TW201702072A - Resin-film forming composite sheet, and method of manufacturing chip having resin film - Google Patents

Abstract

Provided is a resin-film forming composite sheet which has a structure in which a resin-film forming film capable of forming a resin film is directly laminated on a support sheet, and which satisfies the following requirements (I) and (II). Requirement (I): the peel force ([alpha]1) required for peeling the resin-film forming film from a silicon wafer is 0.05-10.0 N/25 mm, which is measured in an environment of 23 DEG C and under peeling conditions (x) of a pulling rate of 300 mm/min and a pulling angle of 180 DEG after a surface ([alpha]) of the resin-film forming film, the surface ([alpha]) being on the side to be adhered to the silicon wafer, has been adhered to the silicon wafer. Requirement (II): the peel force ([beta]1), which is measured under the peeling conditions (x), and which is required for peeling the support sheet from a surface ([beta]) of the resin-film forming film, the surface ([beta]) being on the side directly laminated on the support sheet, has a value equal to or greater than the peel force ([alpha]1).

Description

Composite sheet for forming resin film, and method for producing wafer with resin film

The present invention relates to a method for producing a composite film for forming a resin film and a wafer with a resin film using a composite film for forming a resin film.

In recent years, the manufacture of semiconductor devices, which are known as the flip-down mounting method, is being carried out. In the flip-chip method, a semiconductor wafer (hereinafter also referred to simply as "wafer") having an electrode such as an impact is mounted on a circuit surface of a semiconductor wafer, and electrodes of the wafer are bonded to the substrate. Therefore, the surface of the wafer (hereinafter also referred to as "the back surface of the wafer") on the side opposite to the bonding side of the substrate may be peeled off.

In the back surface of the wafer to be peeled off, a resin film made of an organic material may be formed and incorporated into a semiconductor device as a wafer with a resin film. The resin film may be imparted as a protective film for preventing the occurrence of cracks after the dicing step or packaging, or the obtained wafer may be used as a die pad portion or other semiconductor wafer. The other components are followed by the function of the film.

In general, the wafer with the resin film will contain the composition of the resin. The solution is applied to the back surface of the wafer by spin coating or the like to form a coating film, and then the coating film is dried and cured to form a resin film, which is produced by cutting the obtained resin film wafer.

In addition, the sheet for forming a resin film for curing is adhered to the back surface of the wafer, and the sheet for forming a resin film is cured by irradiation or heating of the energy rays before and after the dicing of the wafer to form a resin film. It is also possible to manufacture a wafer with a resin film or a wafer with a resin film.

As a material for forming a resin film on the back surface of such a wafer or the back surface of a wafer, various films for forming a resin film have been proposed.

For example, Patent Document 1 discloses a film for protecting a wafer, which comprises a polymer component composed of an acrylic copolymer, an energy ray-curable component, a dye or a pigment, an inorganic filler, and a photopolymerization initiator. The wire-curable protective film forming layer was formed by sandwiching two peeling sheets.

According to Patent Document 1, the wafer protective film is irradiated with an energy ray to form a protective film having excellent visibility, hardness, and adhesion to a wafer, and is compatible with a conventional film for wafer protection. Comparison, the simplification of the steps is possible.

Further, Patent Document 2 discloses a dicing tape-integrated wafer back surface protective film which has a dicing tape having an adhesive layer on a substrate, and is colored on the adhesive layer of the dicing tape. A wafer back protective film with a predetermined modulus of elasticity.

According to the description of Patent Document 2, the wafer back surface protective film is diced in the semiconductor wafer, and the holding force with the semiconductor wafer is good.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-138026

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-199543

Therefore, when the protective film described in Patent Documents 1 and 2 is pasted on the wafer, the position of the protective film which is adhered to the wafer is displaced, or a foreign matter adheres to the wafer, which may cause a problem. The protective film is adhered in such a manner that the wafer also contains foreign matter. In such a case, there is a case where the protective film is subjected to rework (reposting) from the wafer.

However, it is often difficult to cleanly reprocess the protective film which is once adhered to the wafer so as not to cause residue on the wafer.

In particular, the protective films disclosed in Patent Documents 1 and 2 are intended to be adhered to the wafer by adhesion to the wafer during adhesion or adhesion to the wafer after adhesion, because The adhesion of the wafer is high and it is very difficult to perform reprocessing.

That is, when the protective film once adhered to the wafer is strongly peeled off, the wafer is damaged by the applied force, or even if the protective film is peeled off, a part of the protective film remains on the wafer, and the crystal cannot be used. The circle is reused.

In Patent Documents 1 and 2, the protective film described above has been studied from the viewpoint of adhesion to a wafer at the time of pasting or adhesion to a wafer after pasting, but is protected against wafer adhesion once. The study of the reworkability of the film is completely absent.

The present invention has an object of providing a method for producing a wafer having a resin film which is excellent in reworkability and which can be peeled off after bonding to a tantalum wafer, and a resin film-attached film using the composite film for forming a resin film.

The present inventors have found that a composite film for forming a resin film having a structure in which a film for forming a resin film on a support sheet is directly laminated is peeled off by a film for forming a resin film by a target, that is, a tantalum wafer. The above-mentioned problems can be solved by the required peeling force and the peeling force required for the film for forming a release resin film and the support sheet, and the present invention has been completed.

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

[1] A composite sheet for forming a resin film, which has a structure in which a film for forming a resin film on which a resin film can be formed on a support sheet is directly laminated, and which satisfies the following requirements (I) and (II), I): after the surface (α) of the film for forming a resin film on the side of the same wafer is pasted on the silicon wafer, the stretching speed is 300 mm/min, and the stretching angle is at 23 ° C. The 180° peeling condition (x) was tested, and the peeling force (α1) required for peeling the resin film forming film from the germanium wafer was 0.05 to 10.0 N/25 mm; (II): a peeling force required to peel the support sheet from the surface (β) of the film for forming a resin film directly on the side of the direct lamination of the support sheet by the peeling condition (x) Β1) is a value equal to or higher than the peeling force (α1).

[2] The composite sheet for forming a resin film according to the above [1], which further satisfies the following requirement (III), and the element (III): when the resin film is formed of the film for forming a resin film, the peeling condition (x) In the test, the peeling force (β2) required to peel the support sheet from the surface (β') of the resin film on the side of the direct lamination of the support sheet was 0.02 to 5.0 N/25 mm.

[3] The composite sheet for forming a resin film according to the above [1] or [2], wherein the peeling force (β1) is 0.05 to 20.0 N/25 mm.

[4] The composite sheet for forming a resin film according to any one of the above [1], wherein the support sheet is a sheet composed only of a substrate.

[5] The composite sheet for forming a resin film according to any one of the above [1], wherein the support sheet is an adhesive sheet having an adhesive layer on a substrate, and an adhesive layer having the adhesive sheet The surface (β) of the film for forming a resin film is directly laminated.

[6] The composite sheet for forming a resin film according to the above [5], wherein the pressure-sensitive adhesive layer is a layer formed of an adhesive composition containing an energy ray-curable resin.

The composite film for forming a resin film according to any one of the above aspects, wherein the film for forming a resin film contains a polymer component (A) and Hardening component (B).

[8] The composite sheet for forming a resin film according to any one of the above [1], wherein the film for forming a resin film is a material for forming a protective film or a film.

[9] A method for producing a wafer with a resin film, comprising the following steps (1) to (4), wherein the step (1): on the back side of the workpiece, is as claimed in any one of claims 1 to 8. Step of adhering the composite sheet for forming a resin film; Step (2): Step of cutting the processed product Step (3): Step of forming a resin film from the film for forming a resin film Step (4): Passing the step (2) The obtained processed product after cutting is picked up to obtain a wafer.

The composite sheet for forming a resin film of the present invention is excellent in reworkability, and can be peeled off even after being adhered to a tantalum wafer, and the tantalum wafer after peeling can be reused. Therefore, the method for producing a wafer with a resin film using the composite sheet for forming a resin film of the present invention is advantageous from the viewpoint of productivity and economy.

1a, 1b, 1c, 1d‧‧‧ composite film for forming a resin film (composite sheet)

10‧‧‧Support sheet

20‧‧‧film for resin film formation

21‧‧‧Surface (α)

22‧‧‧Surface (β)

30‧‧‧ resin film

31‧‧‧Surface (α’)

32‧‧‧Surface (β’)

40‧‧ ‧ fixtures

50‧‧‧ Carrier Sheet

100‧‧‧矽 wafer

Fig. 1 is a cross-sectional view showing a composite sheet for forming a resin film according to an aspect of the present invention.

FIG. 2 is a cross-sectional view showing a configuration in which a composite sheet for forming a resin film according to an aspect of the present invention is adhered to a tantalum wafer.

3 is a cross-sectional view showing a configuration in which a resin film is formed on a tantalum wafer using a composite film for forming a resin film according to an aspect of the present invention.

In the present specification, for example, "(meth) acrylate" is used as a term indicating both "acrylate" and "methyl acrylate", and the same applies to other similar terms.

Further, the "energy line" means, for example, an ultraviolet ray or an electron beam, and is preferably ultraviolet ray.

[Configuration of Composite Sheet for Resin Film Formation]

Fig. 1 is a cross-sectional view showing a composite sheet for forming a resin film according to an aspect of the present invention.

As shown in Fig. 1, the composite sheet for forming a resin film of the present invention (hereinafter also referred to simply as "composite sheet") has a structure in which a film for forming a resin film on which a resin film can be formed on a support sheet is directly laminated.

Further, the form of the composite sheet of the present invention is not particularly limited, and may be, for example, a long tape shape or a single leaf label.

As a composite sheet which is one aspect of the present invention, a composite sheet 1a having a structure in which the resin film forming film 20 is directly laminated on the surface of the support sheet 10 as shown in Fig. 1(a) is exemplified.

A film for forming a resin film of a composite sheet which is one aspect of the present invention The shape of 20 is preferably a shape that may include a shape that is slightly the same as the shape of the wafer, that is, the wafer, or the shape of the wafer.

In the composite sheet 1a of Fig. 1(a), the support sheet 10 and the resin film forming film 20 have substantially the same shape. However, as shown in Fig. 1(b), the shape of the resin film forming film 20 can be more supported. The composite sheet 1b having a smaller shape of the sheet 10.

Further, as a composite sheet according to an aspect of the present invention, a composite sheet 1c having a ring-shaped jig and a layer 40 as shown in Fig. 1(c) can be cited.

When the loop-shaped jig 40 is attached to a jig of a ring-shaped frame or the like, the double-layer adhesive sheet having the base material (core material) may be provided for the purpose of improving the adhesion of the jig. The adhesive is formed.

Further, in the composite sheet 1c shown in Fig. 1(c), the jig adhesive layer 40 is provided on the surface (?) 21 of the resin film forming film 20, but the composite sheet which is one aspect of the present invention may be used. The jig back layer 40 is provided on the surface of the support sheet 10 of the composite sheet 1b as shown in Fig. 1(b).

In addition, for example, the surface (α) 21 of the resin film forming film 20 which is formed in the composite sheet 1a shown in Fig. 1(a) is a bonding surface to the target wafer, that is, the tantalum wafer.

Therefore, the surface (α) 21 can be formed on the surface (α) 21 of the resin film-forming film 20 as a further ytterbium wafer, as shown in Fig. 1(d), in order to prevent foreign matter from adhering or scratching. The composite sheet 1d of the peelable carrier sheet 50 is laminated at the time of bonding.

The composite sheet 1d shown in Fig. 1(d) is a structure in which a carrier sheet 50 is provided on the surface (α) 21 of the resin film forming film 20 which the composite sheet 1a shown in Fig. 1(a) has. The carrier sheet 50 is provided for preventing contamination or the like from adhering to the surface (α) 21 of the film 20 for forming a resin film during storage, and is removed when the composite sheet 1d is adhered to the wafer.

In the carrier sheet 50 of the composite sheet 1d shown in Fig. 1 (d), the base sheet for a carrier sheet such as a resin film may be used, but the substrate for a carrier sheet such as the resin film may be used. It is preferred that the surface is subjected to a release treatment.

Further, similarly to the configuration of the composite sheet 1d, the composite sheet 1b of Fig. 1(b) can be further provided with the surface (α) 21 and the surface of the support sheet 10, as shown in Fig. 1(c). The composite sheet 1c is shown, and the carrier sheet can be provided so as to cover the surface (α) 21 and the surface of the jig attachment layer 40.

Here, the support sheet of the composite sheet according to one aspect of the present invention may be a sheet composed only of a substrate, or an adhesive sheet having an adhesive layer on the substrate.

When the adhesive sheet is used as the supporting sheet, the adhesive layer of the adhesive sheet and the surface (β) 22 of the film 20 for forming a resin film are directly laminated.

Further, the support sheet used as one aspect of the present invention may be a sheet composed of a substrate having a surface subjected to a release treatment. As the support sheet, a composite sheet comprising a sheet composed of a substrate having a surface subjected to the release treatment is used as a release treatment for performing the substrate. The surface and the surface (β) 22 of the film 20 for forming a resin film are directly laminated.

[Removal force (α1), (β1), (β2) of composite sheet for resin film formation]

The composite sheet for forming a resin film of the present invention must satisfy the following requirements (I) and (II).

(I): After the surface (α) of the film for forming a resin film on the side of the same wafer is pasted on the wafer, the film is stretched at a rate of 300 mm/min and pulled at 23 ° C. The peeling condition (x) at an angle of 180° was tested, and the peeling force (α1) required for peeling the film for forming a resin film from the tantalum wafer was 0.05 to 10.0 N/25 mm.

(II): a peeling force required to peel the support sheet from the surface (β) of the film for forming a resin film directly on the side of the direct lamination of the support sheet by the peeling condition (x) Β1) is a value equal to or higher than the peeling force (α1).

Further, in the present specification, the "peeling force (α1)" and the "peeling force (β1)" defined in the above requirements (I) and (II) mean that the conditions and methods described in the examples are measured. value.

2 is a cross-sectional view showing a configuration in which a composite sheet for forming a resin film according to an aspect of the present invention is adhered to a tantalum wafer.

As shown in Fig. 2, the "peeling force (?1)" defined by the requirement (I) defines the interface between the wafer 100 and the surface (?) 21 of the film 20 for resin film formation on the side of the wafer. The peeling force of α1.

In the present invention, the peeling force (α1) must be 0.05~ 10.0N/25mm.

For example, as disclosed in Patent Documents 1 and 2, the conventional film for forming a resin film has many purposes for improving the adhesion and retention of the wafer and the wafer, and is used to increase the peeling force (α1) described above. Value material design.

However, when the peeling force (α1) exceeds 10.0 N/25 mm, it is actually difficult to perform reworking of the film for forming a resin film adhered to the tantalum wafer. In other words, when the film for forming a resin film to be adhered to the silicon wafer is strongly peeled off, it is considered that a part of the film for forming a resin film remains on the wafer, or the wafer is damaged. Reuse the wafer.

Therefore, in the composite sheet of the present invention, in order to obtain excellent reworkability, the above-mentioned peeling force (α1) can be adjusted to 10.0 N/25 mm or less even in the composite sheet which can be peeled off after the enamel wafer is pasted.

On the other hand, when the peeling force (α1) described above is less than 0.05 N/25 mm, it tends to float or peel off particularly at the end portion of the composite sheet after being adhered to the tantalum wafer.

From the above viewpoints, in one aspect of the present invention, the peeling force (α1) is preferably 0.06 to 9.5 N/25 mm, more preferably 0.07 to 9.2 N/25 mm, still more preferably 0.1 to 9.0 N/25 mm, and even more. Preferably, it is 0.2 to 8.0 N/25 mm, more preferably 0.5 to 6.0 N/25 mm, and even more preferably 0.5 to 4.0 N/25 mm, and particularly preferably 0.5 to 3.0 N/25 mm.

In one aspect of the present invention, as a method of adjusting the peeling force (α1), for example, a polymer component, a curable component, an inorganic filler, an additive, and the like which are contained in a film for forming a resin film are appropriately selected. The method of adjusting the class or content. The method of adjusting the specific peeling force (α1) can be adjusted by appropriately considering the items described in the items of the respective components to be described later.

The "peeling force (β1)" defined by the requirement (II) is, for example, as shown in Fig. 2, the surface (β) 22 of the film 20 for forming a resin film directly on the side of the support sheet 10, and the supporting sheet. The peeling force of the boundary interface β1 of 10.

When the adhesive sheet is used as the support sheet, the "peeling force (β1)" is a peeling force which is defined on the surface (β) of the film for forming a resin film and the adhesive layer of the adhesive sheet used as the support sheet. By.

In the present invention, the peeling force (β1) is required to be a value equal to or higher than the above-described peeling force (α1).

When the peeling force (β1) is less than the peeling force (α1), when the composite sheet adhered to the tantalum wafer is reworked, all or part of the film for forming a resin film remains on the tantalum wafer, and the film cannot be reused.矽 Wafer.

From the viewpoint of further improving the reworkability of the composite sheet, the difference [(β1) - (α1)]) between the peeling force (β1) and the peeling force (α1) is preferably 0.01 N/25 mm or more, and more preferably It is 0.1 N/25 mm or more, more preferably 0.15 N/25 mm or more, still more preferably 0.2 N/25 mm or more, still more preferably 0.5 N/25 mm or more, and particularly preferably 1.0 N/25 mm or more.

Further, the difference [β1 - α1] between the peeling force (β1) and the peeling force (α1) is preferably 20 N/25 mm or less, more preferably 12 N/25 mm or less, but when picking up the cut wafer, From the viewpoint of picking property to good, it is more preferably 8.0 N/25 mm or less, and even more preferably 6.0 N/25 mm or less. The best is 4.0N/25mm or less, and even more preferably 2.5N/25mm or less.

In one aspect of the present invention, the peeling force (β1) is preferably 0.05 to 20.0 N/25 mm, more preferably 0.2 to 18.0 N/25 mm, still more preferably 0.5 to 16.0 N/25 mm, and still more preferably. It is 1.0~14.0N/25mm.

When the peeling force (β1) is 0.05 N/25 mm or more, when the composite sheet adhered to the ruthenium wafer is subjected to reworking, the phenomenon of the film for forming the resin film and the support sheet can be finally separated at the boundary interface β1.

On the other hand, if the peeling force (β1) is 20.0 N/25 mm or less, the pick-up property can be improved when picking up the cut wafer.

In one aspect of the present invention, as a method of adjusting the peeling force (β1), for example, the type or content of each of the above-described components included in the film for forming a resin film and the type of the supporting sheet to be used are appropriately selected. (The method of adjusting the type of the resin film to be the base material, the type and amount of the resin constituting the release layer, the blending amount, the type of the resin and the additive constituting the adhesive layer, and the blending amount).

The adjustment method for the specific peeling force (β1) can be adjusted by appropriately considering the items described in the items of the components to be described later.

Further, the composite sheet of one aspect of the present invention preferably further satisfies the following requirement (III).

(III): When the resin film is formed of the film for forming a resin film, the film is tested by the peeling condition (x), and the surface (β') of the resin film on the side directly laminated with the support sheet is The peeling force (β2) required for peeling the support sheet is 0.02 to 5.0 N/25 mm.

Further, in this specification, the "peeling force" specified in the above requirement (III) (β2)" means the value measured by the conditions and methods described in the examples.

3 is a cross-sectional view showing a configuration in which a resin film is formed on a tantalum wafer using a composite sheet for forming a resin film according to an aspect of the present invention.

The "peeling force (β2)" defined by the requirement (III) is, for example, as shown in FIG. 3, which is defined on the surface (β') 32 of the resin film 30 formed of the film for forming a resin film, and the support sheet 10. The peeling force of the boundary interface β2.

When the adhesive sheet is used as the supporting sheet, the "peeling force (β2)" is a peeling force which is defined on the surface (β') of the resin film and the interface layer of the adhesive layer used as the supporting sheet.

When the peeling force (β2) is 0.02 N/25 mm or more, when the wafer is obtained by picking up the cut wafer, since the wafer has a certain holding force, the uneven dispersion of the wafer can be suppressed before picking up.

On the other hand, if the peeling force (β2) is 5.0 N/25 mm or less, the pick-up property can be improved when picking up the cut wafer.

In one aspect of the invention, the peeling force (β2) is preferably from 0.03 to 4.0 N/25 mm, more preferably from 0.05 to 2.5 N/25 mm, even more preferably from 0.10 to 2.0 N/ from the above viewpoint. 25mm, and even more preferably 0.15~1.5N/25mm.

On the other hand, as shown in FIG. 3, the peeling force of the boundary surface α2 of the surface (α') 31 on the side of the tantalum wafer on the side of the tantalum wafer 100 and the resin film 30 formed of the resin film forming film is shown in FIG. (α2), although not particularly limited, is at least larger than the peeling force (α1) and the peeling force (β2) described above. Preferably.

Further, in one aspect of the present invention, the method of adjusting the peeling force (β2) is not particularly limited, and a modulation method similar to the above-described peeling force (β1) can be cited.

Further, when an adhesive sheet is used as the supporting sheet, it is preferable to use an adhesive sheet having an adhesive layer formed of an adhesive composition containing an energy ray-curable resin. By irradiating the energy ray, the adhesive force of the adhesive layer is lowered, and the peeling force (β2) is easily adjusted in such a manner as to fall within the above range.

[Layer constituting the composite sheet for forming a resin film]

Hereinafter, each layer constituting the composite sheet for forming a resin film according to an aspect of the present invention will be described.

<Thin film for forming a resin film>

In the film for forming a resin film of the composite sheet which is one aspect of the present invention, the peeling force (α1) and (β1) may be in the above range, but the polymer component (A) and the curability are included. The film for forming a resin film of the component (B) is preferred.

Further, the film for forming a resin film may further contain, in addition to the components (A) and (B), a film selected from the group consisting of inorganic filler (C), colorant (D), and coupling agent (without the effect of the present invention). E) and one or more of the general-purpose additives (F).

Hereinafter, the above component (A) contained in the film for forming a resin film is included. ~(F) is explained.

Further, the values of the peeling forces (α1), (β1), and (β2) can be adjusted by appropriately combining the appropriate items of the following components.

[Polymer component (A)]

In the present specification, the term "polymer component" means a compound having a mass average molecular weight (Mw) of 20,000 or more and at least one repeating unit.

The film for forming a resin film used in the aspect of the invention can provide flexibility and film-forming property by containing the polymer component (A), and can maintain the sheet property maintainability.

The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, still more preferably 10 as the above viewpoint. 10,000 to 1.5 million.

Further, in the present specification, the value of the mass average molecular weight (Mw) of the polymer component or the like is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically, according to the examples. The value measured by the method described.

The content of the polymer component (A) is preferably from 5 to 50% by mass, more preferably from 8 to 40% by mass, even more preferably from 10 to 35%, based on the total mass (100% by mass) of the film for forming a resin film. The mass% is more preferably 15 to 30% by mass.

In the present specification, for example, the content of the component (A) is "the total mass (100% by mass) of the film for forming a resin film". The content of the other components described below is also the same as that of the content of the component (A) of the total mass (100% by mass) of the active ingredient in the composition for forming a film for forming a resin film.

In other words, the term "the total mass (100% by mass) of the film for forming a resin film" can be changed to "effective for the composition which is a material for forming a film for forming a resin film". The term "full quality (100% by mass) of the ingredients".

Further, the term "active ingredient" as used herein means a component which removes a substance which does not affect the direct or indirect reaction of the solvent in the composition or the physical properties of the formed sheet, and specifically means the composition. A component other than the solvent such as water or an organic solvent contained in the substance.

The polymer component (A) is preferably an acrylic polymer (A1), but may contain a polyester other than the acrylic polymer (A1), a phenoxy resin, a polycarbonate, a polyether, or a polyamine. Non-acrylic polymer (A2) such as ethyl carbureate, polysiloxane or rubber-based polymer.

These polymer components can be used individually or in combination of 2 or more types.

The total mass (100% by mass) of the polymer component (A) contained in the film for forming a resin film used in one aspect of the present invention is preferably 50% as the content of the acrylic polymer (A1). 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass.

(acrylic polymer (A1))

The mass average molecular weight (Mw) of the acrylic polymer (A1), from the pair of trees From the viewpoint of imparting flexibility and film-forming property to the film for forming a lipid film, it is preferably from 20,000 to 3,000,000, more preferably from 100,000 to 1.5 million, and even more preferably from 150,000 to 1.2 million, and even better. It is 250,000 to 1 million.

The glass transition temperature (Tg) of the acrylic polymer (A1) is preferably -40 ° C or more from the viewpoint of adjusting the peeling forces (α1), (β1), and (β2) in the above range, and more preferably -20~50°C, more preferably -10~30°C, and even more preferably 0~20°C.

Calculating the absolute temperature of the still, the following formula will be the value of line (1) at the glass transition temperature of the present specification, the acrylic polymer (Tg) of: glass transition temperature (a Tg of _K) (unit K) expressed in terms of Celsius temperature (Unit: °C) The value.

[In the above formula (1), W ₁ , W ₂ , W ₃ and W ₄ ‧ ‧ ‧ represent the mass fraction (% by mass) of the monomer component constituting the resin component, and Tg ₁ , Tg ₂ , Tg ₃ , Tg ₄ ‧‧‧ indicates the glass transition temperature (unit: K) of the homopolymer constituting each monomer component of the resin component.

Examples of the acrylic polymer (A1) include a polymer having a (meth)acrylic acid alkyl ester as a main component, and specifically, a (meth)acrylic acid having an alkyl group derived from a carbon number of 1 to 18. The acrylic polymer of the ester constituent unit (a1) is preferably a constituent unit (a1) from the viewpoint of adjusting the peeling forces (α1), (β1), and (β2) within the above range. Acrylic copolymerization of other constituent units (a2) other than the constituent unit (a1) Better.

The acrylic polymer (A1) may be used alone or in combination of two or more.

When the acrylic polymer (A1) is a copolymer, the form of the copolymer may be any one of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

The number of carbon atoms of the alkyl group of the (meth)acrylic acid alkyl ester constituting the unit (a1) is preferably from 1 to 18, more preferably from the viewpoint of imparting flexibility and film forming properties to the film for forming a resin film. It is 1~12, and even more preferably 1~8.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentane (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isophthalic acid (meth)acrylate Ester, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.

In addition, these (meth)acrylic acid alkyl esters can be used individually or in combination of 2 or more types.

Among these, an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms is preferred, and more preferably methyl (meth)acrylate.

The content of the constituent unit (a1-1) derived from the alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms in the acrylic polymer (A1), relative to the entire acrylic polymer (A1) The constituent unit (100% by mass) is preferably 5 to 98% by mass, more preferably 10 to 95% by mass, still more preferably 20 to 90% by mass.

Still, adjust the peeling force (α1), (β1), and (β2) The acrylic polymer (A1) used as one aspect of the present invention has a composition derived from an alkyl (meth)acrylate derived from an alkyl group having 1 to 3 carbon atoms, from the viewpoint of the range of the above-mentioned range. a unit (a1-1) and a constituent unit derived from an alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms (preferably 4 to 12, more preferably 4 to 8) (a1-2) The copolymer is preferred.

The content ratio [(a1-1)/(a1-2)]) of the constituent unit (a1-1) and the constituent unit (a1-2) is preferably 1/99 to 99/1, more preferably 10/90. ~90/10, and even better 15/85~85/15.

The content of the constituent unit (a1) in the acrylic polymer (A1) is preferably 50 to 100% by mass, more preferably 60%, based on the total constituent unit (100% by mass) of the acrylic polymer (A1). 99% by mass, and more preferably 70 to 95% by mass.

The acrylic polymer (A1) may have a constituent unit (a2) derived from a monomer other than the above-described constituent unit (a1), insofar as the effects of the present invention are not impaired.

Examples of the monomer constituting the structural unit (a2) include a functional group-containing monomer having a functional group such as a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer; a vinyl ester monomer such as vinyl propionate; an olefin monomer such as ethylene, propylene or isobutylene; an aromatic vinyl monomer such as styrene, methyl styrene or vinyl toluene: butadiene or different a diene monomer such as pentadiene; a nitrile monomer such as (meth)acrylonitrile;

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (methyl). a hydroxy(meth)acrylic acid alkyl ester such as acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; An unsaturated alcohol such as vinyl alcohol or allyl alcohol.

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

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) (methyl). An epoxy group-containing (meth) acrylate such as methyl acrylate or 3-epoxycyclo-2-hydroxypropyl (meth) acrylate; glycidyl crotonate or allyl glycidyl ether; a non-acrylic epoxy group-containing monomer;

In addition, an acrylic polymer having a Mw of 20,000 or more in a constituent unit derived from an epoxy group-containing monomer is thermosetting, but is not a curable component (B) but is included in a polymer component. The concept of (A).

From the viewpoint of adjusting the peeling forces (α1), (β1), and (β2) within the above range, the acrylic polymer (A1) used in one aspect of the present invention, and the constituent unit (a1) A copolymer having a constituent unit (a2-1) derived from a hydroxyl group-containing monomer is preferred.

The content of the constituent unit (a2-1) of the hydroxyl group-containing monomer derived from the acrylic polymer (A1) is preferably 1 in terms of the total constituent unit (100% by mass) of the acrylic polymer (A1). ~40% by mass, more preferably 2 to 30% by mass, still more preferably 5 to 25% by mass.

And, in particular, adjusting the peeling force (α1) to the above range In view of the above, the acrylic polymer (A1) used in one aspect of the present invention preferably has a copolymer having a constituent unit (a2-2) derived from a nitrile monomer together with the constituent unit (a1). .

The content of the constituent unit (a2-2) derived from the nitrile monomer in the acrylic polymer (A1) is preferably 1 to the total constituent unit (100% by mass) of the acrylic polymer (A1). 40% by mass, more preferably 2 to 35% by mass, still more preferably 5 to 30% by mass.

When the content of the constituent unit of the epoxy group-containing monomer in the acrylic polymer (A1) is increased, the adhesion between the obtained film for forming a resin film and the germanium and the wafer is improved, and the peeling force is increased ( The tendency of the value of α1). Therefore, in one aspect of the invention, the content of the constituent unit derived from the epoxy group-containing monomer in the acrylic polymer (A1) is preferably as small as possible.

The content of the constituent unit derived from the epoxy group-containing monomer in the acrylic polymer (A1) is preferably 0 to 4 based on the total constituent unit (100% by mass) of the acrylic polymer (A1). The mass% is more preferably 0 to 3 mass%, more preferably 0 to 2 mass%, and still more preferably 0 mass%.

When an epoxy-based thermosetting component is used as the curable component (B) to be described later, since the carboxyl group and the epoxy-based thermosetting component react with the epoxy group, the acrylic polymer (A1) is derived. The content of the constituent unit of the carboxyl group-containing monomer is preferably as small.

When the epoxy-based thermosetting component is used as the curable component (B), the content of the constituent unit derived from the carboxyl group-containing monomer is based on the total constituent unit (100% by mass) of the acrylic polymer (A1). It is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 2% by mass, and still more Good is 0% by mass.

The content of the constituent unit (a2) in the acrylic polymer (A1) is preferably from 1 to 40% by mass, more preferably from 2 to 40% by mass based on the total constituent unit (100% by mass) of the acrylic polymer (A1). 35 mass%, more preferably 5-30 mass%.

(non-acrylic polymer (A2))

The film for forming a resin film to be used in the present invention may contain a non-acrylic polymer (A2) as a polymer component of Mw 20,000 or more other than the above acrylic polymer (A1).

Examples of the non-acrylic polymer (A2) include polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polyoxyalkylene, and rubber-based polymer.

These non-acrylic polymers (A2) can be used individually or in combination of 2 or more types.

In addition, the phenoxy resin having an epoxy group having a Mw of 20,000 or more has thermosetting property, but is not a curable component (B) but is included in the non-acrylic polymer (A2).

The mass average molecular weight (Mw) of the non-acrylic polymer (A2) is preferably 20,000 or more, more preferably 20,000 to 100,000, still more preferably 20,000 to 80,000.

[Sclerosing ingredient (B)]

The curable component (B) is used to cure the film for forming a resin film. The role of a hard resin film.

The film for forming a resin film to be used in the present invention is preferably one of the thermosetting component (B1) and the energy ray-curable component (B2) as the curable component (B), and is suppressed from the resin film. From the viewpoint of forming the color of the resin film formed of the film, the viewpoint of sufficiently curing the curing reaction, and the viewpoint of cost reduction, it is more preferable to include the thermosetting component (B1).

The thermosetting component (B1) is preferably a compound having at least a functional group having a reaction by heating, and more preferably a compound (B11) having an epoxy group.

Further, as the energy ray-curable component (B2), a compound (B21) having a polymerizable functional group which is reacted by irradiation with an energy ray is preferred.

The functional groups possessed by the hardening component such as this react with each other to form a three-dimensional network structure to effect hardening.

(thermosetting component (B1))

The thermosetting component (B1) is preferably an epoxy thermosetting component.

The epoxy-based thermosetting component is preferably a combination of a thermosetting agent (B12) in combination with a compound (B11) having an epoxy group.

Further, the epoxy group-containing compound (B11) and the thermosetting agent (B12) are compounds having a mass average molecular weight (Mw) of less than 20,000, which are distinguished from the above-mentioned polymer component (A).

A compound having a epoxy group having a mass average molecular weight (Mw) of 20,000 or more and a thermosetting agent are included in the polymer component (A).

Examples of the epoxy group-containing compound (B11) (hereinafter also referred to as "epoxy compound (B11)") include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, and adjacent Novolac type epoxy resin such as phenol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, benzene stretching skeleton A type epoxy resin or the like having an epoxy compound having two or more functional groups in the molecule.

These epoxy compounds (B11) can be used individually or in combination of 2 or more types.

When the mass average molecular weight (Mw) of the epoxy compound (B11) is less than 20,000, it is used in combination with the component (A) to suppress the viscosity of the composition for forming a film for forming a resin film, and to improve the workability. Preferably, it is preferably 10,000 or less, more preferably 100 to 10,000.

In particular, from the viewpoint of adjusting the peeling force (α1) to the above range, the composition which is a material for forming a film for forming a resin film, as the epoxy compound (B11), contains a liquid epoxy at 25 ° C. Compounds and solid epoxy compounds are preferred.

As a content ratio of the liquid epoxy compound to the solid epoxy compound contained in the composition, [liquid epoxy compound/solid epoxy compound], from the viewpoint of adjusting the peeling force (α1) to the above range Preferably, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 20/80 to 80/20, and even more preferably 30/70 to 70/30.

Further, the more the ratio of the epoxy compound having a liquid is increased, the larger the value of the peeling force (α1) is, and the more the ratio of the solid epoxy compound is, the peeling force is increased. The value of (α1) tends to decrease.

The content of the epoxy compound (B11) is preferably from 1 to 500 parts by mass, more preferably from 3 to 300 parts by mass, even more preferably from 10 to 150 parts by mass, more preferably 100 parts by mass based on the component (A). It is 20 to 120 parts by mass.

(thermal hardener (B12))

The heat hardener (B12) functions as a hardener for the epoxy compound (B11).

As the thermosetting agent, a compound having two or more functional groups reactive with an epoxy group in one molecule is preferred.

Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid anhydride. Among these, a phenolic hydroxyl group, an amine group, or an acid anhydride is preferred, and a phenolic hydroxyl group and an amine group are more preferred, and an amine group is more preferred.

Examples of the phenolic thermosetting agent having a phenol group include a polyfunctional phenol resin, a biphenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, a neophenol (xylok) type phenol resin, and an aralkyl group. Type phenol resin, etc.

Examples of the amine-based thermosetting agent having an amine group include dicyandiamide (DICY) and the like.

These heat hardeners (B12) can be used individually or in combination of 2 or more types.

The content of the thermal curing agent (B12) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, per 100 parts by mass of the epoxy compound (B11).

(hardening accelerator (B13))

In order to adjust the rate of thermal hardening of the film for resin film formation, a hardening accelerator (B13) can be used. The hardening accelerator (B13) is preferably used as the thermosetting component (B1) in combination with the epoxy compound (B11).

Examples of the curing accelerator (B13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- An imidazole such as hydroxymethylimidazole; an organic phosphine such as tributylphosphine, diphenylphosphine or triphenylphosphine; tetraphenylphosphonium tetraphenylborate; triphenylphosphine tetraphenylborate; Tetraphenyl boron salt and the like.

These hardening accelerators (B13) can be used individually or in combination of 2 or more types.

The content of the hardening accelerator (B13) is improved from the viewpoint of the improvement of the adhesion of the resin film formed of the film for forming a resin film and the reliability of the wafer with the resin film obtained by using the composite sheet. The total amount of the epoxy compound (B11) and the thermosetting agent (B12) is 100 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, still more preferably 0.3 to 4 parts by mass.

(energy line hardening component (B2))

As the energy ray-curable component (B2), a compound (B21) having a polymerizable functional group which is reacted by irradiation with an energy ray can be used alone, but a photopolymerization initiator (B22) is combined with the compound (B21). Use is better.

(Compound (B21) having a functional group reactive by irradiation with an energy ray)

The compound (B21) (hereinafter also referred to as "energy ray reactive compound (B21)) having a polymerizable functional group which is reacted by irradiation with an energy ray has a (meth) acrylonitrile group, a vinyl group, etc. The compound of the polymerizable functional group may be, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy five ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, oligoester (A) Acrylate, urethane (meth) acrylate oligomer, epoxy (meth) acrylate, polyether (meth) acrylate, itaconic acid oligomer, and the like.

These energy ray-reactive compounds (B21) can be used individually or in combination of 2 or more types.

Further, the energy ray-reactive compound (B21) is a compound having a mass average molecular weight (Mw) of less than 20,000 and is distinguished from the above-mentioned polymer component (A).

An energy ray-reactive compound having a mass average molecular weight (Mw) of 20,000 or more is included in the polymer component (A).

The mass average molecular weight (Mw) of the energy ray-reactive compound (B21) is preferably less than 20,000, but is preferably from 100 to 15,000, more preferably from 300 to 10,000.

The content of the energy ray-reactive compound (B21) is preferably from 1 to 1,500 parts by mass, more preferably from 3 to 100 parts by mass based on the component (A). 1200 parts by mass.

(Photopolymerization initiator (B22))

By using the photopolymerization-reactive compound (B21) together with the above-mentioned photopolymerization initiator (B22), the polymerization hardening time can be shortened, and even if the amount of light irradiation is reduced, the film for forming a resin film can be hardened.

Examples of the photopolymerization initiator (B22) include a benzoin compound, an acetophenone compound, a mercaptophosphine oxide compound, a titanocene compound, a thioxanthone compound, and a peroxide compound.

As a more specific photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethyl Tetramethyl thiuram monosulfide, azobisisobutyronitrile, dibenzyl, diethyl hydrazine, β-chloropurine, 2,4,6-trimethylbenzhydryldiphenyl oxide Phosphine and the like.

These photopolymerization initiators can be used alone or in combination of two or more.

The content of the photopolymerization initiator (B22) is more than 100 parts by mass of the energy ray-reactive compound (B21) from the viewpoint of sufficiently suppressing the curing reaction of the film for forming a resin film and suppressing the formation of the residue. Preferably, it is 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass.

The content of the curable component (B) is preferably from 5 to 50% by mass, more preferably from 8 to 40% by mass, even more preferably from 10 to 30%, based on the total mass (100% by mass) of the film for forming a resin film. The mass% is more preferably 12 to 25% by mass.

Further, the content of the curable component (B) includes the above-mentioned epoxy compound (B11), thermosetting agent (B12), and thermosetting component (B1) of the curing accelerator (B13), and energy is contained therein. The total content of the energy ray-curable component (B2) of the linear reactive compound (B21) and the photopolymerization initiator (B22).

[Inorganic filler (C)]

The film for resin film formation used in one aspect of the invention preferably further comprises an inorganic filler (C).

By including the inorganic filler (C), the coefficient of thermal expansion of the resin film formed of the film for forming a resin film can be adjusted to an appropriate range, and the thermal expansion coefficient of the wafer with the resin film can be optimized to be incorporated into the The reliability of semiconductor devices for wafers. Further, the moisture absorption rate of the resin film formed of the film for forming a resin film can be reduced.

Examples of the inorganic filler (C) include powders such as cerium oxide, aluminum oxide, talc, calcium carbonate, titanium oxide, iron oxide, cerium carbide, and boron nitride, and spheroidized beads and single crystal fibers. And glass fiber and so on.

These inorganic fillers (C) can be used individually or in combination of 2 or more types.

Among these, cerium oxide and aluminum oxide are preferred.

The average particle diameter of the inorganic filler (C) is preferably from 0.01 to 50 μm, more preferably from 0.05 to 30 μm, still more preferably from 0.1 to 10 μm.

Further, in the present invention, the average particle diameter of the inorganic filler (C) means a value measured by a laser diffraction scattering type particle size distribution measuring apparatus, and means a volume median diameter (D ₅₀ ).

The content of the inorganic filler (C) is preferably from 15 to 80% by mass, more preferably from 20 to 75% by mass, even more preferably from 30 to 70%, based on the total mass (100% by mass) of the film for forming a resin film. The mass% is more preferably 40 to 65 mass%, and particularly preferably 45 to 60 mass%.

In addition, as the content of the inorganic filler in the film for forming a resin film increases, the values of the peeling forces (α1) and (β1) (especially the value of the peeling force (β1) tend to decrease.

[Colorant (D)]

In the film for forming a resin film to be used in one aspect of the invention, it is preferred to further contain a colorant (D).

When the film for forming a resin film contains the colorant (D) and the semiconductor wafer having the resin film formed of the film for forming a resin film is assembled in a device, infrared rays or the like generated from the surrounding device can be shielded from being blocked. Failure of the semiconductor wafer.

As the colorant (D), organic or inorganic pigments and dyes can be used.

As the dye, for example, any of an acid dye, a reactive dye, a direct dye, a disperse dye, a cationic dye, or the like can be used.

Further, the pigment is not particularly limited, and can be appropriately selected from known pigments.

Among these, the shielding property from electromagnetic waves or infrared rays is good, and the visibility of the laser marking method is improved, and it is preferably black. material.

Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon. From the viewpoint of improving the reliability of the semiconductor wafer, carbon black is preferred.

In addition, these coloring agents (D) can be used individually or in combination of 2 or more types.

The content of the colorant (D) is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, even more preferably 0.1 to 15% by mass based on the total mass (100% by mass) of the film for forming a resin film. %, and even more preferably 0.15 to 5% by mass.

[coupler (E)]

In the film for forming a resin film to be used in one aspect of the invention, it is preferred to further contain a coupling agent (E).

By including the coupling agent (E), the resin film formed of the obtained film for forming a resin film can improve heat resistance without impairing heat resistance.

As the coupling agent (E), a compound which reacts with a functional group possessed by the component (A) or the component (B) is preferred, and a decane coupling agent is more preferred.

Examples of the decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, and β-(3,4-epoxycyclohexyl). Ethyltrimethoxydecane, γ-(methacryloxypropyl)trimethoxynonane, γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)-γ-amine Propyltrimethoxydecane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ -ureidopropyltriethoxydecane, gamma-mercaptopropyltrimethoxysulfonium Alkane, γ-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfane, methyltrimethoxydecane, methyltriethoxydecane, vinyl trimethyl Oxydecane, vinyl triethoxy decane, imidazolium, and the like.

These coupling agents (E) can be used alone or in combination of two or more.

As the coupling agent (E), an oligomer type coupling agent is preferred.

The molecular weight of the coupling agent (E) which also includes the oligomer-type coupling agent is preferably from 100 to 15,000, more preferably from 150 to 10,000, still more preferably from 200 to 5,000, still more preferably from 250 to 3,000, and further More preferably 350~2000.

In addition, it is considered that the polymer component (A) in the film for forming a resin film or the surface of the wafer which is the object to be deposited is contained in the resin film-forming sheet by the inclusion of the coupling agent (E). The surface of the filler (C) is bonded to enhance adhesion or agglutination, and also increases the value of the peeling force (α1).

Therefore, the content of the coupling agent (E) is from the viewpoint of adjusting the peeling forces (α1), (β1), and (β2) within the above range, particularly from the viewpoint of the adjustment of the peeling force (α1). It is better to use less.

From the above viewpoints, the content of the coupling agent (E) is preferably 0.01 to 4% by mass, more preferably 0.05 to 2% by mass, more preferably 0.05 to 2% by mass, based on the total mass (100% by mass) of the film for forming a resin film. Preferably, it is 0.10 to 1.5% by mass, and more preferably 0.15 to 1% by mass.

[General Additives (F)]

The film for forming a resin film to be used in one aspect of the present invention may contain a general-purpose additive (F), if necessary, in addition to the above-described components, insofar as the effects of the present invention are not impaired.

Examples of the general-purpose additive (F) include a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a getter, a chain transfer agent, and the like.

The content of each of the general-purpose additives (F) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably the total mass (100% by mass) of the film for forming a resin film. It is 0 to 2% by mass.

<Method for Producing Film for Forming Resin Film>

The method for producing a film for forming a resin film which is one aspect of the present invention is not particularly limited, and it can be produced by a known method.

For example, a composition for forming a resin film containing each of the above components is prepared, and then an organic solvent is appropriately added and diluted to obtain a solution of a composition for forming a resin film. Further, the solution for forming the resin film forming composition is applied to the support sheets 10, 10' by a known coating method to form a coating film, and the coating film is dried to form a solution. A film for forming a resin film.

The organic solvent to be used for preparation of the solution for forming a resin film may, for example, be toluene, ethyl acetate or methyl ethyl ketone.

The solid content concentration of the solution of the resin film-forming composition in the case of blending the organic solvent is preferably from 10 to 80% by mass, more preferably from 20 to 70% by mass, and further More preferably 30 to 65 mass%.

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

The film for forming a resin film may be a single layer or a multilayer structure of two or more layers.

When a film for forming a resin film having a multilayer structure of two or more layers is produced, for example, a solution of a composition for forming a specific resin film is applied onto two or more support sheets to form a coating film, and each of the formed coating films is superposed. After the film of the coating film is formed, a film for forming a resin film composed of a multilayer structure can be produced by drying.

In addition, the thickness of the film for forming a resin film of the composite sheet of one aspect of the present invention is preferably 3 to 300 μm, more preferably 5 to 250 μm, still more preferably 7 to 200 μm, although it is appropriately set depending on the application. In addition, even when the film for forming a resin film has a multilayer structure, it is preferable that the total thickness is within the above range.

<support sheet>

The support sheet used in one aspect of the present invention may, for example, be a sheet composed of only a base material or an adhesive sheet having an adhesive layer on the base material.

The support sheet of the composite sheet according to the aspect of the invention is a release sheet which is formed on the surface of the sheet for forming a resin film to prevent adhesion of dust or the like, or a surface for protecting the sheet for forming a resin film in a cutting step or the like. It A function of cutting a sheet or the like.

The thickness of the support sheet is appropriately selected depending on the application, but it is preferably from 10 to 500 μm, more preferably from 20%, from the viewpoint of imparting sufficient flexibility to the composite sheet and improving the adhesion of the tantalum wafer. 350 μm, more preferably 30 to 200 μm.

Further, the thickness of the above-mentioned support sheet is not the thickness of the base material constituting the support sheet, but the thickness of the layer or film is also included in the case of having the adhesive layer.

(substrate)

As the substrate constituting the support sheet, a resin film is preferable.

Examples of the resin film include a polyethylene film such as a low density polyethylene (LDPE) film or a linear low density polyethylene (LLDPE) film, a vinyl propylene copolymer film, a polypropylene film, a polybutylene film, and a poly Butadiene film, polymethylpentene film, polyvinyl chloride film, chlorinated ethylene copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate Diester film, polyurethane film, ethylene ‧ vinyl acetate copolymer film, ionomer resin film, ethylene ‧ (meth) acrylate copolymer film, ethylene ‧ (meth) acrylate copolymer film, Polystyrene film, polycarbonate film, polyimide film, fluororesin film, and the like.

The substrate to be used in one aspect of the present invention may be a single layer film composed of one type of resin film, or a laminated film in which two or more types of resin films are laminated.

Further, in one aspect of the invention, the surface-treated sheet can be used as a support sheet on the surface of the substrate such as the resin film described above.

These resin films may be crosslinked films.

Further, a resin film for coloring these or the like, or a printer or the like can be used.

Further, the resin film may be formed by extruding a thermoplastic resin by extrusion, and may be a stretched one, and may be formed by thinning and hardening a curable resin by a predetermined means.

Among these resin films, since they have excellent heat resistance and moderate flexibility, they have expandability, and a substrate containing a polypropylene film is preferable from the viewpoint of easy pickability.

Further, the structure of the substrate including the polypropylene film may be a single layer structure composed only of a polypropylene film, or a multilayer structure composed of a polypropylene film and another resin film.

When the film for forming a resin film is thermosetting, the resin film constituting the substrate has heat resistance, and damage due to heat of the substrate is suppressed, and occurrence of problems in the manufacturing process of the semiconductor device can be suppressed.

When a sheet composed of only a base material is used as the support sheet, the surface tension of the surface in contact with the surface (β) of the film for forming a resin film of the base material is adjusted from the peeling force (β1) to the above range. From the viewpoint of viewpoint, it is preferably 20 to 50 mN/m, more preferably 23 to 45 mN/m, still more preferably 25 to 40 mN/m.

The thickness of the substrate constituting the support sheet is preferably from 10 to 500 μm, more preferably from 15 to 300 μm, still more preferably from 20 to 200 μm.

(adhesive sheet)

An adhesive sheet which is used as a support sheet in one aspect of the invention may be an adhesive layer formed of an adhesive on a substrate such as the above-mentioned resin film.

The adhesive which is a material for forming the pressure-sensitive adhesive layer may, for example, be an adhesive composition containing an adhesive resin, and the pressure-sensitive adhesive composition may further contain a general-purpose additive such as the above-mentioned crosslinking agent or adhesion-imparting agent.

When the structure of the resin is used as the adhesive resin, for example, an acrylic resin, a urethane resin, a rubber resin, a silicone resin, a vinyl ether resin, or the like is used. In the case of the function, for example, an energy ray-curable adhesive or the like can be cited.

In one aspect of the present invention, from the viewpoint of adjusting the peeling force (β2) to the above range and improving the pick-up property, it is formed of an adhesive composition containing an energy ray-curable resin. The adhesive sheet of the adhesive layer is preferred.

The energy ray-curable resin is preferably a resin having a polymerizable group such as a (meth) acrylonitrile group or a vinyl group, and is preferably an adhesive resin having a polymerizable group.

Further, from the viewpoint of adjusting the peeling force (β1) and (β2) within the above range, it is preferable to use an adhesive containing an acrylic resin.

The acrylic resin is preferably an acrylic polymer having a constituent unit (x1) derived from an alkyl (meth)acrylate, and has a constituent unit (x1) and a monomer derived from a functional group-containing monomer. Unit (x2) of acrylic The copolymer is better.

The number of carbon atoms of the alkyl group of the alkyl (meth)acrylate is preferably from 1 to 18, more preferably from 1 to 12, still more preferably from 1 to 8.

The alkyl (meth)acrylate may be the same as the alkyl (meth)acrylate constituting the above-mentioned constituent unit (a1).

Further, the alkyl (meth)acrylate may be used alone or in combination of two or more.

The content of the constituent unit (x1) is usually 50 to 100% by mass, preferably 50 to 99.9% by mass, more preferably 60 to 99% by mass, based on the total constituent unit (100% by mass) of the acrylic polymer. More preferably, it is 70 to 95% by mass.

Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and an epoxy group-containing monomer. Specific examples of the individual monomers include a constituent unit (a2). The monomer examples are the same.

Further, these may be used alone or in combination of two or more.

The content of the constituent unit (x2) is usually 0 to 40% by mass, preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, more preferably 1 to 30% by mass, based on the total constituent unit (100% by mass) of the acrylic polymer. Good is 5~20% by mass.

Further, the acrylic resin to be used in one aspect of the present invention can be obtained by reacting an acrylic copolymer having the above-mentioned structural units (x1) and (x2) with a compound having an energy ray polymerizable group. An energy ray-curable acrylic resin.

The compound having an energy ray-polymerizable group may be a compound having a polymerizable group such as a (meth)acryl fluorenyl group or a vinyl group.

When the adhesive containing an acrylic resin is used, the crosslinking agent (β1) and (β2) are preferably contained in the above range, and it is preferable to contain a crosslinking agent together with the acrylic resin.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an imide crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent. From the viewpoint of adjusting the peeling force (β1) and (β2) to the above range, an isocyanate crosslinking agent is preferred.

The content of the crosslinking agent is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 15 parts by mass, even more preferably from 0.5 to 15 parts by mass, based on the total mass (100 parts by mass) of the acrylic resin contained in the above-mentioned pressure-sensitive adhesive. 10 parts by mass, and more preferably 1 to 8 parts by mass.

The adhesive film is applied to the above-mentioned resin film by a known coating method, and the formed film is dried to form a release film, thereby obtaining a substrate which is subjected to a release treatment. Support sheet.

Further, the adhesive may be further added to the diluent solvent to form a solution or may be in the form of a latex.

Further, in order to strengthen the substrate, that is, the resin film and the adhesive layer, the surface of the adhesive layer on which the resin film is provided may be subjected to roughening treatment by sandblasting or solvent treatment as desired; corona discharge treatment, Oxidation treatment of electron beam irradiation, plasma treatment, ozone treatment, ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.; and primer treatment.

As the surface tension of the adhesive layer of the adhesive sheet, From the viewpoint of adjusting the peeling force (β1) to the above range, it is preferably 20 to 50 mN/m, more preferably 23 to 45 mN/m, still more preferably 25 to 40 mN/m.

The thickness of the adhesive layer is preferably from 1 to 100 μm, more preferably from 2 to 80 μm, and particularly preferably from 3 to 50 μm.

<Jigs and layers>

The jig adhesive layer may be formed of a double-sided adhesive sheet having a substrate (core material) or an adhesive.

The base material (core material) may be a resin film which can be used as the above-mentioned base material, and is preferably a polypropylene film or a polyvinyl chloride film.

Further, examples of the above-mentioned adhesive include the same as the adhesive which is the material for forming the adhesive layer of the above-mentioned adhesive sheet.

The thickness of the adhesive layer is preferably from 1 to 200 μm, more preferably from 5 to 100 μm, still more preferably from 10 to 70 μm.

<carrier sheet>

The carrier sheet is not particularly limited as long as it can be peeled off during use, and examples thereof include a resin film which can be used as the above-mentioned substrate, or a sheet which is subjected to a release treatment on the surface of the resin film.

The thickness of the carrier sheet is not particularly limited, but is preferably 1 to 200 μm, more preferably 5 to 150 μm, still more preferably 10 to 100 μm.

[Use of Composite Sheet for Resin Film Formation]

The composite sheet of one aspect of the present invention is used in a flip chip type wafer half The back surface of the processed object such as a conductor wafer or a semiconductor wafer is pasted, and a resin film can be formed on the workpiece. This resin film has a function as a protective film for protecting the back surface of a processed object such as a semiconductor wafer or a semiconductor wafer. For example, when it is attached to a semiconductor wafer, since the resin film has a function of reinforcing the wafer, damage of the wafer or the like can be prevented.

The resin film formed of the film for forming a resin film of the composite sheet according to one aspect of the present invention can also impart a function as a film. Then, the film is usually adhered to the back surface of the semiconductor wafer or the like, and is cut into individual wafers by a dicing step, and then placed on a substrate or the like (grain bonding) at a predetermined portion, and the semiconductor wafer is subsequently subjected to a thermal curing step. Fixed and used.

Further, the composite sheet according to an aspect of the present invention can be used as a sheet for fixing a workpiece such as a semiconductor wafer during blade cutting or laser cutting, and can be laminated to a cutting sheet in other manners without cutting. The manufacturing steps of the semiconductor device can be simplified.

In addition, the composite sheet of the present invention, that is, even in the prior cutting method (the semiconductor wafer is formed on the side of the circuit surface to form a groove having a deeper thickness than the wafer, and is thinned from the back side of the semiconductor wafer by at least reaching the groove) The method of obtaining a wafer group can also be used, and can be used by pasting through a chip group.

[Method of Manufacturing Wafer with Resin Film]

Hereinafter, an example of a method of producing a wafer with a resin film will be described using a composite sheet of one aspect of the present invention.

For example, a method for producing a wafer with a resin film as an aspect of the present invention includes a method of cutting by a blade in the following steps (1) to (4).

Step (1): a step of adhering a composite film for forming a resin film according to an aspect of the present invention to a back surface of the workpiece; and (2): a step of cutting the processed product (3): a resin film Step (4) of forming a resin film into a film: a step of picking up the processed product obtained by the step (2) to obtain a wafer.

Further, in the method of manufacturing a wafer with a resin film according to an aspect of the present invention, the steps (2) to (4) after the step (1) may be, for example, "steps (1), (2), ( The order of 3) and (4)" may also be the order of "steps (1), (3), (2), (4)" or "steps (1), (2), (4)). , (3)" order.

<Step (1)>

The step (1) is a step of adhering a film for forming a resin film of a composite sheet of one aspect of the present invention to the back surface of a workpiece such as a tantalum wafer.

The processed material used in this step may be a germanium wafer, and may be a compound semiconductor wafer such as gallium or arsenic. Further, the semiconductor wafer is formed on the surface of the circuit, and is suitable for grinding the back surface or the like, and has a thickness of 50 to 500 μm.

Here, the composite sheet of the present invention is excellent in reworkability, and in this step, if the adhesion between the processed product and the composite sheet cannot be successfully completed, the re-bonding can be performed. That is, on the back of the workpiece In the above, even if the film for forming a resin film of the composite sheet is adhered, the composite sheet can be cleanly peeled off from the workpiece. The surface of the processed product after the peeling of the composite sheet is difficult to be used because the residue of the film for forming a resin film is difficult to be used.

<Step (2)>

Step (2) is a step of cutting the workpiece into each circuit formed on the surface and processing the wafer.

In addition, the processed object which is the object to be cut in this step may be a processed product of the film for forming a resin film obtained by the step (1), or may be subjected to the step (3) after the step (1). A processed product of the resin film obtained.

Still, the cutting of the workpiece can be carried out by a known method.

Here, after the step (1), the processed product of the film for forming a resin film to be formed is obtained by the step, and in the next step (3), the resin film is formed from the film for forming a resin film, thereby obtaining a A processed product of a resin film to be cut.

On the other hand, when the step (1) is followed by the step (3), the processed product of the resin film is cut in this step to obtain a processed product of the cut resin film.

<Step (3)>

The step (3) is a step of forming a resin film from a film for forming a resin film adhered to a composite sheet of a workpiece.

In general, the resin film is formed by curing a film for forming a resin film. However, if the film for forming a resin film itself has a function of a protective film or a film, the film for forming an uncured resin film can be directly used as a resin film.

Further, the formed resin film may be completely cured, and may be partially cured, but it is preferably completely cured.

The curing of the film for forming a resin film can be carried out by any of the types of the curable component contained in the film for forming a resin film, which is cured by thermal curing and irradiation with energy rays.

As a condition for performing thermal curing, the curing temperature is preferably from 100 to 150 ° C, and the curing time is preferably from 1 to 3 hours.

Further, the condition for curing by the irradiation of the energy ray is appropriately set by the type of the energy ray used. For example, when ultraviolet rays are used, the illuminance is preferably 170 to 250 mW/cm ² and the amount of light is 600 to 1000 mJ/cm ² .

<Step (4)>

The step (4) is a step of obtaining a wafer by picking up the processed workpiece obtained by the step (2) by a general means such as a chuck. By this step, individualized wafers can be obtained.

When the resin film forming film is cured to form a resin film in the step (3), the peeling force (β2) required to peel the support sheet from the surface (β') of the resin film is in the above range, and is picked up. The suitability is good, and the productivity of the wafer with the resin film can be improved.

Further, the surface of the film for forming an uncured resin film, Even in the case of the peeling force required for peeling off the supporting sheet, the same range as the peeling force (β2) described above is preferable.

When an unhardened film for forming a resin film and a composite sheet laminated with an adhesive sheet as a supporting sheet are used, the adhesive sheet preferably has an adhesive layer formed of an adhesive composition containing an energy ray-curable resin. .

In the case of the adhesive sheet having such an adhesive layer, the adhesion of the adhesive layer can be lowered by irradiating the energy ray before the picking operation in this step, and the pickup property can be improved. In this way, it is considered that the surface of the film for forming an uncured resin film is easily immersed by irradiation of the energy ray, and the value of the peeling force required to peel off the adhesive sheet is adjusted to be in the same range as the peeling force (β2) described above.

The wafer with the resin film obtained through the above steps can be fabricated by flip-chip mounting on a substrate or the like to obtain a semiconductor device. Further, a wafer with a resin film as a function of a bonding film can be obtained by following a die pad portion or another member such as a semiconductor wafer (on the wafer mounting portion).

[Examples]

In the following description, the mass average molecular weight (Mw) and the glass transition temperature (Tg) of each component are measured or calculated by the method shown below.

<mass average molecular weight (Mw)>

Using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8220GPC"), the measurement was carried out under the following conditions, and the value measured in terms of standard polystyrene conversion was used.

(measurement conditions)

‧Tube: "TSK guard column HXL-H" "TSK gel GMHXL (×2)" "TSK gel G2000HXL" (all manufactured by Tosoh Corporation)

‧column temperature: 40 ° C

‧Expanding solvent: tetrahydrofuran

‧Flow rate: 1.0mL/min

<glass transition temperature (Tg)>

The value calculated by the above formula (1) is used.

Examples 1 to 9 and Comparative Example 1

Each of the components of the type and the amount of the mixture (the ratio of the active ingredient) shown in Table 1 was diluted with methyl ethyl ketone to prepare a resin film-forming composition for a resin film-forming film having a solid content of 61% by mass. Solution.

Further, on the surface of the carrier sheet (manufactured by Linde Co., Ltd., trade name "SP-PET3811", thickness: 38 μm) composed of a resin film having a surface subjected to the release treatment, the resin film was formed and coated. The solution of the composition was dried at 120 ° C for 2 minutes. Further, a film for forming a resin film having a thickness of 25 μm is formed on the carrier sheet. A laminate (1) comprising a carrier sheet and a film for forming a resin film.

Further, any one of the support sheets (I) to (VII) of the type shown in Table 1 is bonded to the film for forming a resin film of the laminate (1) to obtain a support sheet, a film for forming a resin film, and Carrier sheet This laminated laminated body (2).

When the support sheets (I), (II), and (IV) to (VII) are used, the film for forming a resin film and the adhesive layer of the support sheet are bonded together by direct lamination. It can be used as a laminate (2).

The preparation of the resin film-forming composition of the examples and the comparative examples was as follows. The details of the respective components described in Table 1 are as follows.

<polymer composition>

‧ (A-1): an acrylic copolymer (Mw = 850,000, Tg = 12 ° C) composed of ethyl acrylate (EA), n-butyl acrylate (BA), and acrylonitrile (AN).

‧(A-2): Acrylic acid copolymer composed of methyl acrylate (MA) and 2-hydroxyethyl acrylate (HEA) (MA/HEA=85/15 (% by mass), Mw=370,000, Tg= 6 ° C).

‧(A-3): Acrylic acid copolymer composed of methyl acrylate (MA), n-butyl acrylate (BA), 2-hydroxyethyl acrylate (HEA), and methyl glycidyl acrylate (GMA) MA/BA/HEA/GMA=70/10/15/5 (% by mass), Mw=800,000, Tg=-1°C).

<hardenable ingredients>

‧(B-1): A bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828", which is a liquid at 25 ° C and corresponds to a compound of the epoxy compound (B11)).

‧(B-2): bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER1055", which is solid at 25 ° C and corresponds to a compound of epoxy compound (B11)).

(B-3): a dicyclopentadiene type epoxy resin (manufactured by DIC Co., Ltd., trade name "Epiclon HP-7200HH", which is a solid at 25 ° C and corresponds to a compound of the epoxy compound (B11)).

(B-4): an amine-based curing agent (manufactured by ADEKA Co., Ltd., trade name "Adeka Hardener 3636AS", which corresponds to a compound of a thermosetting agent (B12)).

‧ (B-5): a hardening accelerator (manufactured by Shikoku Chemicals Co., Ltd., trade name "Curezo12PHZ", which corresponds to a compound of a hardening accelerator (B13)).

<Inorganic filler>

‧(C-1): cerium oxide filler (manufactured by Admatechs Co., Ltd., trade name "SC2050MA").

<colorant>

‧(D-1): Carbon black (manufactured by Mitsubishi Chemical Corporation, trade name "#MA650").

<decane coupling agent>

‧(E-1): decane coupling agent (manufactured by Japan Unika Co., Ltd., trade name "A-1110").

Further, the details of the support sheets described in Table 1 used in the examples and comparative examples are as follows.

‧Support sheet (I):

On the surface of the polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive sheet having an adhesive layer having a thickness of 90 μm formed of the adhesive (i) (surface tension of the surface of the adhesive layer = 30mN/m).

The adhesive (i) comprises an acrylic resin composed of 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), and 2-hydroxyethyl acrylate (HEA) (2EHA/MMA/ HEA=60/30/10 (% by mass), Mw=500,000) 100 parts by mass (solid content), and a trifunctional phthalic diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name) TAKENATE D110N") 10 parts by mass (solids).

‧Support sheet (II):

On the surface of the polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive sheet having an adhesive layer having a thickness of 90 μm formed of the adhesive (ii) (surface tension of the surface of the adhesive layer = 33mN/m).

The adhesive (ii) comprises an acrylic resin composed of 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), and 2-hydroxyethyl acrylate (HEA) (2EHA/MMA/ HEA=60/30/10 (% by mass), Mw=500,000 parts, 100 parts by mass (solid content), and a trifunctional phthalic diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name "TAKENATE D110N") 5 parts by mass (solid content ratio) .

‧Support sheet (III):

A support sheet composed only of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., surface tension = 35 mN/m) having a thickness of 80 μm.

‧Support sheet (IV):

On the surface of the polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive sheet of an adhesive layer having a thickness of 90 μm formed of an energy ray-curable adhesive (iii) was provided.

The energy ray-curable adhesive (iii) is obtained by dissolving 40 parts by mass of 2-ethylhexyl acrylate (2EHA), 40 parts by mass of vinyl acetate (VAc), and 20 parts by mass of 2-hydroxyethyl acrylate (HEA). Copolymerization of the obtained pre-copolymer (2EHA/VAc/HEA=40/40/20 (% by mass)), further comprising 21.4 parts by mass of methyl 2-isocyanatoethyl acrylate (relative to the hydroxyl group of HEA 100) An energy ray-curable acrylic copolymer obtained by reacting a molar %, an isocyanato group of 2-isocyanatoethyl methacrylate in an amount of 80 mol % (mass average molecular weight: 600,000) 100 parts by mass (solid content) and a trifunctional phthalic diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name "TAKENATE D110N") 5 parts by mass (solid content).

‧Support sheet (V):

On the surface of the polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive sheet having an adhesive layer having a thickness of 10 μm formed of an adhesive (iv) (surface tension of the surface of the adhesive layer = 33mN/m).

The adhesive (iv) comprises an acrylic resin composed of butyl acrylate (BA), methyl acrylate (MA), and 2-hydroxyethyl acrylate (HEA) (BA/MA/HEA=60/30/ 10 (% by mass), Mw = 800,000) 100 parts by mass (solid content), and a trifunctional phthalic diisocyanate crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name "TAKENATE D110N") 1 mass Parts (solids).

‧Support sheet (VI):

On the surface of the polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive sheet having an adhesive layer having a thickness of 10 μm formed of an adhesive (v) (surface tension of the surface of the adhesive layer = 29mN/m).

The adhesive (v) comprises an acrylic resin composed of 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), and 2-hydroxyethyl acrylate (HEA) (2EHA/MMA/ HEA=50/40/10 (% by mass), Mw=800,000) 100 parts by mass (solid content), and a trifunctional phthalic diisocyanate crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name) TAKENATE D110N") 10 parts by mass (solids).

‧Support sheet (VII):

On the surface of one side of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 80 μm, an adhesive having a thickness of 10 μm formed of an adhesive (vi) Adhesive sheet of the layer (surface tension of the surface of the adhesive layer = 33 mN/m).

The adhesive (vi) comprises an acrylic resin composed of butyl acrylate (BA), methyl acrylate (MA), and 2-hydroxyethyl acrylate (HEA) (BA/MA/HEA=60/30/ 10 (% by mass), Mw = 800,000 parts, 100 parts by mass (solid content), and a trifunctional phthalic diisocyanate-based crosslinking agent (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name "TAKENATE D110N") 2 mass Parts (solids).

The laminates (1) and (2) produced in the examples and the comparative examples were subjected to measurement of the peeling forces (α1), (β1), and (β2) by the following methods. Further, using the laminate (2), the evaluation of the reworkability of the tantalum wafer was carried out by the following method. The results of these are shown in Table 1.

<Measurement of peeling force (α1)>

On the surface of the film for forming a resin film, which is shown in the laminate (1), an adhesive tape (product name "PET25PLShin", manufactured by Linde Co., Ltd., having a resin film having a thickness of 25 μm) is used as a backup tape. The adhesive sheet of the adhesive layer having a thickness of 20 μm was adhered and cut into a size of 25 mm in width × 150 mm in length to prepare a test sample.

The carrier sheet of the test sample was removed, and the surface of the film for forming a resin film and the surface of a wafer (diameter: 6 inches, thickness: 500 μm) subjected to dry polishing were used, and a laminator (Fuji Co., Ltd.) was used. The product name "LAMIPACKER LPD3214" was pasted and allowed to stand for another 30 minutes.

After standing, a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS") was used, and a tensile test was performed at a peeling angle of 180°, a measurement temperature of 23° C., and a tensile speed of 300 mm/min. For the wafer, the load when the above-mentioned backup tape and the test sample were peeled off together was measured.

The measurement length was set to 100 mm, and the initial 10 mm and the last 10 mm were excluded from the effective value. The maximum value among the obtained measured values was defined as the peeling force (α1), which is shown in Table 1.

<Measurement of peeling force (β1)>

The laminate (2) was cut into a size of 25 mm in width × 150 mm in length, and the carrier sheet was removed, and the surface of the film for forming a resin film was used as a test sample.

The support plate made of polymethyl methacrylate and the surface of the film for forming a resin film formed on the test sample were passed through a double-sided tape (having a thickness of 25 μm made of polyethylene terephthalate). The double-sided tape having a 10 μm thick adhesive layer made of an acrylic adhesive on both sides of the substrate was bonded and allowed to stand for 30 minutes.

Further, the double-sided tape has the adhesive force for fixing the support sheet and the film for forming a resin film during the tensile test.

After standing, a precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS") was used, and a tensile test was performed at a peeling angle of 180°, a measurement temperature of 23° C., and a tensile speed of 300 mm/min. The surface (β) of the film for forming a resin film was measured for the load when the support sheets (I) to (IV) were peeled off.

The measurement length was set to 100 mm, and the initial 10 mm and the last 10 mm were excluded from the effective value. The minimum value among the obtained measured values was defined as the peeling force (β1), which is shown in Table 1.

<Measurement of peeling force (β2)>

The laminate (2) was cut into a size of 25 mm in width × 150 mm in length, and the carrier sheet was removed, and the surface of the film for forming a resin film was used as a test sample.

The surface of the film for resin film formation and the surface of the wafer (diameter: 6 inches, thickness: 500 μm) which was subjected to dry polishing were used, and a laminator (product name "LAMIPACKER LPD3214" manufactured by Fuji Co., Ltd.) was used. ) Paste and let stand for another 30 minutes.

After standing, it was heated at 130 ° C for 2 hours to cure the film for forming a resin film to form a resin film, and the same as the measurement of the peeling force (β1), and the support sheet was measured from the surface (β') of the resin film ( I)~(IV) The load at the time of peeling.

Yet, for the Example 4, a resin film, using a UV irradiation device (Lintec Corporation, product name "RAD2000m / 8", irradiated with ultraviolet rays (illuminance: 220mW / cm ^2, light amount: 190mJ / cm ^2), the The above measurement was carried out.

The measurement length was set to 100 mm, and the initial 10 mm and the last 10 mm were excluded from the effective value. The minimum value among the obtained measured values was defined as the peeling force (β2), which is shown in Table 1.

<Evaluation of reworkability of tantalum wafers>

The laminate (2) was cut into a size of 25 mm in width × 150 mm in length, and the carrier sheet was removed, and the surface (β) of the film for forming a resin film was used as a test sample.

The surface of the film for resin film formation and the surface of the wafer (diameter: 6 inches, thickness: 500 μm) which was subjected to dry polishing were used, and a laminator (product name "LAMIPACKER LPD3214" manufactured by Fuji Co., Ltd.) was used. ) Paste and let stand for another 30 minutes.

After standing, the precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS") was used, and the peeling angle was 180°, the measurement temperature was 23 ° C, and the tensile speed was 300 mm/min. The test sample (the support sheet and the film for forming a resin film) was peeled off, and a part of the film for forming a resin film was adhered to the surface of the tantalum wafer by visual observation. On top of this, the reworkability of the tantalum wafer was evaluated on the basis of the following criteria.

‧ "A+": No deposit of the film for forming a resin film was observed on the surface of the wafer.

‧ "A": On the surface of the wafer, no deposit of 5 mm or more in diameter of the film for forming a resin film was observed, and the deposit having a diameter of less than 5 mm was confirmed to be extremely small, but it was sufficiently soluble in alcohol or the like. The extent of removal.

‧ "B": On the surface of the wafer, no deposit of 10 mm or more in diameter of the film for forming a resin film was observed, and the number of deposits having a diameter of less than 10 mm was confirmed, but it was sufficiently removed by alcohol or the like. degree.

‧"C": A thin film for resin film formation was confirmed on the surface of the wafer. The deposit having a diameter of 10 mm or more of the film is difficult to remove by using alcohol or the like.

As is apparent from Table 1, it is understood that the film for forming a resin film produced in Examples 1 to 9 is superior in reworkability to the film for forming a resin film of Comparative Example 1.

[Industrial availability]

A composite sheet for forming a resin film according to an aspect of the present invention is suitable as a material for forming a protective film for protecting a back surface of a semiconductor wafer or for forming an adhesive film which can be applied to a die pad portion or other portions. material.

1a, 1b, 1c, 1d‧‧‧ composite film for forming a resin film (composite sheet)

10‧‧‧Support sheet

20‧‧‧film for resin film formation

21‧‧‧Surface (α)

22‧‧‧Surface (β)

40‧‧ ‧ fixtures

50‧‧‧ Carrier Sheet

Claims (9)

A composite sheet for forming a resin film which is formed by directly laminating a film for forming a resin film which can form a resin film on a support sheet, and satisfies the following requirements (I) and (II), and the element (I): After the surface (α) of the film for forming a resin film on the side of the same wafer is pasted on the wafer, the film has a stretching speed of 300 mm/min and a stretching angle of 180° in an environment of 23° C. The peeling condition (x) was tested, and the peeling force (α1) required for peeling the film for forming a resin film from the tantalum wafer was 0.05 to 10.0 N/25 mm; and the requirement (II): the peeling condition (x) In the test, the peeling force (β1) required to peel the support sheet from the surface (β) of the film for forming a resin film directly on the side of the support sheet is a value equal to or higher than the peeling force (α1). The composite sheet for forming a resin film according to claim 1, wherein the following requirement (III) is further satisfied, and the element (III) is tested by the peeling condition (x) when the resin film is formed of the film for forming a resin film. The peeling force (β2) required to peel the support sheet from the surface (β') of the resin film on the direct lamination side of the support sheet is 0.02 to 5.0 N/25 mm. The composite sheet for forming a resin film according to claim 1 or 2, wherein the peeling force (β1) is 0.05 to 20.0 N/25 mm. The composite sheet for forming a resin film according to claim 1 or 2, wherein the support sheet is a sheet composed only of a substrate. A composite sheet for forming a resin film according to claim 1 or 2, wherein the front The support sheet is an adhesive sheet having an adhesive layer on a substrate, and the surface of the adhesive film having the adhesive sheet and the surface (β) of the film for forming a resin film are directly laminated. The composite sheet for forming a resin film according to claim 5, wherein the adhesive layer is a layer formed of an adhesive composition containing an energy ray-curable resin. The composite sheet for forming a resin film according to claim 1 or 2, wherein the film for forming a resin film contains a polymer component (A) and a curable component (B). The composite sheet for forming a resin film according to claim 1 or 2, wherein the film for forming a resin film is a material for forming a protective film or a film. A method for producing a wafer with a resin film, comprising the following steps (1) to (4), wherein the resin film according to any one of claims 1 to 8 is formed on the back surface of the workpiece a step of bonding with a composite sheet; a step (2): a step of cutting the workpiece; a step (3): a step of forming a resin film from the film for forming a resin film; and a step (4): passing the step (2) The step of obtaining the wafer after the obtained processed product is picked up.