KR20220131911A - Peeling method of adherend - Google Patents

Abstract

Step (S1): a step of adhering a plurality of adherends to the pressure-sensitive adhesive layer (X1), and a step (S2): the pressure-sensitive adhesive layer (X1) in a region of the plurality of adherends to which some of the adherends are adhered. a method for peeling an adherend, comprising a step of sublimating at least a portion of the substrate to generate a gas, and lowering the adhesive force between the part of the adherend and the pressure-sensitive adhesive layer (X1); The manufacturing method of the semiconductor chip including the process of implementing the said peeling method; And it is related with the manufacturing method of the semiconductor device including the process of implementing the said peeling method.

Description

Peeling method of adherend

The present invention relates to a method for peeling an adherend.

The pressure-sensitive adhesive sheet may be used not only for semi-permanently fixing a member, but also for temporarily fixing these when processing a building material, an interior material, an optical material, an electronic component, or the like.

In such an adhesive sheet for temporarily fixing use, coexistence of adhesiveness with an adherend at the time of use (at the time of temporarily fixing) and peelability of an adherend after use is calculated|required.

By the way, as a method of peeling a to-be-adhered body from an adhesive sheet, for example, the method using the heat-peelable adhesive sheet in which the adhesive layer containing thermally expansible microparticles|fine-particles was formed on at least single side|surface of a base material is known (patent document 1). see et al.). In this method, when peeling off the adherend adhered to the pressure-sensitive adhesive sheet, the thermally expansible fine particles of the pressure-sensitive adhesive layer are expanded by heating to reduce the contact area between the adherend and the pressure-sensitive adhesive layer, thereby increasing the adhesive force between the pressure-sensitive adhesive layer and the adherend. It is lowered and is trying to peel a to-be-adhered body from an adhesive sheet (for example, refer patent document 1).

Japanese Patent Laid-Open No. 2001-131507

The heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 is generally used in an aspect in which the entire surface of the pressure-sensitive adhesive layer is subjected to heat treatment to decrease the adhesive force between the pressure-sensitive adhesive layer and the adherend on the entire surface of the pressure-sensitive adhesive layer. That is, it is used in the aspect which peels a to-be-adhered body from an adhesive layer collectively.

However, there is a case where it is desired to selectively peel only a part of the adherend, rather than at once from the pressure-sensitive adhesive layer. For example, when a to-be-adhered body is a semiconductor chip with a protective film, out of a plurality of semiconductor chips with a protective film affixed to the adhesive layer, only a part of semiconductor chips with a protective film may be provided in the next process. In such a case, if the adhesive force between the pressure-sensitive adhesive layer and the semiconductor chip with a protective film is reduced in the entire surface of the pressure-sensitive adhesive layer, only the part of the semiconductor chip with a protective film is selectively picked up and moved due to vibration etc. There is a problem in that the position shift of the semiconductor chip with a protective film, peeling from the pressure-sensitive adhesive layer, and the like occur. The same problem may arise in various to-be-adhered bodies, not limited to the semiconductor chip with a protective film.

Then, this invention makes it a subject to provide the to-be-adhered peeling method which can selectively reduce the adhesive force with an adhesive layer only with respect to some to-be-adhered bodies among several to-be-adhered bodies adhering to an adhesive layer.

As a result of repeated intensive studies, the present inventors sublimate at least a part of the pressure-sensitive adhesive layer in the area to which the partial adherend to be peeled is adhered to generate gas, thereby reducing the adhesive force between the partial adherend and the pressure-sensitive adhesive layer. It found that the subject could be solved, and it came to complete this invention by repeating further various examinations.

That is, the present invention relates to the following [1] to [9].

[1] A method for peeling an adherend, comprising the following step (S1) and the following step (S2).

-Step (S1): A step of sticking a plurality of adherends to the pressure-sensitive adhesive layer (X1)

Step (S2): Sublimating at least a part of the pressure-sensitive adhesive layer (X1) in a region to which some adherends are adhered among the plurality of adherends to generate gas, ) to reduce the adhesion of

[2] The pressure-sensitive adhesive layer (X1) is a pressure-sensitive adhesive layer capable of absorbing laser light,

The peeling method according to the above [1], wherein the step (S2) is performed by irradiating the laser beam to at least a part of the pressure-sensitive adhesive layer (X1) in a region to which the partial adherend is adhered.

[3] The following step (SP1) is performed before the step (S2) or after the step (S2), and the following step (SP2) is performed after the step (SP1) and after the step (S2) The peeling method as described in said [1] or [2] which implements.

-Step (SP1): the pressure-sensitive adhesive layer (Z1) of the transfer sheet (Z) having the pressure-sensitive adhesive layer (Z1) is adhered to the opposite side of the adhesive layer (X1) of the plurality of adherends. , a step of laminating the pressure-sensitive adhesive layer (X1) and the transfer sheet (Z) through the plurality of adherends

Step (SP2): The transfer sheet (Z) and the pressure-sensitive adhesive layer (X1) are separated, only the part of the adherend is peeled off from the pressure-sensitive adhesive layer (X1), and the transfer sheet (Z) is placed on the transfer sheet (Z) The process of transferring the complex

[4] The peeling method according to any one of [1] to [3], wherein the pressure-sensitive adhesive sheet (X) having the pressure-sensitive adhesive layer (X1) is used in the step (S1).

[5] The peeling method according to any one of [1] to [4], wherein the adherend is a semiconductor chip.

[6] The peeling method according to any one of [1] to [5], wherein the adherend is a semiconductor chip with a protective film.

[7] The peeling method according to the above [5] or [6], wherein the pressure-sensitive adhesive sheet (X) is a dicing tape.

[8] A method for manufacturing a semiconductor chip, comprising the step of performing the method according to any one of [5] to [7].

[9] A method for manufacturing a semiconductor device, comprising the step of performing the method according to any one of [5] to [7].

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the peeling method of a to-be-adhered body which can reduce the adhesive force with an adhesive layer only with respect to some to-be-adhered bodies among several to-be-adhered bodies adhering to an adhesive layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the process (S1) of the peeling method of this invention, (A) is a top view, (B-1) and (B-2) are schematic cross-sectional views.
It is a schematic sectional drawing which shows an example of the process (S2) of the peeling method of this invention.
Fig. 3 is a schematic cross-sectional view showing the progress of a decrease in adhesive force by enlarging the dotted line enveloping portion of Fig. 2 .
4 : is a figure which shows an example of the process (S1) of the peeling method of this invention about the case where a semiconductor chip with a protective film is used as a to-be-adhered body, (A) is a top view, (B) is a schematic sectional drawing.
5 is a schematic cross-sectional view showing an example of steps (S1-1) to (S1-2) of the peeling method of one embodiment of the present invention in the case where a semiconductor chip with a protective film is used as the adherend.
6 is a schematic cross-sectional view showing an example of the step (S2) of the peeling method of the present invention in the case where a semiconductor chip with a protective film is used as the adherend.
Fig. 7 is a schematic cross-sectional view showing the progress of a decrease in adhesive force by enlarging the dotted line enveloping portion of Fig. 6 .
It is a schematic sectional drawing which shows an example of the process (SP1) - (SP2) of the peeling method of one aspect|mode of this invention.

In the present invention, the "active ingredient" refers to a component excluding the diluent solvent among the components contained in the target composition.

In addition, a mass average molecular weight (Mw) is a standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method, It is a value specifically measured based on the method described in the Example.

In addition, "(meth)acrylic acid" represents both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

Moreover, with respect to a preferable numerical range (for example, the range of content, etc.), the lower limit and upper limit described in stages can be combined independently, respectively. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", "preferred lower limit (10)" and "more preferable upper limit (60)" are combined to "10 to 60" can do.

[Method of peeling adherend]

The peeling method of the to-be-adhered body of this invention includes the following process (S1) and the following process (S2).

-Step (S1): A step of sticking a plurality of adherends to the pressure-sensitive adhesive layer (X1)

Step (S2): Sublimating at least a part of the pressure-sensitive adhesive layer (X1) in a region to which some adherends are adhered among the plurality of adherends to generate gas, ) to reduce the adhesion of

In the following description, the peeling method of the to-be-adhered body of this invention is also simply called "the peeling method of this invention".

In addition, the peeling method of the to-be-adhered body of one aspect|mode of this invention is also simply called "the peeling method of one aspect of this invention".

In addition, the process (S1) is also called a "preparation process."

In addition, the process (S2) is also called "adhesive force reduction process".

Hereinafter, a process (S1) and a process (S2) are demonstrated.

<Step (S1): Preparation Step>

At a process (S1), as shown in FIG. 1, the adhesive sheet X by which the some to-be-adhered body 1 is stuck to the adhesive layer X1 is prepared.

The adherend 1 is not particularly limited, and for example, various substrates such as a semiconductor chip, a semiconductor chip with a protective film, a semiconductor chip with a die attach film (DAF), a glass substrate, a sapphire substrate, and a compound semiconductor substrate. Reorganized goods, etc. are mentioned. In addition, the to-be-adhered body 1 is not necessarily limited to individual pieces, Various wafers, various board|substrates, etc. which are not divided into individual pieces may be sufficient.

Here, in Fig. 1 (B-1), the plurality of adherends 1 are adhered to the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (X) in which the pressure-sensitive adhesive layer (X1) is laminated on one side of the base material (Y). However, this is only an example, and as shown to FIG. 1(B-2), you may make it stick the some to-be-adhered body 1 to the adhesive layer X1 which does not have the base material Y. The adhesive layer (X1) which does not have the base material (Y) is used by sticking and fixing the surface on the opposite side to the sticking surface of the some to-be-adhered body 1 to a hard board|substrate etc., for example.

Moreover, the structure of the adhesive sheet X is not limited to the structural aspect like FIG. 1(B-1), For example, the adhesive layer X1 may be formed in both surfaces of the base material Y. (In this case, the adhesive layer (X2) mentioned later may be sufficient as either adhesive layer (X1).). Moreover, the peeling material may be provided on the adhesive surface of the adhesive layer (X1), and the peeling material is peeled just before sticking the some to-be-adhered body 1 to the adhesive layer (X1), The adhesive of the adhesive layer (X1) You may make it express the surface.

<Step (S2): Adhesion reduction step>

In the step (S2), among the plurality of adherends, at least a portion of the pressure-sensitive adhesive layer (X1) in the region to which the partial adherend is adhered is sublimated to generate gas, and the adhesive force between the partial adherend and the pressure-sensitive adhesive layer (X1) is increased lower it

The present inventors, among a plurality of adherends, as a method for selectively lowering the adhesive force of some adherends with the pressure-sensitive adhesive layer (X1), have at least Recalling that a part is sublimed to generate a gas, the present invention has been completed.

The method for generating gas by sublimating a part of the pressure-sensitive adhesive layer (X1) is not particularly limited, but for example, using the pressure-sensitive adhesive layer (X1) capable of absorbing laser light, the area to which a part of the adherend is adhered. It is preferable to carry out by irradiating a laser beam to at least one part of adhesive layer (X1).

In FIG. 2, the embodiment of the process (S2) using a laser beam is shown. Moreover, FIG. 3 is an enlarged view of the dotted line enveloping part of FIG. 2, and is a figure which shows typically the situation in which the adhesive force with the adhesive layer X1 of some to-be-adhered objects falls among several to-be-adhered bodies.

In the step (S2) using a laser beam, a laser beam is irradiated from the surface on the opposite side to the adherend surface of the adhesive layer (X1), and the pressure-sensitive adhesive layer (X1) in the region where a part of the adherend is adhered. It is preferable to irradiate a laser beam to at least a part. When using the adhesive sheet (X) which has an adhesive layer (X1), for example, as shown to FIG. 2, FIG. 3, laser beam L generated from the laser irradiation apparatus 30 is applied to the adhesive sheet (X) It is preferable to irradiate the laser beam L to at least a part of the adhesive layer X1 of the area|region to which it is made to enter from the base material Y side of the part to-be-adhered body 1a is stuck. Thereby, a part of adhesive layer (X1) ablates, sublimation gas generate|occur|produces, and around the irradiation part of laser beam L WHEREIN: The contact area of a part of to-be-adhered body 1a and adhesive layer X1 falls. And as shown in FIG.3(B), by widening the irradiation area with respect to the adhesive layer X1 of the laser beam L, the adhesive layer X1 ablates extensively, sublimation gas is generated, and a part to-be-adhered body (1a) and the contact area of the adhesive layer (X1) fall further. Thereby, the adhesive force of some to-be-adhered body 1a and the adhesive layer X1 falls.

In addition, even if the sublimation gas leaks around a part of the adherend 1a, the leaked sublimation gas is discharged from the gap 20 between the adherends. Accordingly, it is possible to prevent a decrease in the adhesive force of the adherend 1, which does not require peeling, around a part of the adherend 1a.

In addition, since the step (S2) using laser light does not reduce the adhesive force between the adherend and the pressure-sensitive adhesive layer (X1) by heat treatment, deterioration and warpage of the adherend due to heating can be suppressed. . Moreover, it is preferable to make adhesive layer (X1) absorb most of the irradiated laser beam L. In this case, the damage to the to-be-adhered body resulting from a laser beam can also be suppressed, while improving the sublimation efficiency of the adhesive layer (X1).

The laser irradiation device 30 is not particularly limited as long as it is a device capable of irradiating a laser beam capable of generating sublimation gas from the pressure-sensitive adhesive layer X1. For example, for laser marking a protective film of a semiconductor chip with a protective film. A laser irradiation device or the like can be used.

As such a laser irradiation apparatus, although CSM3000M etc. (solid green laser, wavelength: 532 nm) manufactured by EO Technics are mentioned, It is not necessarily limited to this apparatus, The laser beam which adhesive layer (X1) can absorb is mentioned. Various devices capable of oscillation can be used.

Although the irradiation conditions of a laser beam are not specifically limited as long as the adhesive layer (X1) can absorb the said laser beam, From a viewpoint of peeling only a part to-be-adhered body more efficiently, for example, a frequency becomes like this. Preferably, a frequency is 10,000 Hz - 30,000 Hz. Moreover, the beam diameter of a laser beam becomes like this. Preferably they are 10 micrometers - 100 micrometers, More preferably, they are 20 micrometers - 40 micrometers. The output of the laser beam is preferably 0.1 W to 1.0 W. The scanning speed of a laser beam is 50-200 mm/sec.

In addition, when laser beam irradiation to the pressure-sensitive adhesive layer (X1) is irradiated to at least a part of the pressure-sensitive adhesive layer (X1) in the area to which the adherend to be peeled is adhered, the adhesive force with the pressure-sensitive adhesive layer (X1) may decrease, From the viewpoint of making it easier to lower the adhesive force, laser light irradiation to the pressure-sensitive adhesive layer (X1) in the area where the adherend is to be peeled is adhered to the pressure-sensitive adhesive layer (X1) in the area where the adherend is to be peeled. with respect to the entire surface, preferably 50% or more of the area, more preferably 60% or more of the area, still more preferably 70% or more of the area, still more preferably 80% or more of the area, still more preferably 90% or more of the area, It is especially preferable to apply to a 100% area|region (that is, the whole surface of the adhesive layer (X1) of the area|region to which the to-be-adhered body which requires peeling is sticking).

Moreover, it is preferable not to irradiate the laser beam with respect to the area|region of the adhesive layer (X1) to which the to-be-adhered body is affixed to one area|region unbalancedly, but to spread over a some area|region and to irradiate. For example, by irradiating a laser beam to the periphery and the center of the region of the pressure-sensitive adhesive layer (X1) to which the adherend is adhered, it is easy to effectively reduce the contact area between the adherend and the pressure-sensitive adhesive layer (X1), and therefore, the adherend and the pressure-sensitive adhesive layer It is easy to reduce the adhesive force of (X1) effectively.

Moreover, it is preferable to perform laser beam irradiation with respect to the adhesive layer (X1) toward a to-be-adhered body from the surface on the opposite side to the sticking surface of the some to-be-adhered body of the adhesive layer (X1) as already mentioned. When using the adhesive sheet (X), it is preferable to carry out toward a to-be-adhered body from the base material (Y) side. It is preferable that it is the adhesion surface with the to-be-adhered body of the adhesive layer (X1), or its vicinity. Moreover, it is preferable to adjust so that a laser beam may be irradiated to the sticking surface with the to-be-adhered body of the adhesive layer (X1) or its vicinity. Here, the vicinity of the sticking surface with the to-be-adhered body of the adhesive layer (X1) means the position which exists in the distance within 10 micrometers from the said sticking surface.

[Aspect of the peeling method of the present invention when a semiconductor chip with a protective film is used]

Next, in order to demonstrate more concretely about the peeling method of this invention, the case where the semiconductor chip with a protective film is used as a to-be-adhered body is taken as an example and demonstrated in detail.

<Step (S1) when a semiconductor chip with a protective film is used: preparatory step>

In a process (S1), as shown in FIG. 4, the some semiconductor chip 11 with a protective film is made into the protective film 13 side as a sticking surface, and it sticks to the adhesive layer X1. In addition, in FIG. 4, although the some semiconductor chip 11 with a protective film is made to stick to the adhesive layer X1 of the adhesive sheet X in which the adhesive layer X1 was laminated|stacked on the single side|surface of the base material Y, this It is only an example, and you may make it stick the some semiconductor chip 11 with a protective film to the adhesive layer X1 which does not have the base material Y. The adhesive layer (X1) which does not have the base material (Y) sticks and fixes the surface on the opposite side to the sticking surface of the some semiconductor chip with a protective film 11 on a hard board|substrate etc., and is used, for example.

Moreover, as already mentioned, the adhesive layer (X1) may be formed in both surfaces of the base material (Y) as for the adhesive sheet (X), and the adhesive surface of the adhesive layer (X1) may be equipped with the peeling material.

The semiconductor chip 11 with a protective film is comprised from the semiconductor chip 12 and the protective film 13. The protective film 13 is formed on the surface on the opposite side to the circuit surface 12a of the semiconductor chip 12 , that is, on the back surface 12b of the semiconductor chip 12 .

Although the thickness of the semiconductor chip 12 is not specifically limited, Usually, they are 3 micrometers - 500 micrometers.

Although the thickness of the protective film 13 is not specifically limited, either, Preferably they are 0.05 micrometer - 200 micrometers.

Although the size of the semiconductor chip 12 is not specifically limited, either, Usually, they are 5 micrometers - 15 mm in length, and 5 micrometers - 15 mm in width.

<Step (S1-1), Step (S1-2)>

Here, in the preparatory step of the step (S1) in the case of using a semiconductor chip with a protective film, the plurality of semiconductor chips 11 with a protective film may be adhered to the pressure-sensitive adhesive layer (X1) as described above, and the step (S1) is performed Although the order to be performed is not limited, in the peeling method of one aspect of the present invention, from the viewpoint of efficiently carrying out the present invention, including the step of dividing the semiconductor wafer with a protective film into pieces, the step (S1) is the following step (S1) -1) to (S1-2) are preferably included in this order.

-Step (S1-1): Step of sticking a semiconductor wafer with a protective film to the pressure-sensitive adhesive layer (X1) with the protective film side as a sticking surface

-Step (S1-2): A step of dicing the semiconductor wafer with a protective film to obtain the plurality of semiconductor chips with a protective film

(Step (S1-1))

In a process (S1-1), as shown in FIG. 5, the semiconductor wafer 10 with a protective film is stuck to the adhesive layer X1 making the protective film 13 side a sticking surface. In addition, in FIG. 5, the semiconductor wafer 10 with a protective film is made to stick to the adhesive layer (X1) of the adhesive sheet (X) in which the adhesive layer (X1) was laminated|stacked on the single side|surface of the base material Y, but this is an example It is not too much, and you may make it stick the semiconductor wafer 10 with a protective film to adhesive layer X1 which does not have the base material Y as already mentioned.

The semiconductor wafer 10 with a protective film is comprised from the semiconductor wafer 2 and the protective film 13. As shown in FIG. The protective film 13 is formed on the surface opposite to the circuit surface 2a of the semiconductor wafer 2 , ie, on the back surface 2b of the semiconductor wafer 2 .

As the semiconductor wafer 2, a silicon wafer, a silicon carbide wafer, a compound semiconductor wafer, a glass wafer, a sapphire wafer, etc. are mentioned, for example. Moreover, as for the semiconductor wafer 2, the back surface may be ground suitably, and what became about 3 micrometers - 500 micrometers in thickness may be sufficient as it.

Moreover, the shape of the semiconductor wafer 2 is not limited to a circle, For example, square shapes, such as a square and a rectangle, may be sufficient.

The thickness of the protective film 13 is preferably 0.05 µm to 200 µm.

(Process (S1-2))

At a process (S1-2), as shown in FIG. 5, the semiconductor wafer 10 with a protective film is diced, and the some semiconductor chip 11 with a protective film is obtained.

Although the dicing method is not specifically limited, Well-known methods, such as blade dicing and laser dicing, are employable. Dicing is performed by forming the cutout part 20 so that the semiconductor wafer 2 and the protective film 13 may be penetrated, for example.

Moreover, you may make it expand process after dicing and spread the space|interval (width of the cutout part 20) between the semiconductor chips 11 with a protective film.

(Manufacturing method of semiconductor wafer with protective film)

Although the manufacturing method of the semiconductor wafer with a protective film used in process (S1-1) is not specifically limited, From a viewpoint of making the film thickness of a protective film uniform and making the coating property of the back surface of a semiconductor wafer by a protective film excellent, It is preferable that a semiconductor wafer is what is obtained by hardening a protective film formation film, after affixing a protective film formation film on a semiconductor wafer.

Depending on the kind of curable component contained in the protective film formation film, hardening of a protective film formation film can be performed by either thermosetting and hardening by irradiation of an energy ray.

In addition, in this specification, an "energy beam" means what has an energy proton in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example, Preferably it is an ultraviolet-ray.

As conditions in the case of thermosetting, a curing temperature becomes like this. Preferably it is 100 degreeC - 170 degreeC, and hardening time becomes like this. Preferably it is 1 hour - 3 hours.

Moreover, as conditions in the case of hardening by irradiation of an energy-beam, it determines suitably according to the kind of energy-beam to be used. For example, when using ultraviolet rays, the illuminance is preferably 170 mW/cm 2 to 250 mW/cm 2 , and the amount of light is preferably 600 mJ/cm 2 to 1,000 mJ/cm 2 .

The timing for curing the protective film-forming film may be before the semiconductor wafer to which the protective film-forming film is affixed to the pressure-sensitive adhesive layer (X1), or after the semiconductor wafer to which the protective film-forming film is attached is attached to the pressure-sensitive adhesive layer (X1). may be

Here, when the protective film forming film is cured after the semiconductor wafer to which the protective film forming film is affixed to the pressure sensitive adhesive layer (X1), from the viewpoint of simplification of the process, the protective film forming film and the pressure sensitive adhesive layer (X1) are collectively It is preferable to stick to the back surface 2b of a semiconductor wafer. Specifically, a laminate for forming a protective film in which a protective film forming film is laminated on the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (X) having the pressure-sensitive adhesive layer (X1) is used, and the protective film forming film side of the protective film forming laminate is used. It is preferable to harden a protective film formation film, after sticking together the back surface of a semiconductor wafer.

<Step in case of using semiconductor chip with protective film (S2): Adhesive force lowering step>

In the step (S2) when a semiconductor chip with a protective film is used, at least a part of the pressure-sensitive adhesive layer (X1) in a region to which some semiconductor chips with a protective film are adhered among the plurality of semiconductor chips with a protective film is sublimated to generate gas; The adhesive force of some semiconductor chips with a protective film and adhesive layer (X1) is reduced.

The method for generating gas by sublimating a part of the protective film is not particularly limited, for example, by using a protective film capable of absorbing laser light and irradiating at least a part of the protective film of the semiconductor chip with a partial protective film to at least a part of the protective film by irradiating laser light It is preferable to carry out

In FIG. 6, the embodiment of the process (S2) using a laser beam is shown. 7 is an enlarged view of the dotted line enveloping portion of FIG. 6 , and is a diagram schematically illustrating a situation in which the adhesive force of some semiconductor chips with a protective film to the pressure-sensitive adhesive layer (X1) of the plurality of semiconductor chips with a protective film decreases. to be.

In the process (S2) using a laser beam, it is preferable to irradiate a laser beam from the surface on the opposite side to the sticking surface with the some semiconductor chip with a protective film of the adhesive layer (X1), and to irradiate to the adhesive layer (X1). . When using the adhesive sheet (X) which has an adhesive layer (X1), for example, as shown to FIG. 6, FIG. 7, laser beam L generated from the laser irradiation apparatus 30 is applied to the adhesive sheet (X) It is preferable to make it incident from the base material Y side of , and to irradiate the laser beam L to at least one part of the adhesive layer X1 of the area|region to which the one part semiconductor chip 11a with a protective film is affixing. Thereby, a part of adhesive layer X1 ablates, sublimation gas generate|occur|produces, and around the irradiation part of laser beam L. WHEREIN: The contact area of the one part semiconductor chip 11a with a protective film and adhesive layer X1 falls. And by widening the irradiation area of the laser beam L to the pressure-sensitive adhesive layer (X1), the pressure-sensitive adhesive layer (X1) is ablated extensively to generate sublimation gas, and a part of the semiconductor chip with a protective film (11a) and the pressure-sensitive adhesive layer (X1) ) is further reduced. Thereby, the adhesive force of the one part semiconductor chip 11a with a protective film and adhesive layer X1 falls.

In addition, even if the sublimation gas leaked to the circumference|surroundings of some semiconductor chips 11a with a protective film, the leaked sublimation gas is discharge|released from the cutout 20. As shown in FIG. Therefore, the fall of the adhesive force of the semiconductor chip 11 with a protective film which does not require peeling around the one part semiconductor chip 11a with a protective film can be prevented.

The laser irradiation apparatus 30 can use the apparatus similar to the apparatus mentioned above.

The irradiation conditions of a laser beam are as having already described.

Next, the structure of the adhesive sheet (X) and protective film formation film used in the peeling method of this invention is demonstrated below.

[Adhesive Sheet (X)]

The adhesive sheet (X) has a laminated structure of a base material (Y) and an adhesive layer (X1).

In addition, although the adhesive sheet X shown in FIGS. 1-8 is an aspect provided with the adhesive layer X1 on one side of the base material Y, it is not limited to this, The other one of the base material Y The aspect of the double-sided adhesive sheet which equips the surface with the adhesive layer (X2) may be sufficient.

Moreover, in the peeling method of one aspect of this invention, it is preferable that adhesive sheet (X) is a dicing tape. Hereinafter, each layer which the adhesive sheet (X) may have is demonstrated.

<Reference (Y)>

The base material Y which the adhesive sheet X has functions as a support body which supports the adhesive layer X1, For example, it is comprised from the resin film which has laser-beam transmittance mainly which has a resin-type material.

Specific examples of the resin film include polyethylene films such as low-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, and high-density polyethylene (HDPE) films, polypropylene films, polybutene films, polybutadiene films, polymethyl polyolefin-based films such as pentene films, ethylene-norbornene copolymer films, and norbornene resin films; ethylene-based copolymer films such as an ethylene-vinyl acetate copolymer film, an ethylene-(meth)acrylic acid copolymer film, and an ethylene-(meth)acrylic acid ester copolymer film; polyvinyl chloride-based films such as polyvinyl chloride films and vinyl chloride copolymer films; Polyester-type films, such as a polyethylene terephthalate film and a polybutylene terephthalate film; polyurethane film; polyimide film; polystyrene film; polycarbonate film; A fluororesin film etc. are mentioned. Moreover, you may use the modified|denatured film like the crosslinked film and ionomer film which bridge|crosslinked resin which forms these films.

The base material (Y) may be used individually by 1 type among these resin films, and may use the laminated|multilayer film which used 2 or more types together.

Here, from the viewpoint of versatility, the strength is relatively high and easy to prevent warping, the viewpoint of heat resistance, and the viewpoint of improving laser light transmittance, the resin film is a low-density polyethylene (LDPE) film, a linear low-density polyethylene (LLDPE) film, and a polyethylene film such as a high-density polyethylene (HDPE) film, a polyester-based film such as a polyethylene terephthalate film and a polybutylene terephthalate, and a polypropylene film are preferred. Specifically, the resin film is preferably a single-layer film having one or more layers selected from the group consisting of a polyethylene film, a polyester-based film, and a polypropylene film, or a laminated film in which two or more layers are laminated.

In addition, from the viewpoint of making it easy to ensure high light transmittance with respect to light of a desired wavelength, it is preferable to increase the smoothness on the first surface of the substrate Y (the surface opposite to the surface on which the pressure-sensitive adhesive layer (X1) is formed). do. Specifically, it is preferable that the arithmetic mean roughness Ra in the 1st surface of the base material (Y) is 0.01 micrometer - 0.8 micrometer. In addition, arithmetic mean roughness Ra is a value measured based on JISB0601:1994.

In addition, the base material (Y) may contain a colorant, but when laser light is used in the adhesive force lowering step of the step (S2), from the viewpoint of making a base material more excellent in laser light transmittance, the laser light is absorbed. It is preferable that there is little content of a coloring agent. Specifically, the content of the colorant for absorbing laser light is preferably less than 0.1 mass%, more preferably less than 0.01 mass%, still more preferably less than 0.001 mass%, based on the total amount of the substrate (Y); Even more preferably, it does not contain a colorant.

Although the thickness of the base material (Y) is not specifically limited, Preferably it is 20 micrometers - 450 micrometers, More preferably, it is the range of 25 micrometers - 400 micrometers.

<Adhesive layer (X1)>

The pressure-sensitive adhesive layer (X1) should just contain an adhesive resin, and may contain additives for adhesives, such as a crosslinking agent, a tackifier, a polymeric compound, and a polymerization initiator, as needed.

The adhesive layer (X1) can be formed from the adhesive composition containing adhesive resin.

Hereinafter, each component contained in the adhesive composition which is a forming material of an adhesive layer (X1) is demonstrated.

(Adhesive resin)

It is preferable that adhesive resin has adhesiveness by the said resin independently, and it is a polymer whose mass average molecular weight (Mw) is 10,000 or more.

As a mass average molecular weight (Mw) of adhesive resin, from a viewpoint of the improvement of adhesive force, More preferably, it is 10,000-2 million, More preferably, it is 20,000-1,500,000, More preferably, it is 30,000-1 million. .

Moreover, the glass transition temperature (Tg) of adhesive resin becomes like this. Preferably it is -60 degreeC - -10 degreeC, More preferably, it is -50 degreeC - -20 degreeC.

Examples of the adhesive resin include rubber-based resins such as polyisobutylene-based resins, acrylic resins, urethane-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins.

These adhesive resins may be used individually by 1 type, and may use 2 or more types together.

In addition, when these adhesive resins are copolymers having two or more types of structural units, the form of the copolymer is not particularly limited, and any of block copolymers, random copolymers, alternating copolymers, and graft copolymers may be used. do.

The energy-beam hardening-type adhesive resin which introduce|transduced the polymerizable functional group into the side chain may be sufficient as adhesive resin.

As said polymerizable functional group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.

Moreover, although an ultraviolet-ray, an electron beam, etc. are mentioned as an energy beam, an ultraviolet-ray is preferable.

To [ content of an adhesive resin / the whole amount (100 mass %) of the active ingredient of an adhesive composition), Preferably it is 30-99.99 mass %, More preferably, it is 40 99.95 mass %, More preferably, it is 50-9990 mass %. , More preferably, it is 55-99.80 mass %, More preferably, it is 60-99.50 mass %.

In addition, in the following description of this specification, "content of each component with respect to the total amount of the active ingredient of an adhesive composition" has the same meaning as "content of each component in the adhesive layer formed from the said adhesive composition."

Here, it is preferable that the adhesive resin contains an acrylic resin from a viewpoint of expressing the outstanding adhesive force and suppressing the phenomenon that cutting water penetrates between the adhesive layer (X1) and a protective film at the time of dicing.

As a content rate of the acrylic resin in adhesive resin, with respect to the whole amount (100 mass %) of the adhesive resin contained in an adhesive composition, Preferably it is 30-100 mass %, More preferably, it is 50-100 mass %, More preferably Preferably it is 70-100 mass %, More preferably, it is 85-100 mass %.

(Acrylic resin)

As the acrylic resin usable as the adhesive resin, for example, a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, (meth) acrylate having a cyclic structure and polymers containing structural units derived from

The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.3 million, still more preferably 350,000 to 1.2 million.

As the acrylic resin, a structural unit (a1) derived from an alkyl (meth) acrylate (a1') (hereinafter also referred to as “monomer (a1’)”) and a functional group-containing monomer (a2') (hereinafter referred to as “monomer (a1’)”) The acrylic copolymer (A1) which has a structural unit (a2) derived from "a2')") is more preferable.

The number of carbon atoms in the alkyl group of the monomer (a1') is preferably 1 to 24, from the viewpoint of improving the adhesive properties, and from the viewpoint of suppressing the penetration of cutting water between the pressure-sensitive adhesive layer (X1) and the protective film during dicing, More preferably, it is 1-12, More preferably, it is 2-10, More preferably, it is 4-8.

In addition, a linear alkyl group may be sufficient as the alkyl group which a monomer (a1') has, and a branched chain alkyl group may be sufficient as it.

As the monomer (a1'), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, uryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; and the like.

These monomers (a1') may be used individually by 1 type, and may use 2 or more types together.

As the monomer (a1'), at least one selected from methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is preferable, and methyl (meth) acrylate and butyl ( At least one selected from meth)acrylate is more preferable.

The content of the structural unit (a1) is preferably 50 to 99.9 mass%, more preferably 60 to 99.0 mass%, still more preferably 50 to 99.9 mass%, based on all the constituent units (100 mass%) of the acrylic copolymer (A1). It is 70-97.0 mass %, More preferably, it is 80-95.0 mass %.

As a functional group which a monomer (a2') has, a hydroxyl group, a carboxy group, an amino group, an epoxy group, etc. are mentioned, for example.

That is, as a monomer (a2'), a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer, etc. are mentioned, for example.

These monomers (a2') may be used independently and may use 2 or more types together.

Among these, as a monomer (a2'), a hydroxyl-containing monomer and a carboxy-group-containing monomer are preferable, and a hydroxyl-containing monomer is more preferable.

As a hydroxyl-containing monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate ) hydroxyalkyl (meth)acrylates such as acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Unsaturated alcohols, such as vinyl alcohol and allyl alcohol, etc. are mentioned.

Among these, 2-hydroxyethyl (meth)acrylate is preferable.

As a carboxyl group containing monomer, For example, ethylenically unsaturated monocarboxylic acids, such as (meth)acrylic acid and a crotonic acid; Ethylenically unsaturated dicarboxylic acids and anhydrides thereof, such as fumaric acid, itaconic acid, maleic acid, and citraconic acid, 2-(acryloyloxy)ethyl succinate, 2-carboxyethyl (meth)acrylate, etc. are mentioned. can

The content of the structural unit (a2) is preferably 0.1 to 40 mass%, more preferably 0.5 to 35 mass%, still more preferably 0.1 to 40 mass%, based on all the constituent units (100 mass%) of the acrylic copolymer (A1). It is 1.0-30 mass %, More preferably, it is 3.0-25 mass %.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').

Further, in the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 to 100% by mass based on all the structural units (100% by mass) of the acrylic copolymer (A1). , More preferably, it is 80-100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 95-100 mass %.

As a monomer (a3'), For example, olefins, such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene-based monomers such as butadiene, isoprene, and chloroprene; Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( (meth)acrylates having a cyclic structure such as meth)acrylate and imide (meth)acrylate; Styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, and N-vinylpyrrolidone, etc. can be heard

Moreover, an acryl-type copolymer (A1) is good also as an energy-beam hardening-type acryl-type copolymer which introduce|transduced the polymerizable functional group into the side chain.

As said polymerizable functional group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.

Moreover, although an ultraviolet-ray, an electron beam, etc. are mentioned as an energy beam, an ultraviolet-ray is preferable.

In addition, the polymerizable functional group is an acrylic copolymer having the above-described structural units (a1) and (a2) and a compound having a substituent and a polymerizable functional group capable of bonding with the functional group of the structural unit (a2) of the acrylic copolymer. It can introduce by making it react.

As said compound, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, etc. are mentioned, for example.

(crosslinking agent)

It is preferable that an adhesive composition contains a crosslinking agent further.

The said crosslinking agent reacts with the adhesive resin which has a functional group like the above-mentioned acrylic copolymer (A1), uses the said functional group as a bridge|crosslinking origin, and bridge|crosslinks adhesive resins.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned, for example.

These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.

Among these crosslinking agents, an isocyanate-type crosslinking agent is preferable from a viewpoint of raising cohesive force and improving adhesive force, and a viewpoint of availability, etc.

The content of the crosslinking agent is appropriately adjusted according to the number of functional groups in the adhesive resin, but with respect to 100 parts by mass of the adhesive resin having a functional group, preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, further Preferably it is 0.05-5 mass parts.

(Tackifier)

In this embodiment, the adhesive composition may contain a tackifier further from a viewpoint of improving adhesive force more.

In the present specification, the term "tackifier" refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000 as a component that auxiliaryly improves the adhesive strength of the above-described adhesive resin, and is distinguished from the above-described adhesive resin. will be.

The mass average molecular weight (Mw) of a tackifier becomes like this. Preferably it is 400-less than 10,000, More preferably, it is 500-8,000, More preferably, it is 800-5,000.

As the tackifier, for example, rosin-based resin, terpene-based resin, styrene-based resin, pentene produced by thermal decomposition of petroleum naphtha, isoprene, piperine, and C5 fractions such as 1,3-pentadiene obtained by copolymerizing and C9 petroleum resins obtained by copolymerizing C5 petroleum resins, C9 fractions such as indene and vinyltoluene produced by thermal decomposition of petroleum naphtha, and hydrogenated resins obtained by hydrogenating them.

The softening point of a tackifier becomes like this. Preferably it is 60-170 degreeC, More preferably, it is 65-160 degreeC, More preferably, it is 70-150 degreeC.

In addition, in this specification, the "softening point" of a tackifier means the value measured based on JISK2531.

A tackifier may be used individually by 1 type, and may use together 2 or more types from which a softening point, a structure, etc. differ.

And when using 2 or more types of some tackifier, it is preferable that the weighted average of the softening point of these some tackifier belongs to the said range.

To [ content of a tackifier / the whole amount (100 mass %) of the active ingredient of an adhesive composition), Preferably it is 0.01-65 mass %, More preferably, it is 0.05-55 mass %, More preferably, it is 0.1-50 mass %. %, still more preferably 0.5 to 45 mass%, still more preferably 1.0 to 40 mass%.

(Photoinitiator)

In this embodiment, when an adhesive composition contains energy ray hardening-type adhesive resin as adhesive resin, it is preferable to contain a photoinitiator further.

By containing a photoinitiator, hardening reaction can fully advance also by irradiation of a comparatively low energy energy ray.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, and 8-chloranthraquinone; and the like.

These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

To [ content of a photoinitiator / 100 mass parts of energy ray hardening-type adhesive resins ], Preferably it is 0.01-10 mass parts, More preferably, it is 0.03-5 mass parts, More preferably, it is 0.05-2 mass parts.

(laser light absorber)

In this embodiment, when using a laser beam in the adhesive force fall process of a process (X2), it is preferable that an adhesive composition contains a laser beam absorber.

As a laser beam absorber, 1 or more types chosen from a pigment and dye are mentioned, for example.

An organic pigment or an inorganic pigment may be sufficient as a pigment.

Examples of the dye include a basic dye, an acid dye, a disperse dye, and a direct dye.

Examples of the black pigment include carbon black, copper oxide, iron tetraoxide, manganese dioxide, aniline black, and activated carbon.

Examples of the yellow pigment include yellow lead, zinc sulfur, cadmium yellow, iron oxide yellow, mineral first yellow, nickel titanium yellow, naples yellow, naphthol yellow S, hanja yellow, benzidine yellow G, benzidine yellow GR, quinoline yellow lake. , permanent yellow NCG, and tartrazine lake.

Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, balkan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GKM.

Examples of the red pigment include Bengal, Cadmium Red, Podium, Mercury Sulfide, Cadmium, Permanent Red 4R, Ritol Red, Pyrosolone Red, Watching Red, Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhoda. Min Lake B, Alizarin Lake, Brilliant Carmine 3B, and the like.

Examples of the purple pigment include manganese violet, first violet B, and methyl violet lake.

Examples of the blue pigment include royal blue, cobalt blue, alkali blue lake, victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and indanthrene blue BC. .

Examples of the green pigment include chrome green, chromium oxide, pigment green B, malachite green lake, and final yellow green G.

Examples of the dye include nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

To [ content of a laser beam absorber / the whole quantity of an adhesive composition ], Preferably it is 0.01-10 mass %, More preferably, it is 0.05-7 mass %, More preferably, it is 0.1-5 mass %.

(additive for adhesive)

The adhesive composition which is a forming material of an adhesive layer (X1) may contain the additive for adhesives used for a general adhesive other than the additive mentioned above.

Examples of such additives for pressure-sensitive adhesives include antioxidants, softeners (plasticizers), rust inhibitors, retarders, reaction accelerators (catalysts), and ultraviolet absorbers.

In addition, these additives for adhesives may be used individually by 1 type, respectively, and may use 2 or more types together.

To [ content of each additive for adhesives ] when these additives for adhesives are contained with respect to 100 mass parts of adhesive resins, Preferably it is 0.0001-20 mass parts, More preferably, it is 0.001-10 mass parts.

<Adhesive layer (X2)>

When the pressure-sensitive adhesive sheet (X) is a double-sided pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet may contain an adhesive resin, and as needed, a crosslinking agent, a tackifier, a polymerizable compound, a polymerization initiator, etc. You may contain the additive for adhesives of.

The preferable aspect of the composition and form of adhesive layer (X2) is the same as that of adhesive layer (X1). However, the composition of an adhesive layer (X1) and an adhesive layer (X2) may be same or different. Moreover, the form of an adhesive layer (X1) and an adhesive layer (X2) may be same or different.

Although the thickness of an adhesive layer (X1) and an adhesive layer (X2) is not specifically limited each independently, It is preferable that it is about 1-50 micrometers, and it is more preferable that it is 2-30 micrometers.

The thickness of the pressure-sensitive adhesive layer (X1) and the pressure-sensitive adhesive layer (X2) may be the same or different.

<Releasable material>

A release material may be further formed in the adhesive surface of either one or both of the adhesive layer (X1) which the adhesive sheet (X) has, and the adhesive layer (X2) which the adhesive sheet (X) may have.

As a release material, the release sheet by which the double-sided peeling process was given, the release sheet by which the single-sided peeling process was carried out, etc. are used, What apply|coated the release agent on the base material for release materials, etc. are mentioned.

As a base material for release materials, For example, Paper, such as fine paper, glassine paper, and kraft paper; plastic films such as polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin, and olefin resin films such as polypropylene resin and polyethylene resin; and the like.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

Although the thickness in particular of a release material is not restrict|limited, Preferably it is 10-200 micrometers, More preferably, it is 25-170 micrometers, More preferably, it is 35-80 micrometers.

<Method for Producing Adhesive Sheet (X)>

There is no restriction|limiting in particular as a manufacturing method of adhesive sheet (X), It can manufacture by a well-known method. For example, an organic solvent is added to a raw material composition (hereinafter also referred to as "adhesive layer forming composition") containing each of the above-described components to form a solution of the raw material composition, and the solution is placed on the substrate (Y). After apply|coating by a well-known coating method to form a coating film, it can dry and can form the adhesive layer (X1) on the base material (Y).

Moreover, after apply|coating the said solution by a well-known coating method on the above-mentioned peeling material by a well-known coating method and forming a coating film, drying and forming an adhesive layer (X1) on a peeling material, the base material (Y) and an adhesive layer (X1) can also be bonded together and the adhesive sheet (X) which has the laminated structure of a peeling material / adhesive layer (X1) / base material (Y) can also be manufactured.

Toluene, ethyl acetate, methyl ethyl ketone, etc. are mentioned as an organic solvent to be used.

Solid content concentration of the solution of the adhesive layer formation composition at the time of mix|blending an organic solvent becomes like this. Preferably it is 10-80 mass %, More preferably, it is 25-70 mass %, More preferably, it is 45-65 mass %.

Examples of the coating method include a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll coat method, a roll knife coat method, a blade coat method, a die coat method, and a gravure coat method. .

[Protective Film Forming Film]

Although there is no restriction|limiting in particular as a protective film formation film, It is preferable to contain a polymer component (B) and a sclerosing|hardenable component (C), Furthermore, a coloring agent (D), a coupling agent (E), an inorganic filler (F), general purpose You may contain an additive (G).

Hereinafter, the said (B)-(G) component contained in a protective film formation film is demonstrated.

<Polymer component (B)>

A "polymer component" means a compound having a mass average molecular weight (Mw) of 20,000 or more and having at least one repeating unit. By containing a polymeric component (B) in a protective film formation film, flexibility and film-forming property can be mainly provided to a protective film formation film, and sheet|seat property maintenance can be made favorable.

As a mass average molecular weight (Mw) of a polymer component (B), Preferably it is 20,000-3 million, More preferably, it is 50,000-2 million, More preferably, it is 100,000-1,500,000.

To [ content of a polymer component (B) / total amount (100 mass %) of a protective film formation film), Preferably it is 5-50 mass %, More preferably, it is 8-40 mass %, More preferably, it is 10-30 mass %. %, more preferably 12 to 25 mass%.

As the polymer component (B), an acrylic polymer (B1) is preferable, and non-acrylic polymers other than the acrylic polymer (B1), such as polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polysiloxane, rubber polymer, etc. (B2) may be used.

These polymer components may be used individually by 1 type, and may use 2 or more types together.

(Acrylic polymer (B1))

The mass average molecular weight (Mw) of the acrylic polymer (B1) is preferably 20,000 to 3,000,000, more preferably 100,000 to 1.5,000,000, still more preferably from the viewpoint of imparting flexibility and film formability to the protective film forming film. Preferably it is 150,000 to 1.2 million, More preferably, it is 250,000 to 1 million.

The glass transition temperature (Tg) of the acrylic polymer (B1) is preferably -60 to 50°C from the viewpoint of the adhesiveness of the protective film formed from the protective film forming film to the adherend, and from the viewpoint of improving the reliability of the chip with the protective film. , More preferably, it is -50 to 40 degreeC, More preferably, it is -40 to 30 degreeC, More preferably, it is -35-20 degreeC.

Examples of the acrylic polymer (B1) include a polymer containing an alkyl (meth) acrylate as a main component, and specifically includes a structural unit (b1) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms. An acrylic polymer to be used is preferable, and an acrylic copolymer including a structural unit (b2) derived from a functional group-containing monomer together with the structural unit (b1) is more preferable.

A component (B1) may be used individually by 1 type, and may use 2 or more types together.

When the component (B1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

(constituent unit (b1))

The number of carbon atoms of the alkyl group of the alkyl (meth)acrylate constituting the structural unit (b1) is preferably 1 to 18, more preferably 1 to 12, from the viewpoint of imparting flexibility and film formability to the protective film forming film. , more preferably 1 to 8.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Uryl (meth)acrylate, stearyl (meth)acrylate, etc. are mentioned.

In addition, these alkyl (meth)acrylates may be used individually by 1 type, and may use 2 or more types together.

Among these, the alkyl (meth)acrylate which has a C4 or more alkyl group is preferable, the alkyl (meth)acrylate which has a C4-6 alkyl group is more preferable, and butyl (meth)acrylate is still more preferable.

The content rate of the structural unit derived from the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably 1 to 70 mass%, more preferably 1 to 70 mass% with respect to all the constituent units (100 mass%) of the acrylic polymer (B1). is 5 to 65 mass%, more preferably 10 to 60 mass%.

Moreover, from a viewpoint of the reliability improvement of a chip|tip with a protective film, the alkyl (meth)acrylate which has a C1-C3 alkyl group is preferable, and methyl (meth)acrylate is more preferable.

From the said viewpoint, the content rate of the structural unit derived from the alkyl (meth)acrylate which has a C1-C3 alkyl group with respect to all the structural units (100 mass %) of acrylic polymer (B1), Preferably 1-60. It is mass %, More preferably, it is 3-50 mass %, More preferably, it is 5-40 mass %.

The content rate of the structural unit (b1) is preferably 50 mass% or more, more preferably 50 to 99 mass%, still more preferably 55 to all the structural units (100 mass%) of the acrylic polymer (B1). -90 mass %, More preferably, it is 60-80 mass %.

(constituent unit (b2))

Examples of the functional group-containing monomer constituting the structural unit (b2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and a nitrogen atom-containing ring. The monomer which has, the alkoxy silyl group containing monomer, etc. are mentioned.

These functional group containing monomers may be used individually by 1 type, and may use 2 or more types together.

Among these, a hydroxyl-containing monomer is preferable.

As a hydroxyl-containing monomer, although what was illustrated in description of the hydroxyl-containing monomer in an adhesive layer (X1) is mentioned, 2-hydroxyethyl (meth)acrylate is preferable.

As a carboxyl group-containing monomer, what was illustrated as a carboxyl group-containing monomer in an adhesive layer (X1) is mentioned.

By using a carboxyl group-containing monomer, when a carboxyl group is introduced into the acrylic polymer (B1) and the protective film forming film contains an energy ray-curable component as the curable component (C), compatibility of component (C) and component (B) sex is improved

In addition, when using an epoxy-type thermosetting component as a curable component (C) mentioned later, since a carboxyl group and the epoxy group in an epoxy-type thermosetting component will react, it is preferable that the content of the structural unit derived from a carboxyl group-containing monomer is small.

When an epoxy thermosetting component is used as the curable component (C), the content of the structural unit derived from the carboxyl group-containing monomer is preferably 0 to 10 with respect to all the structural units (100 mass%) of the acrylic polymer (A1). It is mass %, More preferably, it is 0-5 mass %, More preferably, it is 0-2 mass %, More preferably, it is 0 mass %.

Examples of the epoxy-containing monomer include an epoxy group-containing (meth)acrylic acid ester and a non-acrylic epoxy group-containing monomer.

As the epoxy group-containing (meth)acrylic acid ester, for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate and 3-epoxycyclo-2-hydroxypropyl (meth)acrylate.

Moreover, as a non-acrylic epoxy group containing monomer, glycidyl crotonate, allyl glycidyl ether, etc. are mentioned, for example.

Among these, epoxy group containing (meth)acrylic acid ester is preferable, and glycidyl (meth)acrylate is more preferable.

These functional group containing monomers may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of more easily improving the sublimability of the protective film, the content rate of the structural units derived from the epoxy group-containing monomer is preferably 1 to 30% by mass relative to all the structural units (100% by mass) of the acrylic polymer (B1), More preferably, it is 5-27 mass %, More preferably, it is 10-24 mass %.

The content of the structural unit (b2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, still more preferably 10 to all the structural units (100% by mass) of the acrylic polymer (B1). - 40 mass %, More preferably, it is 20-40 mass %.

(Structural units derived from other monomers)

In addition, in the range which does not impair the effect of this invention, the acrylic polymer (B1) may have structural units derived from other monomers other than the said structural units (b1) and (b2).

As another monomer, vinyl acetate, styrene, ethylene, alpha-olefin etc. are mentioned, for example.

(Non-acrylic resin (B2))

The protective film formation film may contain non-acrylic resin (B2) as a resin component other than the above-mentioned acrylic polymer (B1) as needed.

Examples of the non-acrylic resin (B2) include polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polysiloxane, and rubber-based polymer.

These resins may be used individually by 1 type, and may use 2 or more types together.

As a mass average molecular weight of non-acrylic resin (B2), Preferably it is 20,000 or more, More preferably, it is 20,000 - 100,000, More preferably, it is 20,000 - 80,000.

Although the non-acrylic resin (B2) may be used individually by 1 type, by using together with the above-mentioned acrylic polymer (B1), when an adhesive sheet and a protective film forming film are laminated|stacked, delamination can be performed easily, , voids and the like can be suppressed.

When the non-acrylic resin (B2) is used together with the above-mentioned acrylic polymer (B1), the mass ratio [(B2)/(B1)] of the non-acrylic resin (B2) to the acrylic polymer (B1) is from the above viewpoint, Preferably it is 1/99 - 60/40, More preferably, it is 1/99 - 30/70.

In addition, when the structural unit constituting the acrylic polymer (B1) contains a structural unit derived from an epoxy group-containing monomer, the acrylic polymer (B1) and the phenoxy resin having an epoxy group have thermosetting properties, but these are curable components ( It is not C) and shall be included in the concept of a polymer component (B).

<Curable component (C)>

A sclerosing|hardenable component (C) hardens a protective film formation film, bears the role of forming a hard protective film, and is a compound whose mass average molecular weight is less than 20,000.

As the curable component (C), it is preferable to use a thermosetting component (C1) and/or an energy ray-curable component (C2), and from the viewpoint of sufficiently advancing the curing reaction, and from the viewpoint of cost reduction, at least the thermosetting component (C1) ) is more preferable to use.

It is preferable to contain the compound which has a functional group which reacts by heating at least as a thermosetting component (C1).

Moreover, an energy-beam-curable component (C2) contains the compound (C21) which has a functional group which reacts by energy-beam irradiation, and when irradiated with energy rays, such as an ultraviolet-ray and an electron beam, polymerization-hardening.

The functional groups of these curable components react with each other to form a three-dimensional network structure, whereby curing is realized.

The mass average molecular weight (Mw) of the curable component (C) is preferably used in combination with the component (B) from the viewpoint of suppressing the viscosity of the composition forming the protective film forming film and improving handling properties. It is less than 20,000, More preferably, it is 10,000 or less, More preferably, it is 100-10,000.

(thermosetting component (C1))

As the thermosetting component (C1), an epoxy-based thermosetting component is preferable.

It is preferable to use what combined the thermosetting agent (C12) with the compound (C11) which has an epoxy group as an epoxy-type thermosetting component.

Examples of the compound (C11) having an epoxy group (hereinafter also referred to as “epoxy compound (C11)”) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated substances thereof, orthocresol novolac epoxy resins. and dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and phenylene skeleton-type epoxy resins.

These epoxy compounds (C11) may be used individually by 1 type, and may use 2 or more types together.

The content of the epoxy compound (C11) is preferably from 1 to 500 parts by mass, more preferably from 3 to 300 parts by mass, still more preferably from 10 to 150 parts by mass, further with respect to 100 parts by mass of the component (B). Preferably it is 20-120 mass parts.

(thermosetting agent (C12))

The thermosetting agent (C12) functions as a curing agent for the epoxy compound (C11).

As a thermosetting agent, the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is preferable.

Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group (acid anhydride structure). Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride group is preferable, a phenolic hydroxyl group or an amino group is more preferable, and an amino group is still more preferable.

Examples of the phenolic thermosetting agent having a phenol group include polyfunctional phenol resins, biphenols, novolak phenol resins, dicyclopentadiene phenol resins, xylok phenol resins, and aralkylphenol resins. have.

As an amine-type thermosetting agent which has an amino group, dicyandiamide (DICY) etc. are mentioned, for example.

These thermosetting agents (C12) may be used individually by 1 type, and may use 2 or more types together.

To [ content of a thermosetting agent (C12) / 100 mass parts of epoxy compounds (C11)), Preferably it is 0.1-500 mass parts, More preferably, it is 1-200 mass parts.

(curing accelerator (C13))

In order to adjust the rate of thermosetting of the protective film formation film, you may use a hardening accelerator (C13). It is preferable to use a hardening accelerator (C13) together with an epoxy compound (C11) as a thermosetting component (C1).

Examples of the curing accelerator (C13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -imidazoles, such as hydroxymethyl imidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; and tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.

These hardening accelerators (C13) may be used individually by 1 type, and may use 2 or more types together.

The content of the curing accelerator (C13) is 100 parts by mass of the total amount of the epoxy compound (C11) and the thermosetting agent (C12) from the viewpoint of improving the adhesiveness of the protective film formed from the protective film forming film, and from the viewpoint of improving the reliability of the chip with the protective film , Preferably it is 0.01-10 mass parts, More preferably, it is 0.1-6 mass parts, More preferably, it is 0.3-4 mass parts.

(Energy-ray-curable component (C2))

As the energy ray-curable component (C2), a compound (C21) having a functional group that reacts with energy ray irradiation may be used alone, but it is preferable to use a photopolymerization initiator (C22) in combination with the compound (C21). do.

(Compound (C21) having a functional group that reacts with energy ray irradiation)

Examples of the compound (C21) having a functional group that reacts with energy ray irradiation (hereinafter also referred to as “energy ray-reactive compound (C21)”) include trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate , urethane acrylate oligomers, epoxy acrylates, polyether acrylates, itaconic acid oligomers, and the like.

These energy-beam reactive compounds (C21) may be used individually by 1 type, and may use 2 or more types together.

Moreover, the mass average molecular weight (Mw) of an energy-beam-reactive compound (C21) becomes like this. Preferably it is 100-30,000, More preferably, it is 300-10,000.

To [ content of an energy-beam-reactive compound (C21) / 100 mass parts of component (B)), Preferably it is 1 - 1,500 mass parts, More preferably, it is 3 - 1,200 mass parts.

(Photoinitiator (C22))

By using together with a photoinitiator (C22) with the energy-beam reactive compound (C21) mentioned above, polymerization hardening time can be shortened and hardening of a protective film formation film can be advanced at least in the amount of light irradiation.

As a photoinitiator (C22), the thing mentioned above is mentioned.

The content of the photoinitiator (C22) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the energy ray-reactive compound (C21) from the viewpoint of sufficiently advancing the curing reaction and suppressing the production of residues, more Preferably it is 1-5 mass parts.

To [ content of component (C) ] the whole amount (100 mass %) of a protective film formation film, Preferably it is 5-50 mass %, More preferably, it is 8-40 mass %, More preferably, it is 10-30 mass %. , More preferably, it is 12-25 mass %.

In addition, the content of the component (C) is a thermosetting component (C1) containing the above-mentioned epoxy compound (C11), a thermosetting agent (C12), and a curing accelerator (C13), and an energy-beam reactive compound (C21), and the total content of the energy ray-curable component (C2) containing the photopolymerization initiator (C22).

<Colorant (D)>

The protective film formation film may contain the coloring agent (D) further.

When a laser beam is irradiated to adhesive layer (X1) by containing a coloring agent (D) in a protective film formation film, a protective film can also be sublimated with adhesive layer (X1), and a gas can be generated, and the semiconductor with a protective film which peels off is desired. The adhesive force of a chip|tip with the adhesive layer (X1) can be reduced more efficiently.

However, it is not necessarily necessary to make the laser beam reach the protective film. By not allowing a laser beam to reach a protective film, the said semiconductor chip with a protective film can be selectively peeled, without generating a laser mark in the protective film of the semiconductor chip with a protective film which peels off.

As a coloring agent (D), the thing similar to what was mentioned as a laser beam absorber is mentioned.

Moreover, a coloring agent (D) may be used individually by 1 type, and may use 2 or more types together.

To [ content of a coloring agent (D) / total amount (100 mass %) of a protective film formation film), Preferably it is 0.1-30 mass %, More preferably, it is 0.5-25 mass %, More preferably, it is 1.0-15 mass %. , More preferably, it is 1.2-5 mass %.

<Coupling agent (E)>

It is preferable that the protective film formation film further contains a coupling agent (E).

By including a coupling agent (E), the polymer component in a protective film formation film and the semiconductor chip surface or filler surface which are to-be-adhered can be couple|bonded, and adhesiveness and cohesion can be improved. Moreover, water resistance can also be improved, without impairing the heat resistance of the protective film formed from a protective film formation film.

As a coupling agent (E), the compound which reacts with the functional group which a component (B) or a component (C) has is preferable, and a silane coupling agent is more preferable.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. -(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ- Aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. are mentioned.

These coupling agents (E) may be used individually by 1 type, and may use 2 or more types together.

As a coupling agent (E), the coupling agent of an oligomer type is preferable.

The molecular weight of the coupling agent (E) including the oligomeric coupling agent is preferably 100 to 15,000, more preferably 150 to 10,000, still more preferably 200 to 5,000, still more preferably 250 to 3,000, still more Preferably it is 350-2,000.

To [ content of a coupling agent (E) / total amount (100 mass %) of a protective film formation film), Preferably it is 0.01-10 mass %, More preferably, it is 0.05-7 mass %, More preferably, it is 0.10-4 mass % %, and still more preferably 0.15 to 2 mass%.

<Inorganic filler (F)>

It is preferable that the protective film formation film further contains an inorganic filler (F).

By including the inorganic filler (F), it becomes possible to adjust the thermal expansion coefficient in the protective film after curing of the protective film forming film to an appropriate range, and by optimizing the thermal expansion coefficient of the protective film after curing for the semiconductor chip, the reliability of the semiconductor device is improved can do it Moreover, it also becomes possible to reduce the moisture absorption of the protective film after hardening.

Examples of the inorganic filler (F) include powders such as silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide and boron nitride, beads obtained by spheroidizing these, single crystal fibers, and glass fibers. .

These inorganic fillers (F) may be used individually by 1 type, and may use 2 or more types together.

Among these, silica or alumina is preferable.

As an average particle diameter of an inorganic filler (F), from a viewpoint of improving the gloss value of the protective film formed from a protective film formation film, Preferably it is 0.3-50 micrometers, More preferably, it is 0.5-30 micrometers, More preferably, it is 0.7-10 is μm.

In addition, in this invention, the average particle diameter of an inorganic filler (F) means the value measured using the laser diffraction-scattering type particle size distribution analyzer.

To [ content of an inorganic filler (F) / total amount (100 mass %) of a protective film formation film), Preferably it is 25-80 mass %, More preferably, it is 30-70 mass %, More preferably, it is 40-65 mass %. %, still more preferably 45 to 60 mass%.

<General purpose additive (G)>

In addition to the above, various additives may be mix|blended with the protective film formation film as needed.

As various additives, a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, antioxidant, an ion trapping agent, a gettering agent, a chain transfer agent, etc. are mentioned.

<The manufacturing method of a protective film formation film>

There is no restriction|limiting in particular as a manufacturing method of a protective film formation film, It can manufacture by a well-known method. For example, an organic solvent is added to a raw material composition (hereinafter also referred to as "protective film forming composition") containing each of the above-described components to form a solution of the protective film forming composition, and the solution is used as the above-described release sheet It can be manufactured by coating by a known coating method on the surface to form a coating film, followed by drying, and forming a protective film forming film on a release sheet.

Toluene, ethyl acetate, methyl ethyl ketone, etc. are mentioned as an organic solvent to be used.

Solid content concentration of the solution of the protective film formation composition in the case of mix|blending an organic solvent becomes like this. Preferably it is 10-80 mass %, More preferably, it is 20-70 mass %, More preferably, it is 30-65 mass %.

Examples of the coating method include a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll coat method, a roll knife coat method, a blade coat method, a die coat method, and a gravure coat method. .

A single layer may be sufficient as a protective film formation film, and 2 or more types of multilayered structures may be sufficient as it.

The thickness of the protective film forming film is not particularly limited, but is preferably 3 to 300 µm, more preferably 5 to 250 µm, still more preferably 7 to 200 µm, and even when the protective film forming film has a multilayer structure, the entire It is preferable that thickness (summary of the thickness of each layer) is the said range.

<The manufacturing method of the laminated body for protective film formation>

There is no restriction|limiting in particular as a manufacturing method of the laminated body for protective film formation containing the laminated structure of a protective film formation film and adhesive sheet (X), It can manufacture by a well-known method.

First, as demonstrated in the manufacturing method of a protective film formation film, a protective film formation film is formed on a peeling sheet. Next, by bonding the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (X) and the protective film forming film formed on the release sheet, a laminate for forming a protective film having a laminate structure of release sheet/protective film forming film/adhesive layer (X1) can be manufactured.

[How to pick up the desired adherend]

Although the method of picking up the to-be-adhered body by which the adhesive force with the adhesive layer (X1) fell by the process (S2) is not specifically limited, For example, For example, it pushes up from the lower side with a pin etc. through the adhesive sheet (X), and vacuum The method of picking up with a collet etc. is mentioned.

Here, in the manufacturing method of one aspect of this invention, it is preferable to pick up the to-be-adhered body in which the adhesive force with the adhesive layer (X1) fell by the process (S2) by the method shown below.

That is, it is preferable to carry out the following step (SP1) before the step (S2) or after the step (S2), and to perform the following step (SP2) after the step (SP1) and after the step (S2). do.

-Step (SP1): the pressure-sensitive adhesive layer (Z1) of the transfer sheet (Z) having the pressure-sensitive adhesive layer (Z1) is applied to the adhesive layer (X1) of the plurality of adherends with the opposite side to the adherend surface and laminating the pressure-sensitive adhesive layer (X1) and the transfer sheet (Z) through the plurality of adherends.

Step (SP2): The transfer sheet (Z) and the pressure-sensitive adhesive layer (X1) are separated, only the part of the adherend is peeled off from the pressure-sensitive adhesive layer (X1), and the transfer sheet (Z) is placed on the transfer sheet (Z) The process of transferring the complex

In the following description, this method is also referred to as a "transfer method".

In the step (SP1), as shown in FIG. 8 , the pressure-sensitive adhesive layer (Z1) of the transfer sheet (Z) having the pressure-sensitive adhesive layer (Z1) is applied to the plurality of adherends (1) (some adherends for which peeling is desired ( The adhesive layer (X1) and the transfer sheet (Z) are adhered to each other with a surface opposite to the adhered surface of the adhesive layer (X1) of (including 1a)) as a bonding surface, and a plurality of adherends (1) are interposed therebetween. to stack

<Transfer sheet (Z)>

The transfer sheet (Z) has a laminated structure of the base material (Y') and the pressure-sensitive adhesive layer (Z1).

As the base material (Y'), the same thing as what was mentioned as the base material (Y) of the adhesive sheet (X) can be used, and thickness is also the same as that of the base material (Y).

Moreover, the thing similar to what was mentioned as adhesive layer (X1) of adhesive sheet (X) can also be used for adhesive layer (Z1).

The step (SP1) may be performed before the step (S2) or may be performed after the step (S2). Even if it implements at any timing, it does not affect the adhesive force fall process in process (S2).

And the process (S2) is performed, and as shown in FIG. 8 in the state in which the adhesive force with the adhesive layer (X1) of a part to-be-adhered body 1a fell, the transfer sheet Z and the adhesive sheet (X) separate Thereby, only a part of to-be-adhered body 1a is peeled from the adhesive sheet X, and a part to-be-adhered body 1a can be transcribe|transferred to the transfer sheet Z.

Here, the transfer method is not limited to the above method. For example, in a state in which the step (S2) is carried out and the adhesive force of a part of the adherends 1a with the pressure-sensitive adhesive layer (X1) is reduced, the porous table is placed on the pressure-sensitive adhesive layer (X1) of the plurality of adherends 1 . ), it may be arranged so as to be in contact with the surface opposite to the adhered surface, and a part of the adherend 1a may be adsorbed and transferred to the porous table. The adsorption|suction by a porous table may be selectively performed only with respect to some to-be-adhered body 1a in which the adhesive force fell, and you may make it perform with respect to the whole surface of the adhesive layer X1. When adsorption by the porous table is performed with respect to the entire surface of the pressure-sensitive adhesive layer (X1), by separating the pressure-sensitive adhesive layer (X1) adsorbed on the porous table from the porous table, only a portion of the adherend 1a having reduced adhesive strength It can be transferred by adsorption to the porous table. In addition, the average pore diameter of the porous table used at this time is preferable from the viewpoint of adsorbing and transferring only a portion of the adherend 1a whose adhesion with the pressure-sensitive adhesive layer X1 is lowered by sucking the entire surface with a weak force. Preferably it is 60 micrometers or less, More preferably, it is 55 micrometers or less. Moreover, porosity becomes like this. Preferably it is 30 % - 60 %, More preferably, they are 45 % - 60 %.

Further, for example, the step (S2) is performed, and in a state in which the adhesive force of a part of the adherend 1a to the pressure-sensitive adhesive layer X1 is decreased, the electrostatic chuck is applied to the plurality of semiconductor chips 11 with a protective film. It may be arrange|positioned so that it may contact with the surface opposite to the protective film side, and it may be made to transfer by holding a part of to-be-adhered body 1a by an electrostatic chuck. The gripping by the electrostatic chuck may be selectively performed only with respect to a part of the adherend 1a in which the adhesive force has decreased, or may be performed with respect to the entire surface of the pressure-sensitive adhesive layer X1. When gripping by the electrostatic chuck is performed with respect to the entire surface of the pressure-sensitive adhesive layer (X1), by separating the pressure-sensitive adhesive layer (X1) gripped by the electrostatic chuck from the electrostatic chuck, only a portion of the adherend 1a with reduced adhesive force is used. It can be transferred by gripping it with an electrostatic chuck. In addition, at this time, from the viewpoint of gripping and transferring only a part of the adherend 1a whose adhesive strength with the pressure-sensitive adhesive layer X1 is lowered by gripping the entire surface with a weak force, the base material and the pressure-sensitive adhesive layer are laminated on the electrostatic chuck You may make it affix an adhesive sheet as a cushioning material, and make holding force weak.

[Method for manufacturing semiconductor chip with protective film]

The method for manufacturing a semiconductor chip according to one aspect of the present invention is the method for producing a semiconductor chip according to the present invention, comprising steps (S1) and (S2), in which an adherend is a semiconductor chip or a semiconductor chip with a protective film; performing the method.

In particular, in the manufacturing method of the semiconductor chip with a protective film of this invention, the to-be-adhered body is a semiconductor chip with a protective film, and process (S1) is this invention which includes process (S1-1) - (S1-2) in this order. Since it is possible to efficiently manufacture a semiconductor chip with a protective film from the semiconductor wafer with a protective film, it is preferable by including the process of implementing the peeling method of one aspect|mode.

Moreover, the to-be-adhered body is made into a semiconductor chip with a protective film, and a process (S1) includes processes (S1-1) - (S1-2) in this order, and also implements the manufacturing method of the semiconductor wafer with a protective film mentioned above. Since it is possible to efficiently manufacture a semiconductor chip with a protective film from a semiconductor wafer by also including the process of doing, it is preferable.

[Method for manufacturing semiconductor device]

In this specification, the term "semiconductor device" refers to an overall device that can function by using semiconductor characteristics used for a processor, a memory, a sensor, and the like.

The method for manufacturing a semiconductor device according to an aspect of the present invention is the method for manufacturing a semiconductor device according to the present invention, including steps (S1) and (S2), in which an adherend is a semiconductor chip or a semiconductor chip with a protective film performing the method. Therefore, among the plurality of semiconductor chips or semiconductor chips with a protective film, only a part of semiconductor chips or semiconductor chips with a protective film can be used in the processing process of a semiconductor device. Specifically, among a plurality of semiconductor chips or semiconductor chips with a protective film, only a part of semiconductor chips or semiconductor chips with a protective film can be used in the process of mounting on a semiconductor device. For example, it becomes possible to provide, for example, only a high quality semiconductor chip or a semiconductor chip with a protective film to a process of selectively mounting on a semiconductor device, etc., contributing to the improvement of the yield of a semiconductor device.

Example

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.

10 pieces of semiconductor chips with a protective film (chip size: 1 mm x 1 mm, chip thickness: 200 µm, protective film thickness: 25 µm) to the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (X) are 30 µm It was lined up in series, the protective film side was made into a sticking surface, and it stuck, and the adhesive sheet (X) which stuck the some semiconductor chip with a protective film was prepared.

The adhesive sheet (X) was made into the structure which laminated|stacked the adhesive layer (X1) on the base material (Y). The details of the base material (Y) and the pressure-sensitive adhesive layer (X1) were as follows.

Substrate (Y): polyethylene film, thickness 80 µm, arithmetic mean roughness Ra = 0.1 µm on the surface opposite to the surface on which the pressure-sensitive adhesive layer (X1) is formed

·Adhesive layer (X1): a pressure-sensitive adhesive layer formed from the following pressure-sensitive adhesive composition, 10 μm in thickness,

The adhesive sheet (X) was produced in the following procedure.

First, an adhesive composition was prepared. Specifically, 80 moles relative to the acrylic copolymer obtained by reacting butyl acrylate/methyl methacrylate/2-hydroxyethyl acrylate = 80/5/15 (mass ratio) and the 2-hydroxyethyl acrylate % of methacryloyloxyethyl isocyanate (MOI) was made to react, and the energy-beam curable polymer was obtained. The mass average molecular weight (Mw) of this energy ray-curable polymer was 400,000. Moreover, the glass transition temperature (Tg) was -44 degreeC.

100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, product name "Irgacure 184") as a photoinitiator, and tolylene diisocyanate-based crosslinking agent (Japanese polyurethane) as a crosslinking agent The Kogyo Co., Ltd. product, product name "Colonate L") 0.49 mass part and 1 mass part of carbon black (The Mitsubishi Chemical Corporation make, product name "M100") were mixed in a solvent, and the adhesive composition was obtained.

Then, on the base material (Y), the said adhesive composition was apply|coated, it heat-dried, and the adhesive sheet (X) was produced.

The protective film formation film and curing conditions used in order to form the protective film of the semiconductor chip with a protective film were as follows.

・Protection film forming film: ADWILL LC2850 (25)

Curing conditions: 130℃, 2 hours

A laser beam was irradiated from the base material (Y) side toward one semiconductor chip with a protective film among the adhesive sheets (X) which stuck several semiconductor chips with a protective film. Irradiation conditions were as follows.

(Laser light irradiation conditions)

・Laser light irradiation device: manufactured by EO Technics, CSM3000M, solid green laser (wavelength: 532 nm)

Frequency: 20,000 Hz ∼ 25,000 Hz

Scanning speed: 100 mm/sec

Output: 0.12 W ∼ 0.82 W

·Beam diameter: 35 ㎛

(Experiment result)

Among the adhesive sheets (X) to which a plurality of semiconductor chips with a protective film are adhered, the adhesive layer (X1) in the region to which one semiconductor chip with a protective film is adhered toward the vicinity of the adhesion surface with the semiconductor chip with a protective film, the base material (Y ) side was irradiated with a laser beam.

As a result, it can be visually confirmed from the base material (Y) side that air is gathered and formed at the interface of the said one semiconductor chip with a protective film, and the adhesive layer (X1), and the adhesive layer only about this one semiconductor chip with a protective film. It turned out that the adhesive force with (X1) can be greatly reduced. On the other hand, the remaining semiconductor chip with a protective film does not collect air at the interface with the pressure-sensitive adhesive layer (X1) and is firmly adhered to the pressure-sensitive adhesive layer (X1) without reducing the adhesive force with the pressure-sensitive adhesive layer (X1). state was maintained.

Moreover, a laser trace was not observed in the protective film of the said one semiconductor chip with a protective film, but deterioration of the protective film resulting from laser beam irradiation was also suppressed.

1, 1a: adherend
2: semiconductor wafer
10: semiconductor wafer with protective film
11, 11a: semiconductor chip with protective film
12: semiconductor chip
13: Shield
20: Gap between adherends, cutout
30: laser irradiation device
X: adhesive sheet
X1: adhesive layer
Y: description
Z: transfer sheet
Z1: adhesive layer
Y': substrate

Claims (9)

A method for peeling an adherend, comprising the following step (S1) and the following step (S2).
-Step (S1): Step of sticking a plurality of adherends to the pressure-sensitive adhesive layer (X1)
Step (S2): Sublimating at least a part of the pressure-sensitive adhesive layer (X1) in a region to which some adherends are adhered among the plurality of adherends to generate gas, ) to reduce the adhesion of The method of claim 1,
The pressure-sensitive adhesive layer (X1) is a pressure-sensitive adhesive layer capable of absorbing laser light,
The peeling method in which the said process (S2) is implemented by irradiating the said laser beam to at least a part of the said adhesive layer (X1) of the area|region to which the said part to-be-adhered body is sticking. 3. The method according to claim 1 or 2,
The following step (SP1) is performed before the step (S2) or after the step (S2), and the following step (SP2) is performed after the step (SP1) and after the step (S2), peeling method.
-Step (SP1): the pressure-sensitive adhesive layer (Z1) of the transfer sheet (Z) having the pressure-sensitive adhesive layer (Z1) is adhered to the opposite side of the adhesive layer (X1) of the plurality of adherends. , a step of laminating the pressure-sensitive adhesive layer (X1) and the transfer sheet (Z) through the plurality of adherends
Step (SP2): The transfer sheet (Z) and the pressure-sensitive adhesive layer (X1) are separated, only the part of the adherend is peeled off from the pressure-sensitive adhesive layer (X1), and the transfer sheet (Z) is placed on the transfer sheet (Z) The process of transferring the complex 4. The method according to any one of claims 1 to 3,
The peeling method which uses the adhesive sheet (X) which has the said adhesive layer (X1) in the said process (S1). 5. The method according to any one of claims 1 to 4,
The peeling method in which the said to-be-adhered body is a semiconductor chip. 6. The method according to any one of claims 1 to 5,
The peeling method in which the said to-be-adhered body is a semiconductor chip with a protective film. 7. The method according to claim 5 or 6,
The peeling method in which the said adhesive sheet (X) is a dicing tape. The manufacturing method of a semiconductor chip including the process of implementing the method in any one of Claims 5-7. A method for manufacturing a semiconductor device, comprising the step of performing the method according to any one of claims 5 to 7.

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