pick-up device can be improved.

In the aforementioned pick-up step, peeling occurs between the second surface 130b' of the resin film 130' in the wafer with resin film 901 and the first surface 12a of the adhesive layer 12 in the support sheet 10.

Here, a state in which the wafer 901 with the resin film is pulled off in the direction of the arrow P is shown using a pull-off mechanism 7 such as a vacuum collet. Furthermore, the sectional representation of the tear-off mechanism 7 is omitted here. The wafer 901 with the resin film can be picked up by a known method.

In the case where the adhesive layer 12 is energy ray curable, the adhesive layer 12 may be cured to form a hardened product (not shown) by irradiating the adhesive layer 12 with energy rays in the aforementioned picking-up step. , the wafer 901 with the resin film is pulled off from the supporting sheet 10 . In this case, peeling occurs between the resin film 130' in the wafer with resin film 901 and the cured product of the adhesive layer 12 in the support sheet 10 in the aforementioned pick-up step. In this case, the adhesive force between the cured product of the adhesive layer 12 and the resin film 130' is smaller than the adhesive force between the cured product of the adhesive layer 12 and the substrate 11, so the wafer with the resin film can be easily picked up. 901.

In this specification, even after energy ray curing of the energy ray-curable adhesive layer, as long as the laminated structure of the base material and the cured product of the energy ray-curable adhesive layer is maintained, the laminated structure is referred to as " support sheet".

On the other hand, when the adhesive layer 12 is non-energy ray curable, the wafer 901 with the resin film can be directly pulled off from the adhesive layer 12 without hardening the adhesive layer 12. The wafer with resin film 901 is picked up in simplified steps.

In the aforementioned pick-up step, the pick-up of the wafers 901 with the resin film is carried out for all the wafers 901 with the resin film that are targeted.

In Manufacturing Method 1, by proceeding up to the aforementioned pick-up step, the target wafer 901 with a resin film can be obtained.

In the description of the production method 1 so far, the production method 1 in the case of using the resin film forming composite sheet 101 provided with the support sheet 10 shown in FIG. The resin film forming composite sheet of this embodiment other than the resin film forming composite sheet 101 such as the resin film forming composite sheet 102, the resin film forming composite sheet 103, or the resin film forming composite sheet 104 shown in FIG. 3 to FIG. .

[manufacturing method 2] The manufacturing method of the second embodiment is a method of manufacturing a wafer with a resin film, wherein the wafer with a resin film includes a wafer and a resin film provided on the inner surface of the wafer; and the manufacturing of the wafer with a resin film The method has the following steps: affix the resin film forming layer in the kit 1 of the embodiment of the present invention above to the inner surface of the workpiece, and manufacture the first resin film forming layer and the workpiece formed by laminating the above resin film forming layer and the workpiece in the thickness direction thereof. laminated film, and then attach the adhesive layer of the support sheet in the aforementioned kit 1 to the aforementioned resin film forming layer in the aforementioned first laminated film, thereby making the aforementioned resin film forming layer and the aforementioned workpiece sequentially on the aforementioned supporting sheet The step of forming the first laminated composite sheet formed by laminating these layers in the thickness direction: heating the first laminated composite sheet in a state where the peripheral portion of the first laminated composite sheet is attached to a fixing jig to form the resin film layer hardening to form the aforementioned resin film, thereby fabricating a second laminated composite sheet formed by laminating the aforementioned resin film and the aforementioned workpiece sequentially in the thickness direction on the aforementioned support sheet; cooling the aforementioned second laminated composite sheet, and then A step of dividing the aforementioned workpiece in the aforementioned second laminated composite sheet on the aforementioned supporting sheet, cutting the aforementioned resin film, thereby manufacturing a third laminated composite sheet having a plurality of wafers with resin films fixed on the aforementioned supporting sheet; and , a step of tearing off the aforementioned wafer with the resin film in the aforementioned third laminated composite sheet from the aforementioned support sheet, thereby picking up the aforementioned wafer with the resin film. Hereinafter, in this specification, the production method of the second embodiment may be referred to as "production method 2".

8 and 7A to 7E are cross-sectional views schematically illustrating the manufacturing method 2 . Here, the manufacturing method 2 will be described by taking, as an example, the case of using the kit 1 of FIG. 6 provided with the supporting sheet 10 shown in FIG. 1 .

In the step of manufacturing the aforementioned first laminated composite sheet in the manufacturing method 2, first, the resin film forming layer 13 in the aforementioned kit 1 is pasted on the inner surface 9b of the workpiece 9, thereby as shown in FIG. The layer 13 and the workpiece 9 are laminated in the thickness direction of these first laminated films 601 . Also in this case, the first surface 13 a of the resin film forming layer 13 in the first laminate 5 is attached to the inner surface 9 b of the workpiece 9 in the same manner as in the case of the manufacturing method 1 .

Here, the case where the first release film 151 is removed from the first laminated body 5 of the kit 1 shown in FIG. The second peeling film 152 can be removed from the resin film forming layer 13 of the kit 1 shown in FIG. It is also possible to abut a circular stamping knife against the first laminated body 5 of the kit 1 shown in FIG. The outer side is removed together with the first peeling film 151 , and the first surface 13 a of the obtained circular resin film forming layer 13 is attached to the inner surface 9 b of the workpiece 9 .

The attachment of the resin film forming layer 13 to the workpiece 9 can be performed by a known method. For example, the resin film forming layer 13 may be attached to the workpiece 9 while heating.

Then, the adhesive layer 12 of the support sheet 10 in the kit 1 is attached to the resin film forming layer 13 in the first laminated film 601, thereby making the resin film forming layer 13 and the workpiece 9 on the support sheet 10 in sequence. The first laminated composite sheet 501 formed by laminating these in the thickness direction.

The second release film 152 is removed from the resin film forming layer 13 in the first laminate film 601 . Next, on the second surface 13b of the resin film formation layer 13 newly exposed by this, as shown in FIG. 7A, the one surface 10a of the support sheet 10 is attached. The adhesive layer 16 for the jig can also be provided thereafter. The support sheet 10 shown here is composed of a base material 11 and an adhesive layer 12 provided on one side 11a of the base material 11, and the adhesive layer 12 in the support sheet 10 is attached to the resin film forming layer 13. . The first surface 12 a of the resin film forming layer 13 side of the adhesive layer 12 is the same as the first surface 10 a of the support sheet 10 .

In manufacturing method 2, the first laminated composite sheet 501 is the same as the first laminated composite sheet 501 in manufacturing method 1.

In the production method 2, the step of producing the second laminated composite sheet can be performed by the same method as in the case of the step of producing the second laminated composite sheet in the production method 1.

In Manufacturing Method 2, the step of producing the aforementioned third laminated composite sheet can be performed by the same method as in the case of the step of manufacturing the third laminated composite sheet in Manufacturing Method 1.

In manufacturing method 2, the aforementioned picking-up step can be performed by the same method as the aforementioned picking-up step of manufacturing method 1.

In the manufacturing method 2 of the embodiment of the present invention, since the supporting sheet 10 has the above-mentioned structure, even if the peripheral portion of the first laminated composite sheet 501 is attached to the fixing jig and heated, the second laminated composite sheet 501 is then heated. The cooling of the composite sheet 502 can also eliminate the influence of the relaxation of the third laminated composite sheet 503 and improve the recognition of the chip in the pick-up device.

[manufacturing method 3] The manufacturing method of the third embodiment is a manufacturing method of a wafer with a resin film, wherein the wafer with a resin film includes a wafer and a resin film provided on the inner surface of the wafer; and the manufacturing of the wafer with a resin film The method has the following steps: affixing the resin film forming layer of the resin film forming composite sheet according to the embodiment of the present invention to the inner surface of the workpiece, or affixing the kit according to the embodiment of the present invention to the inner surface of the workpiece. For the resin film forming layer in 1, a first laminated film formed by laminating the resin film forming layer and the workpiece in the thickness direction thereof is produced, and the kit 1 is attached to the resin film forming layer in the first laminated film The adhesive layer of the support sheet in the above-mentioned support sheet is made by making the first laminated composite sheet formed by laminating the aforementioned resin film forming layer and the aforementioned workpiece sequentially in the thickness direction of the aforementioned support sheet; on the aforementioned support sheet, The step of dividing the aforementioned workpiece in the aforementioned first laminated composite sheet, cutting the aforementioned resin film forming layer, thereby manufacturing a fourth laminated composite sheet in which a plurality of wafers having resin film forming layers are fixed on the aforementioned supporting sheet; The peripheral portion of the fourth laminated composite sheet is attached to the jig for fixing, and the fourth laminated composite sheet is heated and cooled to harden the resin film forming layer in the fourth laminated composite sheet to form the resin film, A step of manufacturing a third laminated composite sheet in which a plurality of chips with resin films are fixed on the aforementioned support sheet; and, tearing the aforementioned wafers with resin films in the third laminated composite sheet from the aforementioned support sheet, thereby The step of picking up the aforementioned wafer with resin film. Hereinafter, in this specification, the production method of the third embodiment may be referred to as "production method 3".

9A to 9C and 7D to 7E are cross-sectional views for schematically illustrating the manufacturing method 3 . Here, the manufacturing method 3 is demonstrated using the case where the composite sheet 101 for resin film formation of FIG. 2 provided with the support sheet 10 shown in FIG. 1 is used as an example.

In the step of producing the aforementioned first laminated composite sheet in the manufacturing method 3, as shown in FIG. On the supporting sheet 10, the resin film formation layer 13 and the workpiece|work 9 are laminated|stacked sequentially in the thickness direction of these and the 1st laminated composite sheet 501 which consists. The first laminated composite sheet 501 in FIG. 9A is the same as the first laminated composite sheet 501 in FIG. 7A.

Next, in the step of producing the aforementioned fourth laminated composite sheet in Manufacturing Method 3, as shown in FIG. . The workpiece 9 is divided into individual pieces to form a plurality of wafers 90 .

The division of the workpiece 9 and the cutting of the resin film forming layer 13 may be performed by known methods. For example, division of the workpiece 9 and cutting of the resin film formation layer 13 are performed by blade cutting, laser cutting using laser irradiation, or water cutting by spraying water containing abrasives, and the like, and The cutting of the resin film forming layer 13 is carried out along the outer periphery of the wafer 90 regardless of the cutting method.

In this way, by dividing the workpiece 9 and cutting the resin film forming layer 13, the cut resin film forming layer (in this specification, sometimes simply referred to as "resin film forming layer" provided on the wafer 90 and the inner surface 90b of the wafer 90) is obtained. A plurality of wafers 902 having a resin film forming layer) 130. Reference numeral 130b represents a surface (in this specification, sometimes referred to as "the second surface") that is the second surface 13b of the resin film forming layer 13 in the resin film forming layer 130 after cutting.

In the step of producing the fourth laminated composite sheet in the manufacturing method 3, the fourth laminated composite sheet 504 in which the plurality of chips 902 having resin film forming layers are fixed on the support sheet 10 is produced through the above operations.

Next, in the step of manufacturing the aforementioned third laminated composite sheet in Manufacturing Method 3, as shown in FIG. The four-laminated composite sheet 504 is heated and cooled, and as shown in FIG. 7D , the resin film forming layer 130 in the fourth laminated composite sheet 504 is cured to form the aforementioned resin film 130 ′.

In manufacturing method 3, the third laminated composite sheet 503 is the same as the third laminated composite sheet 503 in manufacturing method 1.

In manufacturing method 3, the aforementioned picking-up step can be performed by the same method as the aforementioned picking-up step of manufacturing method 1.

In the manufacturing method 3 of the embodiment of the present invention, since the supporting sheet 10 has the above-mentioned structure, even if the peripheral edge of the fourth laminated composite sheet 504 is attached to the fixing jig 18 such as a ring frame, it is heated, and then the The cooling of the third laminated composite sheet 503 can also eliminate the influence of the relaxation of the third laminated composite sheet 503, and improve the recognition of the chip of the pick-up device.

In the description of the manufacturing method 3 so far, the manufacturing method 3 in the case of using the resin film forming composite sheet 101 provided with the support sheet 10 shown in FIG. The resin film forming composite sheet of this embodiment other than the resin film forming composite sheet 101 such as the resin film forming composite sheet 102, the resin film forming composite sheet 103, or the resin film forming composite sheet 104 shown in FIG. 3 to FIG. .

It is also possible to use the kit 1 shown in FIG. 6 in the step of making the aforementioned first laminated composite sheet in the manufacturing method 3, and attach the resin film forming layer 13 in the aforementioned kit 1 to the inner surface 9b of the workpiece 9, thereby As shown in FIG. 8 , the first laminated film 601 formed by laminating the resin film forming layer 13 and the workpiece 9 in the thickness direction thereof is produced, and further, the resin film forming layer 13 in the first laminated film 601 is attached to the kit 1 Adhesive layer 12 of the support sheet 10, thereby making the first laminated composite sheet 501.

◇Manufacturing method of substrate device (method of using wafer with resin film) After obtaining a wafer with a resin film by the above-mentioned manufacturing method, the wafer with a resin film is used instead of the previous wafer with a resin film, except for this aspect, the substrate can be manufactured by the same method as the manufacturing method of the previous substrate device device.

For example, when the aforementioned resin film-forming layer is a protective film-forming film, and the wafer with the resin film is a wafer with a protective film, a manufacturing method having the following step of flip-chip connection is enumerated: The resulting chip with protective film is picked up from the supporting sheet, so that the protruding electrodes on the chip with resin film contact the connection pads on the circuit substrate, thereby electrically connecting the protruding electrodes and the connection pads on the circuit substrate. connect.

In the case where the aforementioned resin film forming layer is a film-like adhesive and the wafer with the resin film is a wafer with a film-like adhesive, a manufacturing method including the following steps of connecting: The wafer with the resin film forming layer is picked up from the supporting sheet, and the obtained wafer with the resin film is bonded on the circuit board through the aforementioned film-like adhesive. [Example]

Hereinafter, the present invention will be described in more detail by specific examples. However, this invention is not limited at all by the Example shown below.

[Example 1] In Example 1, the support sheet 10 shown in FIG. 1 and the composite sheet 101 for resin film formation shown in FIG. 2 whose resin film formation layer is a protective film formation film were manufactured as follows.

(1) Fabrication of the first laminate including the protective film forming film The following components (a) to (g) were mixed, diluted with methyl ethyl ketone so that the solid content concentration became 50% by mass, and a composition for forming a protective film was prepared.

(a) Polymer composition: (meth)acrylate copolymer (10 mass parts of n-butyl acrylate, 70 mass parts of methyl acrylate, 5 mass parts of glycidyl methacrylate and 15 mass parts of 2-hydroxyethyl acrylate 120 parts by mass (in terms of solid content, the same below) (b-1) Thermosetting component: 60 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent 184g/eq to 194g/eq) (b-2) Thermosetting component: 10 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent 800g/eq to 900g/eq) (b-3) Thermosetting component: dicyclopentadiene type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., product name "Epiclone HP-7200HH", epoxy equivalent 255g/eq to 260g/eq) 30 parts by mass (c) Thermally active latent epoxy resin hardener: 3 parts by mass of dicyandiamide (manufactured by ADEKA Co., Ltd., Adeka Hardener EH3636AS, active hydrogen content 21g/eq) (d) Hardening accelerator: 3 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "Curezole 2PHZ") (e) Filler: Silica filler (manufactured by Admatechs Co., Ltd., product name "SC2050MA", average particle size: 0.5 μm) 290 parts by mass (f) Colorant: 1.2 parts by mass of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., product name "#MA650", average particle diameter: 28 nm) (g) Silane coupling agent: (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") 2 parts by mass

The first release film (manufactured by Lintec Co., Ltd., manufactured by Lintec Co., Ltd.) was prepared by forming a polysiloxane-based release agent layer on one side of a polyethylene terephthalate (PET) film with a thickness of 38 μm. name "SP-PET381031"), and a second release film (manufactured by Lintec Co., Ltd., product name " SP-PET381130").

First, the protective film-forming composition was coated on the peeling surface of the first peeling film with a knife coater, and dried to form a protective film-forming film with a thickness of 25 μm. Then, the peeling surface of the 2nd peeling film was laminated|stacked on the protective film forming film, and both were bonded, and the laminated body which consists of a 1st peeling film, a protective film forming film (thickness: 25 micrometers), and a 2nd peeling film was obtained. The laminated body is a long strip, which is rolled up to form a roll-shaped rolled-up body.

(2) Fabrication of the second laminate including the support sheet The following components (h) and (i) were mixed, and diluted with methyl ethyl ketone so that the solid content concentration became 25 mass %, and the adhesive agent composition was prepared.

(h) Adhesive main agent: (meth)acrylate copolymer (obtained by copolymerizing 60 parts by mass of 2-ethylhexyl acrylate, 30 parts by mass of methyl methacrylate and 10 parts by mass of 2-hydroxyethyl acrylate Copolymer, weight average molecular weight: 600,000) 100 parts by mass (i) Crosslinking agent: xylene diisocyanate adduct of trimethylolpropane (manufactured by Mitsui Takeda Chemical Co., Ltd., product name "Takenate D110N") 20 parts by mass

As a release film, a release film (manufactured by Lintec Co., Ltd., product name "SP-PET381031") in which a silicone-based release agent layer was formed on one side of a PET film with a thickness of 38 μm was prepared.

As the material for the base material of the support sheet, prepare a polypropylene film 1 (thickness) with a no-load stretch rate of 99% in the MD direction/99% in the CD direction, a tensile modulus of 370 MPa in the MD direction/350 MPa in the CD direction, and a melting point of 138°C. : 80 μm). The aforementioned polypropylene film 1 was stretched only in the MD direction at a temperature of 120° C. for 1 minute and a tension of 2 N/m to produce a base material. In addition, the measuring methods of the no-load expansion rate, tensile elastic modulus, and melting point are as shown in the test example mentioned later (it is the same below).

First, the aforementioned adhesive composition was coated on the peeling surface of the release film with a knife coater, and dried at 100° C. for 1 minute to form an adhesive layer with a thickness of 5 μm. Then, the base material was pasted on the adhesive layer to obtain a second laminate composed of the support sheet and the release film of Example 1. The support sheet of Example 1 was composed of the base material and the adhesive layer. This laminate is a long strip. Then, the laminated body is wound up to form a roll-shaped wound body.

(3) Fabrication of the third laminate including the adhesive layer 16 for jigs The following components (j) and (k) were mixed, diluted with toluene so that the solid content concentration became 15 mass %, and the adhesive composition for jigs was prepared.

(j) Adhesive main agent: (meth)acrylate copolymer (a copolymer obtained by copolymerizing 69.5 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate, and 0.5 parts by mass of 2-hydroxyethyl acrylate, weight average Molecular weight: 500,000) 100 parts by mass (k) Cross-linking agent: 5 parts by mass of toluene diisocyanate-based cross-linking agent (manufactured by Tosoh Co., Ltd., Coronate L)

Prepare the first release film and the second release film (manufactured by Lintec Co., Ltd., product name "SP-PET381031") formed by forming a polysiloxane-based release agent layer on one side of a PET film with a thickness of 38 μm. ”), and a polyvinyl chloride film (manufactured by Okamoto Co., Ltd., thickness: 50 μm) as a core material.

First, the above-mentioned adhesive composition for jigs was coated with a knife coater on the peeling surface of the first release film, and dried to form a first adhesive layer with a thickness of 5 μm. Then, the above-mentioned core material was pasted on the first adhesive layer to obtain a laminate A composed of the core material, the first adhesive layer, and the first release film. This laminated body A is a long strip, and is wound up to form a roll-shaped rolled body.

Next, on the peeling surface of the second peeling film, the aforementioned adhesive composition for jigs was coated with a knife coater, and dried to form a second adhesive layer with a thickness of 5 μm. Then, attach the exposed surface of the core material in the above-mentioned laminate A to the second adhesive layer to obtain a composition consisting of the first release film/first adhesive layer/core material/second adhesive layer/second release film. The third layered body. The laminated body is a long strip, which is rolled up to form a roll-shaped rolled-up body.

(4) Production of the fourth laminate The second release film was peeled off from the first laminate obtained in the above (1) to expose the protective film forming film. On the other hand, the release film was peeled off from the second laminate obtained in the above (2) to expose the adhesive layer. In such a manner that the above-mentioned protective film-forming film contacts the adhesive layer, the first laminate and the second laminate are bonded to obtain a support sheet (consisting of a base material and an adhesive layer), a protective film-forming film, and a second laminate. A fourth laminate formed by laminating a release film. The fourth laminate is a long strip, which is rolled up to form a roll-shaped roll-up body.

(5) Production of composite sheets for protective film formation The second release film was peeled off from the third laminate obtained in (3) above to leave the first release film, and the inner peripheral edge of the adhesive layer for jigs was half-cut to remove the inner circular portion. At this time, the diameter of the inner peripheral edge of the adhesive layer for jigs was set to 345 mm.

The first release film was peeled off from the fourth laminate obtained in the above (4), and the exposed protective film forming film and the exposed clip adhesive layer in the third laminate were laminated and bonded under pressure. Then, the first release film in the third laminate was left, and the outer peripheral edge of the composite sheet for forming a protective film was half-cut to remove the outer part. At this time, the diameter of the outer peripheral edge of the composite sheet for protective film formation was 370 mm.

In this way, the composite sheet for protective film formation of Example 1 was obtained. The composite sheet for protective film formation of Example 1 is a support sheet formed by laminating an adhesive layer (thickness: 5 μm) on a base material, laminated on The protective film forming film on the side of the adhesive layer of the support sheet, the ring-shaped adhesive layer for jigs laminated on the peripheral portion of the protective film forming film on the side opposite to the support sheet, and the adhesive layer for jigs laminated on the adhesive layer for jigs Consists of a release film on the opposite side to the protective film forming film. The composite sheet for forming a protective film is a composite sheet for forming a protective film. The peeling film in the composite sheet for forming a protective film is a series of long strips, and the peeling film is used as a support and wound into a roll to form a roll.

[Example 2 to Example 6, Comparative Example 1] As a material of the base material of the support sheet, the aforementioned polypropylene film 1 (thickness: 80 μm) was prepared. Then, the above-mentioned polypropylene film 1 was stretched in the direction, temperature, time, and tension shown in Table 1, and each substrate was produced in the same manner as in Example 1, and a support sheet and a composite sheet for forming a protective film were produced. .

[Comparative example 2] As the material for the base material of the support sheet, prepare a polypropylene film 2 (thickness) with a no-load stretch rate of 100% in the MD direction/100% in the CD direction, a tensile modulus of 450 MPa in the MD direction/440 MPa in the CD direction, and a melting point of 155°C. : 80 μm). The aforementioned polypropylene film 2 was stretched only in the MD direction at a temperature of 120° C., for 1 minute, and at a tension of 1 N/m. A substrate was prepared in the same manner as in Example 1, and a support sheet and a protective film-forming composite were produced. piece.

[Test example 1] [Measurement of no-load stretch rate] For the above-mentioned polypropylene film 1 and the above-mentioned polypropylene film 2 used in the examples and comparative examples, the short side becomes the CD direction and the long side becomes the MD direction, respectively, and is cut into a size of 22 mm on the short side and 110 mm on the long side, as the MD direction The test piece. Mark the test piece with 100mm in the central part of the longitudinal direction out of the length of 110mm as the distance between measurements, and attach a clip with a mass of 2.2g to one end of the test piece in the longitudinal direction (the 5mm portion of the end).

The above-mentioned test piece was suspended in the oven using clips. After heating in the above-mentioned oven at 130°C and 30%RH for 2 hours, the test piece was taken out from the oven and cooled to 23°C. Then, the distance between the marked measurements of the test piece was measured again, and the no-load expansion and contraction rate (%) of the substrate was calculated based on the following formula. No-load stretch rate (%)=(distance between measurements after heating/distance between measurements before heating)×100

In addition, the aforementioned polypropylene film 1 and the aforementioned polypropylene film 2 used in Examples and Comparative Examples were cut into dimensions of 22 mm on the short side and 110 mm on the long side with the short sides in the MD direction and the long sides in the CD direction, respectively. CD orientation test piece. For the test piece in the CD direction, the no-load stretch rate (%) was calculated in the same manner as above.

[Test Example 2] [Measurement of Tensile Elastic Modulus] For the above-mentioned polypropylene film 1 and the above-mentioned polypropylene film 2 used in the examples and comparative examples, they were respectively cut into test pieces of 15mm×140mm, and the tensile modulus of elasticity (Young's modulus) at 23°C was measured according to JIS K7127:1999 number). Specifically, the above-mentioned test piece was pulled at a speed of 200 mm/min after setting the distance between chucks to 100 mm in a tensile testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS 500N"). Tensile test to measure the tensile modulus of elasticity (MPa). In addition, the measurement of the tensile elastic modulus was performed on both the MD direction and the CD direction of the substrate.

[Test Example 3] [Measurement of Melting Point] The melting points of the polypropylene film 1 and the polypropylene film 2 used in Examples and Comparative Examples were measured using a thermogravimetric measuring device (manufactured by Perkin Elmer, product name "Pyris 1"). Specifically, the substrate was heated from 50° C. to 250° C. at 10° C. per minute, and DSC (Differential Scanning Calorimetry, Differential Scanning Calorimetry) measurement was performed, and the temperature at which an endothermic peak was observed was taken as the melting point.

[Test Example 4] [Slack Evaluation] The release film was peeled off from the composite sheets for protective film formation manufactured in Examples and Comparative Examples, and the obtained composite sheet for protective film formation was attached to a silicon wafer (#6000 grinding, diameter: 12 mm) as shown in FIG. 7A inches, thickness: 300 μm, mass: 50 g) and a ring frame (made of stainless steel, with an inner diameter of 350 mm). In this state, only the ring frame was held so that the surface of the silicon wafer was horizontal, and heated at 130°C for 2 hours to harden the protective film forming film to form a protective film, and then cooled to room temperature.

Then, the difference between the height of the lower end surface of the protective film forming composite sheet located on the lower side of the ring frame and the lower end surface of the protective film forming composite sheet located on the lower side of the silicon wafer (amount of sinking; mm ), and evaluate this difference as slack. The evaluation criteria are as follows. The results are shown in Table 1. A (excellent): less than 1.2 mm. B (good): 1.2 mm or more to less than 3.0 mm. C (defective): 3.0 mm or more.

The above results were evaluated as A (excellent) for the protective film-forming composite sheets of Examples 1 to 6, and B (good) for the protective film-forming composite sheets of Comparative Examples 1 to 2.

[Test Example 5] [Thermomechanical Analysis (TMA)] The MD direction of the support sheets of the examples and comparative examples was set as the long side direction, and a short strip-shaped test piece with a length of 20 mm and a width of 5 mm was cut out. Using a thermomechanical analysis device ("TMA-4000SA" manufactured by Bruker AXS Co., Ltd.), the temperature was raised from 23°C to 130°C at a chuck interval of 15mm, a load of 0.8g, and a heating rate of 10°C/min, and held for 30 minutes. Then, it cooled from 130°C to 50°C with a load of 0.8 g and a cooling rate of 1°C/min. Measure the displacement [μm] during this period with sampling frequency: 1s ^-1 .

The CD direction of the support sheets of the examples and comparative examples was set as the long side direction, and a short strip-shaped test piece with a length of 20 mm and a width of 5 mm was cut out. Similarly, using a thermomechanical analysis device ("TMA-4000SA" manufactured by Bruker AXS Co., Ltd.), the temperature was raised from 23°C to 130°C at a chuck interval of 15mm, a load of 0.8g, and a heating rate of 10°C/min. minute. Thereafter, it was cooled from 130°C to 50°C with a load of 0.8 g and a cooling rate of 1°C/min. The displacement [μm] during this period was measured at a sampling frequency of 1s ^-1 .

Calculate the average displacement per 1°C from 60°C to 130°C (A _{60 → 130} ) relative to the average displacement per 1°C from 23°C to 130°C (A _{23 →130} ) ratio [(A _60→130 )/(A _23→130 )].

The average displacement (A _{23 → 130} ) per 1°C when the temperature was raised from 23°C to 130°C was obtained as follows. A _{23 → 130} = (A ₁₃₀ - A ₂₃ )/107 = A ₁₃₀ /107 [μm/°C].

The average displacement per 1°C (A _60→130 ) when the temperature was raised from 60°C to 130°C was obtained as follows. A _{60 → 130} = (A ₁₃₀ −A ₆₀ )/70 [μm/°C].

Displacement at 23°C (A ₂₃ ) = 0 μm; displacement at 60°C (A ₆₀ ) [μm]; displacement at 130°C (A ₁₃₀ ) [μm].

The average displacement per 1°C (B _{130 → 50} ) when slowly cooling from 130°C to 50°C was obtained by the following formula. B _130→50 = (B ₅₀ -B ₁₃₀ )/80 [μm/°C].

The absolute value (|B _130→50 |) of the average displacement per 1°C when slowly cooling from 130°C to 50°C was obtained by the following formula. |B _{130 → 50} |=|B ₅₀ -B ₁₃₀ |/80 [μm/°C].

Displacement (B ₁₃₀ ) [μm] after holding at 130°C for 30 minutes; displacement (B ₅₀ ) [μm] at 50°C after slow cooling.

Calculate the value [(A _23→130 )-|B _130→50 |] obtained by subtracting the absolute value of the average displacement (|B _130→50 |) from the above-mentioned average displacement (A _23→130 ).

Table 1 shows the evaluation results of the above thermomechanical analysis (TMA).

Here, subtract the value of [(A _23→130 )-|B in the vertical direction (CD) from the value of [(A _23→130 )-|B _130→50 |] _{130 → 50} |] The absolute value of the obtained value is used as the "balance evaluation value of MD and CD". The calculation results are shown in Table 1. The balance evaluation value of MD and CD is preferably at most 3.0, more preferably at most 2.5, still more preferably at most 2.0, and most preferably at most 1.8. Since the balance evaluation value of MD and CD is small, it is possible to reduce the possibility that the support sheet or the composite sheet for resin film formation peels from the jig for fixing after heating and cooling, and falls off from this as a starting point.

[Test Example 6] [Evaluation of Wafer Visibility] [Manufacture of semiconductor wafer with protective film] Using a chip mounter (manufactured by Lintec Co., Ltd., product name: Adwill (registered trademark) RAD2500) on a silicon wafer (#6000 grinding, diameter: 12 inches, thickness: 300 μm, mass: 50g) The protective film forming film side surface of the protective film forming composite sheet attached to the polished surface is formed on the support sheet so that the protective film forming film and the silicon wafer are sequentially laminated in the thickness direction of these first laminated composite sheets. The peripheral portion of the first laminated composite sheet was fixed to a ring frame for wafer dicing (made of stainless steel, with an inner diameter of 350 mm) ( FIG. 7A ). Next, keep only the ring frame so that the surface of the silicon wafer becomes horizontal, and heat it in an oven manufactured by Espec at 130°C for 2 hours (Fig. 7B) to harden the protective film forming film and form For the second laminated composite sheet formed by laminating the protective film and the silicon wafer sequentially in the thickness direction on the support sheet, the second laminated composite sheet was cooled to 23° C. ( FIG. 7C ).

Then, use a cutting device (manufactured by Disco Co., Ltd., DFD6361) to cut the silicon wafer and protective film on the support sheet into a wafer size of 3mm×3mm at a cutting speed of 30mm/s and a rotation speed of 40,000rpm. A third laminated composite sheet with a plurality of wafers with protective films fixed on the support sheet was formed (FIG. 7D). The amount of incision during cutting is set to cut into the support sheet 20 μm. The cutting blade is ZH05-SD2000-D1-90 CC manufactured by Disco Co., Ltd. Using a pick-and-die device ("BESTEM D-510" manufactured by Canon Machinery Co., Ltd.), 500 wafers were identified using the automatic tracking function, and all 500 wafers could be identified as A (excellent). The case where the number of recognizable wafers was less than 500 was evaluated as B (defective). The results are shown in Table 1.

Similarly, use a cutting device (manufactured by Disco Co., Ltd., DFD6361) to cut the silicon wafer and protective film into 3mm×1.5mm wafers on the support sheet at a cutting speed of 30mm/s and a rotation speed of 40,000rpm. Size, formed on the support sheet with a plurality of wafers with a protective film fixed on the third laminated composite sheet (Figure 7D). The amount of incision during cutting is set to cut into the support sheet 20 μm. Similarly, using a pick-and-die device ("BESTEM D-510" manufactured by Canon Machinery Co., Ltd.), 500 wafers were identified using the automatic tracking function, and the case where all 500 wafers could be identified was evaluated as A ( Excellent), and the case where the number of recognizable wafers was less than 500 was evaluated as B (poor). The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Substrate Polypropylene film 1 Polypropylene film 1 Polypropylene film 1 Polypropylene film 1 Polypropylene film 1 Polypropylene film 1 Polypropylene film 1 Polypropylene film 2 Additional heating and stretching treatment on the base material Extension direction MD only MD only CD only CD only Both MD and CD Both MD and CD MD only MD only temperature, time 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute 120°C, 1 minute tension 2N/m 3N/m 2N/m 3N/m 2N/m 3N/m 1N/m 1N/m TMA evaluation of support sheet Measurement direction MD cd MD cd MD cd MD cd MD cd MD cd MD cd MD cd Displacement at 130°C (A ₁₃₀ ) μm 208 390 92 360 302 226 281 186 130 209 110 138 520 635 380 480 Average displacement (A _23→130 ) μm/℃ 1.94 3.64 0.86 3.36 2.82 2.11 2.62 1.74 1.21 1.95 1.03 1.29 4.86 5.93 3.56 4.49 Average displacement (A _60→130 ) μm/℃ 1.54 3.69 0.39 3.29 2.37 1.75 2.16 1.31 0.58 1.61 0.42 0.85 5.43 7.80 3.23 5.55 (A _60→130 ／A _23→130 ) 0.79 1.01 0.45 0.98 0.84 0.83 0.82 0.75 0.48 0.83 0.41 0.66 1.12 1.32 0.91 1.24 Average displacement (B _130→50 ) μm/℃ -3.02 -4.38 -3.15 -4.13 -2.65 -3.53 -3.55 -3.33 -3.34 -3.43 -3.57 -3.62 -4.00 -3.18 -3.14 -3.75 Absolute value｜B _130→50 ｜ μm/℃ 3.02 4.38 3.15 4.13 2.65 3.53 3.55 3.33 3.34 3.43 3.57 3.62 4.00 3.18 3.14 3.75 (A _23→130 )－｜B _130→50 ｜ μm/℃ -1.08 -0.73 -2.29 -0.76 0.17 -1.42 -0.93 -1.59 -2.13 -1.48 -2.54 -2.33 0.86 2.75 0.41 0.74 Balance evaluation value of MD and CD μm/℃ 0.35 1.53 1.59 0.66 0.65 0.21 1.89 0.32 Slack evaluation A A A A A A B B Chip identification [3mm×3mm] A A A A A A B B Chip identification [3mm×1.5mm] B A B A A A B B

When evaluating wafer recognizability by cutting into a wafer size of 3mm×3mm, the number of identifiable wafers in Comparative Example 1 to Comparative Example 2 is less than 500, which is B (bad). In contrast, Embodiment 1 to Embodiment The number of identifiable wafers in all 6 is 500, which is A (excellent).

When evaluating wafer recognizability by cutting into a wafer size of 3mm×1.5mm, the number of identifiable wafers in Comparative Example 1 to Comparative Example 2 is less than 500, which is B (bad). In Example 4 to Example 6, the number of identifiable wafers is 500, which is A (excellent). [Industrial availability]

The present invention can be used to manufacture various substrate devices represented by semiconductor devices.

1: Kit 5: The first laminate 7: Pull away from the mechanism 9: Workpiece 9b: Inner surface of workpiece 10,20: support sheet 10a: One side of the support sheet (first side) 11: Substrate 11a: one side of the substrate (first side) 12: Adhesive layer 12a: the first side of the adhesive layer 13,23: Resin film forming layer 13a, 23a: the first surface of the resin film forming layer 13b, 23b: the second surface of the resin film forming layer 13': resin film 13a': One side of the resin film (the first side) 13b': the other side of the resin film (second side) 15: Peel off film 16: Adhesive layer for fixture 16a: The first side of the fixture with adhesive 18: Fixtures for fixing 90: Wafer 90b: Inner face of wafer 101, 102, 103, 104: Composite sheet for resin film formation 130: Resin film forming layer after cutting 130b: the second surface of the resin film forming layer after cutting 130': Resin film after cutting 130b': the second side of the resin film after cutting 151: The first release film 152: Second release film 501: The first laminated composite sheet 502: The second laminated composite sheet 503: The third laminated composite sheet 504: The fourth laminated composite sheet 601: The first laminated film 901: Wafer with resin film 902: Wafer with resin film forming layer P: pull away direction

[ Fig. 1 ] is a cross-sectional view schematically showing an example of a support sheet according to an embodiment of the present invention. [ Fig. 2 ] is a cross-sectional view schematically showing an example of a composite sheet for forming a resin film according to an embodiment of the present invention. [ Fig. 3] Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a resin film according to the embodiment of the present invention. [ Fig. 4] Fig. 4 is a cross-sectional view schematically showing still another example of the composite sheet for forming a resin film according to the embodiment of the present invention. [ Fig. 5] Fig. 5 is a cross-sectional view schematically showing still another example of the composite sheet for forming a resin film according to the embodiment of the present invention. [ Fig. 6 ] is a cross-sectional view schematically showing an example of a kit according to an embodiment of the present invention. [ Fig. 7A] Fig. 7A is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 7B] Fig. 7B is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 7C] Fig. 7C is a partial cross-sectional view schematically illustrating an example of a method for manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 7D ] is a partial cross-sectional view schematically illustrating an example of a method of manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 7E ] is a partial cross-sectional view schematically illustrating an example of a method for manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 8] Fig. 8 is a partial cross-sectional view schematically illustrating another example of a method of manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 9A] Fig. 9A is a partial cross-sectional view schematically illustrating another example of a method of manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 9B] Fig. 9B is a partial cross-sectional view schematically illustrating another example of a method for manufacturing a wafer with a resin film according to an embodiment of the present invention. [ Fig. 9C ] is a partial cross-sectional view schematically illustrating another example of the method for manufacturing a wafer with a resin film according to the embodiment of the present invention.

10: Support sheet

10a: One side of the support sheet (first side)

11: Substrate

11a: one side of the substrate (first side)

12: Adhesive layer

12a: the first side of the adhesive layer

Claims (17)

A support sheet used for heating workpieces or wafers obtained by dividing the workpiece; when the above-mentioned support sheet is subjected to thermomechanical analysis by stretching mode in any one of the traveling direction or the vertical direction under the following conditions, 130°C The displacement A ₁₃₀ is less than 500μm; the average displacement A _23→130 per 1°C when the temperature rises from 23°C to 130°C is less than the average displacement per 1°C when the temperature is slowly cooled from 130°C to 50°C Absolute value｜B _130→50 ｜; The conditions of thermomechanical analysis are as follows: Sample size: length 20mm, width 5mm Interval between clamps: 15mm, with a load of 0.8g and a heating rate of 10℃/min from 23℃ to 130℃, Hold for 30 minutes; then, cool from 130°C to 50°C with a load of 0.8g and a cooling rate of 1°C/min; measure the displacement [μm] during the preceding period. The support sheet as described in claim 1, wherein when the above-mentioned support sheet is subjected to thermomechanical analysis by the tensile mode in the traveling direction and the tensile mode in the vertical direction under the aforementioned conditions, the displacement A ₁₃₀ at 130°C is equal to It is less than 500μm; the average displacement per 1°C from 23°C to 130°C A _23→130 is less than the absolute value of the average displacement per 1°C from 130°C to 50°C when it is slowly cooled to 50°C｜B _{130 → 50} |. The support sheet as described in claim 1 or 2, wherein when the above-mentioned support sheet is subjected to thermomechanical analysis in the tensile mode in either the traveling direction or the vertical direction under the aforementioned conditions, when the temperature is raised from 23°C to 130°C The average displacement per 1°C A _23→130 is a positive value. The support sheet as described in claim 3, wherein when the above-mentioned support sheet is subjected to thermomechanical analysis under the aforementioned conditions through the tensile mode in the traveling direction and the tensile mode in the vertical direction, when the temperature is raised from 23°C to 130°C The average displacement A _23→130 per 1°C is positive. The support sheet as described in claim 3 or 4, wherein when the above-mentioned support sheet is subjected to thermomechanical analysis in the tensile mode in either the traveling direction or the vertical direction under the aforementioned conditions, when the temperature is raised from 60°C to 130°C The ratio of the average displacement A _60→130 per 1°C to the average displacement A _23→130 per 1°C when the temperature rises from 23°C to 130°C is less than 1. The support sheet as described in claim 5, wherein when the above-mentioned support sheet is subjected to thermomechanical analysis by the tensile mode in the traveling direction and the tensile mode in the vertical direction under the aforementioned conditions, when the temperature is raised from 60°C to 130°C The ratio of the average displacement A _60→130 per 1°C to the average displacement A _23→130 per 1°C from 23°C to 130°C did not reach 1. The supporting sheet as described in any one of Claims 1 to 6, wherein the aforementioned supporting sheet is composed of a base material only, or has a base material and an adhesive layer disposed on one side of the aforementioned base material, and the aforementioned The constituent material of the substrate contains polyolefin resin. The supporting sheet as described in any one of Claims 1 to 7, wherein the aforementioned supporting sheet is composed of a base material only, or has a base material and an adhesive layer disposed on one side of the aforementioned base material, and the aforementioned The substrate is a stretched film. The support sheet according to any one of claims 1 to 8, wherein the support sheet is in the shape of a roll. A composite sheet for forming a resin film, comprising the support sheet according to any one of Claims 1 to 8, and a resin film forming layer provided on one side of the support sheet. The composite sheet for forming a resin film according to claim 10, wherein the resin film forming layer is a protective film forming film. The composite sheet for forming a resin film according to Claim 10 or 11, wherein the composite sheet for forming a resin film is in the shape of a roll. A kit comprising: a first laminate formed by sequentially laminating a first release film, a resin film forming layer, and a second release film; and a support sheet as described in any one of Claims 1 to 9, It is used to support the workpiece to be attached to the aforementioned resin film forming layer and the aforementioned resin film forming layer. The kit according to claim 13, wherein the resin film-forming layer is a protective film-forming film. The kit according to claim 13 or 14, wherein the first laminate is in the shape of a roll. A method for manufacturing a wafer with a resin film, the aforementioned wafer with a resin film comprises a wafer and a resin film disposed on the inner surface of the aforementioned wafer; the method for manufacturing the aforementioned wafer with a resin film comprises the following steps: Attaching the resin film forming layer in the resin film forming composite sheet as described in any one of Claims 10 to 12 on the inner surface of the workpiece, or attaching any one of Claims 13 to 15 on the inner surface of the workpiece. The resin film-forming layer in the kit described in item 1 is used to manufacture the first laminated film formed by laminating the aforementioned resin film-forming layer and the workpiece in the thickness direction, and then attach the aforementioned resin film-forming layer in the aforementioned first laminated film The supporting sheet in the aforementioned kit, whereby the first laminated composite sheet formed by laminating the aforementioned resin film forming layer and the aforementioned workpiece sequentially in the thickness direction on the aforementioned supporting sheet; In the state where the peripheral portion of the first laminated composite sheet is attached to a jig for fixing, the first laminated composite sheet is heated to harden the resin film forming layer to form the resin film, thereby forming the above-mentioned supporting sheet so that the The second laminated composite sheet formed by laminating the resin film and the aforementioned workpieces sequentially in the thickness direction; Cool the second laminated composite sheet, then divide the workpiece in the second laminated composite sheet on the support sheet, and cut the resin film, thereby manufacturing a plurality of wafers with resin films fixed on the support sheet the step of the third laminated composite sheet; and A step of pulling the aforementioned wafer with the resin film in the aforementioned third laminated composite sheet from the aforementioned support sheet, thereby picking up the aforementioned wafer with the resin film. A method of manufacturing a wafer with a resin film, the aforementioned wafer with a resin film is equipped with a wafer and a resin film disposed on the inner surface of the aforementioned wafer; the manufacturing method of the aforementioned wafer with a resin film has the following steps: Attaching the resin film forming layer in the resin film forming composite sheet as described in any one of Claims 10 to 12 on the inner surface of the workpiece, or attaching any one of Claims 13 to 15 on the inner surface of the workpiece. The resin film-forming layer in the kit described in item 1 is used to manufacture the first laminated film formed by laminating the aforementioned resin film-forming layer and the workpiece in the thickness direction, and then attach the aforementioned resin film-forming layer in the aforementioned first laminated film The supporting sheet in the aforementioned kit, whereby the first laminated composite sheet formed by laminating the aforementioned resin film forming layer and the aforementioned workpiece sequentially in the thickness direction on the aforementioned supporting sheet; Dividing the aforementioned workpiece in the aforementioned first laminated composite sheet on the aforementioned support sheet, and cutting the aforementioned resin film forming layer, thereby manufacturing a fourth laminated composite sheet in which a plurality of wafers having resin film forming layers are fixed on the aforementioned supporting sheet the steps of In the state where the peripheral portion of the fourth laminated composite sheet is attached to a fixing jig, the fourth laminated composite sheet is heated and cooled to harden the resin film-forming layer in the fourth laminated composite sheet to form the resin film, whereby a step of manufacturing a third laminated composite sheet in which a plurality of wafers with resin films are fixed on the aforementioned supporting sheet; and The step of pulling the wafer with the resin film in the third laminated composite sheet from the support sheet, thereby picking up the wafer with the resin film.

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