KR102343970B1 - Resin film-forming sheet, resin film-forming composite sheet, and silicon wafer regeneration method - Google Patents

Abstract

There is provided a sheet for forming a resin film attached to a silicon wafer to form a resin film on the silicon wafer, the sheet for forming a resin film satisfying the following requirements (I) to (III) and excellent in reworkability and end adhesion. Requirement (I): The surface roughness (Ra) of the surface (?) of the sheet for forming a resin film on the side to be adhered to the silicon wafer is 50 nm or less. Requirement (II): The adhesive force (α1) of the surface (α) of the sheet for forming a resin film to a silicon wafer is 1.0 to 7.0 N/25 mm. Requirement (III): The surface (β) of the sheet for forming a resin film on the side opposite to the side to be adhered to the silicon wafer with respect to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer of 10 to 50 µm in thickness formed of a specific pressure-sensitive adhesive The adhesive force (β1) is 4.0N/25mm or more.

Description

A sheet for forming a resin film, a composite sheet for forming a resin film, and a method of regenerating a silicon wafer

The present invention relates to a sheet for forming a resin film, a composite sheet for forming a resin film having a structure in which the sheet for forming a resin film is laminated on a support sheet, and a method for regenerating a silicon wafer.

DESCRIPTION OF RELATED ART In recent years, manufacture of the semiconductor device using the mounting method called a so-called face-down method is performed. In the face-down method, a semiconductor chip having electrodes such as bumps (hereinafter, simply referred to as a “chip”) is mounted on a circuit surface of a substrate, and the electrodes of the chip are joined to the substrate. For this reason, the surface of the chip on the opposite side to the side joined to the board|substrate (henceforth "the back surface of a chip") may become exposed.

A resin film containing an organic material is formed on the back surface of the exposed chip, and may be introduced into a semiconductor device as a chip with a resin film. The resin film functions as a protective film for preventing the occurrence of cracks after a dicing process or packaging, or as an adhesive film for adhering the obtained chip onto other members such as a die pad unit or a separate semiconductor chip. .

In general, this chip with a resin film is obtained by applying a solution of a composition containing a resin to the back surface of a wafer by a spin coating method or the like to form a coating film, then drying and curing the coating film to form a resin film. It is manufactured by dicing a wafer with a resin film.

In addition, by affixing a curable sheet for forming a resin film to the back surface of the wafer, and curing the sheet for forming a resin film by irradiation or heating with energy rays before and after dicing of the wafer to obtain a resin film, the wafer with a resin film Alternatively, a chip with a resin film may be manufactured.

As a material for forming a resin film that also functions as a protective film or an adhesive film on the back surface of such a chip or a wafer, various sheets for forming a resin film have been proposed.

For example, in Patent Document 1, an energy ray-curable protective film forming layer containing a polymer component containing an acrylic copolymer, an energy ray-curable component, a dye or a pigment, an inorganic filler, and a photoinitiator is sandwiched between two release sheets. A film for chip protection having is disclosed.

According to the description of Patent Document 1, the chip protection film can form a protective film with good laser marking recognition, hardness, and adhesion to the wafer by irradiation with energy rays, and compared with the conventional chip protection film, the process Simplification is possible.

Further, in Patent Document 2, a dicing tape integrated wafer back surface protective film having a dicing tape having a base material and an adhesive layer, and a wafer back surface protective film colored and having a predetermined elastic modulus on the adhesive layer of the dicing tape This is disclosed.

According to description of patent document 2, the said wafer back surface protective film WHEREIN: In the dicing process of a semiconductor wafer, the holding|maintenance force with a semiconductor wafer becomes favorable.

Japanese Patent Laid-Open No. 2009-138026 Japanese Patent Laid-Open No. 2010-199543

By the way, in the step of attaching the protective film described in Patent Documents 1 and 2 on the wafer, a shift in the position of the protective film to be attached on the wafer occurs, or the foreign material is also included on the wafer in a state where the foreign material is attached to the wafer. It may happen that the protective film is attached. In such a case, it is difficult to rework (re-peel) the protective film once affixed on the wafer from the wafer.

In particular, since the protective films disclosed in Patent Documents 1 and 2 are for the purpose of improving the adhesion to the wafer at the time of attachment and the holding force with the wafer after attachment, once attached on the wafer, the adhesion to the wafer is high, It is very difficult to work.

That is, when force is applied to forcibly peel the protective film adhered to the wafer, the wafer is damaged, or even if the protective film can be peeled without damaging the wafer, a part of the protective film may remain on the wafer.

In Patent Documents 1 and 2, with respect to the described protective film, examination is made from the viewpoint of adhesiveness with the wafer at the time of attachment and the holding force with the wafer after attachment, but examination of the reworkability of the protective film once adhered to the wafer is not done at all

In addition, recognizing the necessity of re-attaching the protective film is not only immediately after attaching the protective film and the wafer, but also after attaching, in the state of the laminate with the protective film on the wafer, when recognized after standing for about 24 hours there are many

Since the adhesiveness of a wafer and a protective film improves as time passes after attaching a protective film to a wafer, it is common that it is difficult to rework a protective film.

In addition, it is also conceivable to use a protective film in which the surface on the side to be attached to the wafer is designed to be rough with emphasis on reworkability after attachment to the silicon wafer. is easy to occur, and the problem of inferior end adhesiveness arises.

The present invention has been made in view of the above problems, a sheet for forming a resin film excellent in reworkability and edge adhesion, and a composite sheet for forming a resin film having a structure in which the sheet for forming a resin film is laminated on a support sheet, and a silicone An object of the present invention is to provide a method for regenerating a wafer.

The present inventors adjusted the surface roughness and adhesive force to the silicon wafer on the surface of the side to be adhered to the silicon wafer, and the adhesive force of the general adhesive sheet to the adhesive layer on the other surface opposite to the surface. It discovered that the sheet|seat for resin film formation could solve the said subject, and completed this invention.

That is, the present invention provides the following [1] to [10].

[1] A sheet for forming a resin film, which is adhered to a silicon wafer to form a resin film on the silicon wafer, and satisfies the following requirements (I) to (III).

Requirement (I): The surface roughness (Ra) of the surface (?) of the sheet for forming a resin film on the side to be adhered to the silicon wafer is 50 nm or less.

Requirement (II): The adhesive force (α1) of the surface (α) of the sheet for forming a resin film to a silicon wafer is 1.0 to 7.0 N/25 mm.

Requirement (III): A pressure-sensitive adhesive comprising 100 parts by mass of an acrylic resin having a structural unit derived from butyl acrylate and acrylic acid and having a mass average molecular weight of 600,000 to 1,000,000 and 0.01 to 10 parts by mass of a crosslinking agent, a thickness of 10 to 50 The adhesive force (β1) of the surface (β) of the sheet for forming a resin film on the opposite side to the side to be adhered to the silicon wafer with respect to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer of μm is 4.0 N/25 mm or more.

[2] The sheet for forming a resin film according to [1], wherein the storage elastic modulus at 23°C is 0.10 to 20 GPa.

[3] The sheet for forming a resin film according to [1] or [2], wherein a contact angle with respect to water on the surface (β) of the sheet for forming a resin film is 70 to 110°.

[4] The sheet for forming a resin film according to any one of [1] to [3], comprising a polymer component (A) and a curable component (B).

[5] The sheet for forming a resin film according to [4], wherein the polymer component (A) contains the acrylic polymer (A1).

[6] The resin film according to [5], wherein the acrylic polymer (A1) is an acrylic copolymer having a structural unit (a1) derived from an alkyl (meth)acrylate and a structural unit (a2) derived from a nitrile-based monomer. sheet for forming.

[7] The sheet for forming a resin film according to any one of [1] to [6], which is a sheet for forming a protective film for forming a protective film on a silicon wafer.

[8] A composite sheet for forming a resin film, wherein the sheet for forming a resin film according to any one of [1] to [7] is laminated on a support sheet.

[9] The composite sheet for forming a resin film according to [8], wherein the sheet for forming a resin film has a configuration in which the sheet is sandwiched by two supporting sheets.

[10] Rework of the sheet for forming a resin film from the laminate to which the surface (α) of the sheet for forming a resin film according to any one of [1] to [7] is directly adhered onto a silicon wafer, A method of regenerating wafers,

A method of regenerating a silicon wafer, comprising the following steps (1) to (2).

Process (1): The process of affixing the said adhesive layer of the adhesive sheet which has a base material and an adhesive layer on the surface (beta) of the said sheet|seat for resin film formation of the said laminated body.

Step (2): A step of reworking the sheet for forming a resin film adhered on the silicon wafer by pulling the pressure-sensitive adhesive sheet adhered to the surface (β) of the sheet for forming a resin film in the step (1).

The sheet for resin film formation of this invention is excellent in rework property and edge part adhesiveness.

Therefore, after the sheet for forming a resin film of the present invention is adhered to a silicon wafer once, when the necessity of re-attachment arises, the silicon wafer is not damaged, and a part of the adhered sheet for forming a resin film is placed on the silicon wafer. The said sheet for resin film formation can be reworked from a silicon wafer, suppressing adhering and remain|surviving. As a result, the said sheet for resin film formation can be reused about the silicon wafer after rework.

In addition, in this specification, "rework the sheet|seat for resin film formation" refers to peeling again the sheet for resin film formation once adhered on a silicon wafer.

In addition, the "rework property of the sheet for resin film formation" means that, when reworked after being attached to a silicon wafer, the silicon wafer is not damaged, and a part of the sheet for forming a resin film is not left on the silicon wafer. It refers to the property of being able to peel.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the composite sheet for resin film formation of one embodiment of this invention.

In the description of this specification, the values of the mass average molecular weight (Mw) and number average molecular weight (Mn) of each component are values in terms of standard polystyrene measured by gel permeation chromatography (GPC), specifically in Examples It is a value measured based on the described method.

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

In addition, in this specification, an "energy beam" points out, for example, an ultraviolet-ray, an electron beam, etc., and an ultraviolet-ray is preferable.

[Sheet for forming a resin film]

The sheet for forming a resin film of the present invention is a sheet for attaching to a silicon wafer and forming a resin film on the silicon wafer, and satisfies the following requirements (I) to (III).

Requirement (I): The surface roughness (Ra) of the surface (α) of the sheet for forming a resin film on the side to be adhered to the silicon wafer (hereinafter also simply referred to as “surface roughness (Ra) of the surface (α)”) is 50 nm or less.

Requirement (II): The adhesive force (α1) of the surface (α) of the sheet for forming a resin film to a silicon wafer (hereinafter also simply referred to as “adhesive force (α1) of the surface (α)”) is 1.0 to 7.0 N/25 is mm.

Requirement (III): A pressure-sensitive adhesive comprising 100 parts by mass of an acrylic resin having a structural unit derived from butyl acrylate and acrylic acid and having a mass average molecular weight of 600,000 to 1,000,000 and 0.01 to 10 parts by mass of a crosslinking agent, a thickness of 10 to 50 Adhesive force (β1) of the surface (β) of the sheet for forming a resin film on the opposite side to the side to be adhered to the silicon wafer with respect to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (hereinafter simply referred to as “surface (β)” also referred to as "adhesive force (β1)") is 4.0 N/25 mm or more.

The surface (α) of the sheet for forming a resin film of the present invention is the surface on the side to be adhered to the silicon wafer, and the surface (β) is for reworking the sheet for forming a resin film from the silicon wafer after adhesion to the silicon wafer. It is an adhesion surface with the adhesive layer of the general-purpose adhesive sheet to be affixed.

In addition, there is no restriction|limiting in particular in the form of the sheet|seat for resin film formation of this invention, For example, the form of a long tape shape, a single-leaf label, etc. may be sufficient.

The sheet for forming a resin film of one embodiment of the present invention may be a single-layer body formed of one type of composition, or a multi-layer body composed of two or more layers formed of two or more types of compositions.

Further, when the sheet for forming a resin film of one embodiment of the present invention is a multilayer body comprising two or more layers, the composition (α′), which is a material for forming the layer on the surface (α) side, and the layer on the surface (β) side are formed With respect to the composition (β'), which is a material, it is preferable to adjust the type and compounding amount of each component contained therein so as to satisfy the above requirements (I) to (III). Therefore, it is preferable that the composition (α′) and the composition (β′) are different from each other.

<Requirement (I)>

By satisfying the above requirement (I), the sheet for forming a resin film of the present invention suppresses the occurrence of floating or peeling at the edge of the wafer after adhesion to the wafer, and is excellent in edge adhesion.

That is, when the surface roughness (Ra) of the surface (α) exceeds 50 nm, when the sheet for forming a resin film obtained is adhered to a silicon wafer, the adhesion to the silicon wafer is insufficient, and particularly, the edge of the silicon wafer floats or It becomes easy to generate|occur|produce peeling and is inferior to edge part adhesiveness. When such a decrease in adhesiveness, particularly a decrease in edge adhesion, occurs, the washing water used for dicing enters the interface between the sheet for forming a resin film and the silicon wafer to contaminate the surface of the silicon wafer, or when dicing It causes the occurrence of chipping.

From the above viewpoint, the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film of one embodiment of the present invention is preferably 40 nm or less, more preferably 35 nm or less, still more preferably 30 nm or less. , more preferably 25 nm or less.

In addition, from the viewpoint of providing a sheet for forming a resin film with further improved reworkability, the surface roughness (Ra) of the surface (α) is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 more than nanometers.

In addition, in this specification, the surface roughness (Ra) of the surface (alpha) is a value measured based on JISB0601:2001, More specifically, it means the value measured by the method described in an Example.

In addition, the surface roughness (Ra) of the surface (α) can be adjusted by appropriately setting the type, average particle diameter, content, etc. of particulate components such as inorganic fillers and colorants that may be contained in the sheet for forming a resin film, for example. Moreover, on the surface (alpha) of the sheet|seat for resin film formation, the uneven|corrugated surface of the peeling film which has a rough surface is bonded together, and it can adjust also by the method of transcribe|transferring an uneven|corrugated shape.

<Requirement (II)>

By satisfying the requirement (II), the sheet for forming a resin film of the present invention can be reworked even after about 24 hours have elapsed while maintaining good adhesion after adhesion to a silicon wafer, particularly end adhesion, while maintaining good adhesion.

For example, as disclosed in Patent Documents 1 and 2, the conventional sheet for forming a resin film is often for the purpose of improving adhesion and retention with a silicon wafer, and the surface (α) specified in the requirement (II) The material design is made to increase the value of the adhesive force of

However, when the adhesive force (α1) of the surface (α) exceeds 7.0 N/25 mm, the rework after affixing the sheet for forming a resin film obtained to a silicon wafer tends to become difficult. In particular, since the adhesion between the silicon wafer and the sheet for forming a resin film improves as time elapses after adhesion to the silicon wafer, if the sheet for forming a resin film is forcibly reworked from the silicon wafer, the rework force As a result, the silicon wafer may be damaged.

On the other hand, when the adhesive force (α1) of the surface (α) is less than 1.0 N/25 mm, the adhesion to the silicon wafer is insufficient, and particularly, when the sheet for forming a resin film obtained is attached to the silicon wafer, it floats on the edge of the silicon wafer. It is easy to generate|occur|produce and peeling is inferior, and edge part adhesiveness is inferior.

Accordingly, in the sheet for forming a resin film of the present invention, the adhesive force (α1) of the surface (α) is adjusted within the range specified by the requirement (II).

The adhesive force (α1) of the surface (α) of the sheet for forming a resin film of one embodiment of the present invention is from the viewpoint of making the sheet for forming a resin film with improved adhesion to a silicon wafer, particularly, adhesion to an edge after adhesion to a silicon wafer, Preferably it is 1.3 N/25 mm or more, More preferably, it is 1.5 N/25 mm or more, More preferably, it is 1.8 N/25 mm or more, More preferably, it is 2.0 N/25 mm or more, and rework property is improved. From the viewpoint of forming a sheet for forming a resin film, preferably 6.8 N/25 mm or less, more preferably 6.5 N/25 mm or less, still more preferably 6.0 N/25 mm or less, still more preferably 5.5 N or less. /25mm or less.

In addition, in this specification, the adhesive force (α1) of the surface (α) means a value measured by the method described in Examples.

In addition, the adhesive force (α1) of the surface (α) is determined by the type and content of polymer components, curable components, inorganic fillers and additives, etc. contained in the composition, which is a material for forming a layer on the surface (α) side of the sheet for forming a resin film. It can be adjusted so that it may become the said range by selecting suitably. Concretely, if the matter in the item of each component contained in the sheet|seat for resin film formation is considered combining suitably, it can adjust easily.

<Requirement (III)>

By satisfying the requirement (III), the sheet for forming a resin film of the present invention can be reworked even after about 24 hours have elapsed.

After attaching the sheet for forming a resin film of the present invention to a silicon wafer, when it is necessary to peel the sheet for forming a resin film again, an adhesive layer of a general-purpose pressure-sensitive adhesive sheet on the surface (β) of the sheet for forming a resin film. By affixing and pulling the said adhesive sheet, the said sheet|seat for resin film formation can be reworked from a silicon wafer.

At this time, if the adhesive force (β1) of the surface (β) is less than 4.0 N/25 mm, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is attached to the surface (β), and the sheet for forming a resin film is peeled together with the pressure-sensitive adhesive sheet. Even if it does, the tendency for a part of the said sheet|seat for resin film formation to remain|survive on a silicon wafer is high, and the silicon wafer after rework cannot be reused.

From the above viewpoint, the adhesive force (β1) of the surface (β) of the sheet for forming a resin film of one embodiment of the present invention is preferably 4.5 N/25 mm or more, and more preferably 5.0 N/25 mm or more.

Moreover, although there is no restriction|limiting in particular as an upper limit of the adhesive force of the surface (beta), The adhesive force (beta) of the surface (beta) is normally 20 N/25 mm or less.

100 mass of an acrylic resin having a structural unit derived from butyl acrylate and acrylic acid and having a mass average molecular weight of 600,000 to 1,000,000, the adhesive force (β1) of the surface (β) of the sheet for resin film formation prescribed in the requirement (III) It is the adhesive force with respect to the said adhesive layer of the adhesive sheet which has a 10-50 micrometers-thick adhesive layer formed of part and the adhesive containing 0.01-10 mass parts of crosslinking agents.

The composition of this pressure-sensitive adhesive stipulates a commercially available general acrylic pressure-sensitive adhesive, and the requirement (III) defines the adhesive force of the surface (β) to the pressure-sensitive adhesive layer formed of the general acrylic pressure-sensitive adhesive.

In addition, the pressure-sensitive adhesive satisfying the requirement (III) is an extremely general acrylic pressure-sensitive adhesive widely distributed in the market.

Therefore, the selectivity of the pressure-sensitive adhesive sheet used when reworking the sheet for forming a resin film of the present invention from a silicon wafer is very wide. do.

In addition, the adhesive force (β1) of the surface (β) means the value measured by the method described in the Example more specifically.

In addition, the adhesive force (β1) of the surface (β) is the type and content of polymer components, curable components, inorganic fillers and additives, etc. contained in the composition which is a material for forming a layer on the surface (β) side of the sheet for forming a resin film. It can be adjusted so that it may become the said range by selecting suitably. Concretely, if the matter in the item of each component contained in the sheet|seat for resin film formation is considered combining suitably, it can adjust easily.

In the sheet for forming a resin film of one embodiment of the present invention, from the viewpoint of providing a sheet for forming a resin film with further improved reworkability, the adhesive force (β1) of the surface (β) is the adhesive force (α1) of the surface (α) It is preferable that it is a value higher than the adhesive force of

From the above viewpoint, the difference [(β1)-(α1)] between the adhesive force (β1) and the adhesive force (α1) is preferably 0 to 8.0 N/25 mm, more preferably 0.1 to 7.0 N/25 mm, further Preferably it is 0.5-6.0N/25mm, More preferably, it is 1.5-5.5N/25mm.

The storage elastic modulus at 23°C of the sheet for forming a resin film of one embodiment of the present invention is preferably 0.10 to 20 GPa, more preferably 0.15 to 15 GPa, still more preferably 0.20 to 10 GPa, still more preferably 0.30 to 5.0 GPa.

When the storage elastic modulus is 0.10 GPa or more, when the sheet for forming a resin film is attached to a silicon wafer and then peeled off again, a phenomenon in which the sheet for forming a resin film is changed as if pulling a thread is suppressed, and a resin film is formed on the silicon wafer The sheet for forming a resin film can be peeled off without leaving a part of the sheet for use.

On the other hand, if the said storage elastic modulus is 20 GPa or less, the adhesiveness to a silicon wafer can be made favorable.

In addition, in this specification, the storage elastic modulus of the sheet|seat for resin film formation means the value measured by the method described in an Example.

The contact angle with respect to water on the surface (β) of the sheet for forming a resin film of one embodiment of the present invention is preferably 70 to 110°, more It is preferably 75 to 100°, more preferably 80 to 95°, still more preferably 83 to 93°.

In addition, in this specification, the contact angle with respect to water in the surface (beta) of the sheet|seat for resin film formation means the value measured by the method described in an Example.

<Components of the sheet for forming a resin film>

Although the sheet for forming a resin film of one embodiment of the present invention is not particularly limited as long as it has a surface (α) and a surface (β) satisfying the requirements (I) to (III), the polymer component (A) and the curable component ( It is preferred to include B).

In addition, the sheet for forming a resin film of one embodiment of the present invention forms the surface (α) and the surface (β) that satisfy the requirements (I) to (III) in a range that does not impair the effects of the present invention. , together with the components (A) and (B), comprising at least one selected from an inorganic filler (C), a colorant (D), a coupling agent (E), a leveling agent (F), and a general-purpose additive (G), there may be

Hereinafter, the said component (A) - (G) which can become a structural component of the sheet|seat for resin film formation of one embodiment of this invention is demonstrated.

[Polymer component (A)]

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

When the sheet for resin film formation used in one embodiment of the present invention contains the polymer component (A), flexibility and film formability can be provided, and sheet-like shape retention can be made favorable. As a result, the storage elastic modulus in 23 degreeC of the sheet|seat for resin film formation can be adjusted to the above-mentioned range.

As a mass average molecular weight (Mw) of a polymer component (A), from a viewpoint of adjusting the storage elastic modulus at 23 degreeC of the sheet|seat for resin film formation obtained to the above-mentioned range, Preferably it is 20,000 or more, More preferably, it is 20,000 to 3 million, more preferably 50,000 to 2 million, still more preferably 100,000 to 1.5 million.

The content of the polymer component (A) in the sheet for forming a resin film of one embodiment of the present invention is preferably 5 to 50 mass%, more preferably 8 to 50 mass%, based on the total amount (100 mass%) of the sheet for forming a resin film. 40 mass %, More preferably, it is 10-35 mass %, More preferably, it is 15-30 mass %.

In addition, in this specification, "content of component (A) with respect to the total amount of the sheet|seat for resin film formation" means "content of component (A) with respect to the total amount of the active ingredient in the composition which is a forming material of the sheet|seat for resin film formation" It is synonymous with and it is the same also about content of the other component demonstrated below.

That is, the term "with respect to the total amount (100 mass %) of the sheet for forming a resin film" in the content regulation of each component means "the total amount of the active ingredient of the composition which is a forming material for the sheet for forming a resin film (100 mass %)" Even if it is substituted with the term "about", the definition of content is synonymous.

In addition, the above-mentioned "active ingredient" means a component excluding substances that do not directly or indirectly react with a solvent in the composition or affect the physical properties of the sheet to be formed, specifically, other than solvents such as water and organic solvents means the components of

The polymer component (A) preferably contains an acrylic polymer (A1), but other than the acrylic polymer (A1), polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polysiloxane, rubber polymer, etc. of non-acrylic polymer (A2) may be contained.

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

As content of the acrylic polymer (A1) with respect to the total amount (100 mass %) of the polymer component (A) contained in the sheet|seat for resin film formation of one embodiment of this invention, Preferably it is 50-100 mass %, More preferably is 60 to 100 mass %, more preferably 70 to 100 mass %, still more preferably 80 to 100 mass %.

(Acrylic polymer (A1))

The mass average molecular weight (Mw) of the acrylic polymer (A1) imparts flexibility and film formability to the sheet for forming a resin film, and from the viewpoint of adjusting the storage elastic modulus at 23° C. of the sheet for forming a resin film to the above-mentioned range, Preferably it is 20,000 to 3 million, More preferably, it is 100,000 to 1.5 million, More preferably, it is 150,000 to 1.2 million, More preferably, it is 250,000 to 1 million.

The acrylic polymer (A1) is preferably an acrylic polymer having a structural unit (a1) derived from an alkyl (meth)acrylate from the viewpoint of adjusting the adhesive force (α1) and (β1) of the sheet for resin film formation to the above ranges. In particular, from the viewpoint of adjusting the adhesive force (α1) of the sheet for forming a resin film within the above range, it is more preferably an acrylic copolymer having the structural unit (a1) and the structural unit (a2) derived from a nitrile-based monomer.

In addition, the acrylic polymer (A1) used in one embodiment of the present invention has structural units (a3) derived from other monomers other than the structural units (a1) and (a2) other than alkyl (meth)acrylates and nitrile monomers. ) may have more.

In addition, you may use an acrylic polymer (A1) individually or in combination of 2 or more type.

In addition, when the acrylic polymer (A1) is a copolymer, any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer may be sufficient as the form of the said copolymer.

(constituent unit (a1))

As carbon number of the alkyl group of the alkyl (meth)acrylate which comprises a structural unit (a1), from a viewpoint of providing flexibility and film-forming property to the sheet|seat for resin film formation, Preferably it is 1-18, More preferably, it is 1 to 12, more preferably 1 to 8.

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

In addition, you may use these alkyl (meth)acrylates individually or in combination of 2 or more type.

Among these, the alkyl (meth)acrylate which has a C1-C3 alkyl group is preferable, and methyl (meth)acrylate is more preferable.

The content of the structural unit (a1-1) derived from an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms in the acrylic polymer (A1) is based on the total structural units (100% by mass) of the acrylic polymer (A1), Preferably it is 5-99 mass %, More preferably, it is 10-98 mass %, More preferably, it is 20-97 mass %, More preferably, it is 25-97 mass %.

The content of the structural unit (a1) in the acrylic polymer (A1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, with respect to all the structural units (100% by mass) of the acrylic polymer (A1), more Preferably it is 55-98 mass %, More preferably, it is 60-97 mass %.

(constituent unit (a2))

Examples of the nitrile-based monomer constituting the structural unit (a2) include (meth)acrylonitrile, α-chloro(meth)acrylonitrile, α-ethoxy(meth)acrylonitrile, fumaronitrile, and the like. can

In addition, these nitrile-type monomers may be used individually or in combination of 2 or more type.

Among these, (meth)acrylonitrile is preferable.

The content of the structural unit (a2) derived from the nitrile monomer in the acrylic polymer (A1) is preferably 1 to 50% by mass, more preferably 1 to 50% by mass, based on all the structural units (100% by mass) of the acrylic polymer (A1). 5-45 mass %, More preferably, it is 10-42 mass %, More preferably, it is 15-40 mass %, More preferably, it is 20-35 mass %.

When content of a structural unit (a2) is 1 mass % or more, it will be easy to adjust the adhesive force ((alpha)1) of the surface (alpha) of the sheet|seat for resin film formation obtained to the said range. On the other hand, if content of a structural unit (a2) is 50 mass % or less, it will be easy to adjust the adhesive force ((beta)1) of the surface (beta) of the said sheet|seat for resin film formation to the said range.

(constituent unit (a3))

The acrylic polymer (A1) is a composition derived from other monomers that do not correspond to alkyl (meth)acrylates and nitrile monomers, in addition to the above structural units (a1) and (a2), within the scope not impairing the effects of the present invention. You may have a unit (a3).

Examples of the other monomer constituting the structural unit (a3) include a functional group-containing monomer having a functional group, such as a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer; vinyl ester monomers such as vinyl acetate and vinyl propionate; olefin monomers such as ethylene, propylene and isobutylene; Aromatic vinyl monomers, such as styrene, methylstyrene, and vinyltoluene: diene-type monomers, such as butadiene and isoprene; and the like.

From the viewpoint of adjusting the adhesive force (α1) and (β1) of the sheet for forming a resin film within the above ranges, the acrylic polymer (A1) used in one embodiment of the present invention is a structural unit (a3-1) derived from a hydroxyl group-containing monomer. It is preferable to include

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

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

The content of the structural unit (a3-1) derived from the hydroxyl group-containing monomer in the acrylic polymer (A1) is adjusted from the viewpoint of adjusting the adhesive force (α1) and (β1) of the sheet for forming a resin film to the above ranges, the acrylic polymer (A1) With respect to the total structural unit (100 mass %) of preferably 0.5 to 30 mass %, more preferably 1 to 25 mass %, still more preferably 2 to 20 mass %, still more preferably 3 to 15 mass % %, particularly preferably 3.5 to 12% by mass.

Further, when the content of the structural unit derived from the epoxy group-containing monomer in the acrylic polymer (A1) increases, the adhesion between the resulting sheet for forming a resin film and the silicon wafer is improved, and the value of the adhesive force (α1) tends to increase. Therefore, it is so preferable that there is little content of the structural unit derived from the epoxy-group containing monomer in an acrylic polymer (A1).

As the content of the structural unit (a3-2) derived from the epoxy group-containing monomer in the acrylic polymer (A1) used in one embodiment of the present invention, from the above point of view, to all the structural units (100% by mass) of the acrylic polymer (A1) To that, it is preferably 0 to 15 mass%, more preferably 0 to 10 mass%, still more preferably 0 to 5 mass%, still more preferably 0 to 3.5 mass%.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-epoxycyclo- Epoxy group-containing (meth)acrylic acid esters, such as 2-hydroxypropyl (meth)acrylate; non-acrylic epoxy group-containing monomers such as glycidyl crotonate and allyl glycidyl ether; and the like.

As the curable component (B) to be described later, when an epoxy thermosetting component is used, the carboxyl group and the epoxy group in the epoxy thermosetting component react, so the content of the structural unit derived from the carboxyl group-containing monomer in the acrylic polymer (A1) is small. more preferably.

When an epoxy thermosetting component is used as the curable component (B), the content of the structural unit (a3-3) derived from the carboxyl group-containing monomer used in one embodiment of the present invention is the total structural unit (100) of the acrylic polymer (A1). % by mass), preferably 0 to 10 mass%, more preferably 0 to 5 mass%, still more preferably 0 to 2 mass%, still more preferably 0 mass% (structural unit (a3-3) ) is not included).

In addition, in the present specification, the acrylic polymer having a structural unit derived from an epoxy group-containing monomer and having a mass average molecular weight of 20,000 or more has thermosetting properties, but is included in the concept of the polymer component (A), not the curable component (B). make it to be

As a carboxyl group-containing monomer, (meth)acrylic acid, a maleic acid, a fumaric acid, itaconic acid etc. are mentioned, for example.

The content of the structural unit (a3) in the acrylic polymer (A1) used in one embodiment of the present invention is preferably 0 to 30% by mass, more preferably 0 to 30% by mass, based on all the structural units (100% by mass) of the acrylic polymer (A1). Preferably it is 1-20 mass %, More preferably, it is 2-10 mass %.

(Non-acrylic resin (A2))

The sheet for resin film formation of one embodiment of the present invention may contain a non-acrylic polymer (A2) as a polymer component other than the above-mentioned acrylic polymer (A1) as needed.

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

You may use these non-acrylic polymers (A2) individually or in combination of 2 or more type.

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.

[Curable component (B)]

A curable component (B) hardens the sheet|seat for resin film formation, bears the role of forming a hard resin film, and is a compound whose mass average molecular weight (Mw) is less than 20,000.

The sheet for forming a resin film used in the present invention preferably contains, as the curable component (B), at least one of a thermosetting component (B1) and an energy ray-curable component (B2), and a resin formed from the sheet for forming a resin film It is more preferable to contain a thermosetting component (B1) from a viewpoint of suppressing coloring of a film|membrane, a viewpoint of fully advancing hardening reaction, and a viewpoint of cost reduction.

As a thermosetting component (B1), it is preferable to contain the compound which has a functional group which reacts by heating at least, and it is more preferable to contain the compound (B11) which has an epoxy group.

Moreover, it is preferable that the energy-beam curable component (B2) contains the compound (B21) which has a functional group which reacts by energy-beam irradiation.

The functional groups of these sclerosing|hardenable components react and hardening is implement|achieved by forming a three-dimensional network structure.

The mass average molecular weight (Mw) of the curable component (B) is preferably used in combination with the component (A) from the viewpoint of suppressing the viscosity of the composition which is a material for forming the sheet for forming a resin film, improving handleability, etc. Preferably less than 20,000, more preferably less than or equal to 10,000, even more preferably from 100 to 10,000.

(thermosetting component (B1))

As a thermosetting component (B1), an epoxy type thermosetting component is preferable.

It is preferable to use what combined the thermosetting agent (B12) with the compound (B11) which has an epoxy group as an epoxy-type thermosetting component.

Examples of the compound (B11) having an epoxy group (hereinafter also referred to as “epoxy compound (B11)”) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated substances thereof, cresol novolac epoxy resins, etc. Novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenylene skeleton-type epoxy resins, etc. can be heard

You may use these epoxy compounds (B11) individually or in combination of 2 or more type.

Among these, it is preferable to include at least one selected from a novolak-type epoxy resin and a biphenyl-type epoxy resin from the viewpoint of adjusting the adhesive force (α1) and (β1) of the sheet for resin film formation to the above ranges, In particular, from the viewpoint of adjusting the adhesive force (α1) of the sheet for forming a resin film within the above range, it is more preferable to include a biphenyl-type epoxy resin, and it is still more preferable to include a biphenyl aralkyl-type epoxy resin.

The total content of one or more selected from a novolak-type epoxy resin and a biphenyl-type epoxy resin is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, based on the total amount (100 mass%) of the epoxy compound (B11). 100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 95-100 mass %.

In addition, from the viewpoint of adjusting the adhesive force (α1) of the sheet for forming a resin film within the above range, the content of the biphenyl type epoxy resin is preferably 70 to 100 with respect to the total amount (100% by mass) of the epoxy compound (B11). It is mass %, More preferably, it is 80-100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 95-100 mass %.

To [ content of the epoxy compound (B11) / 100 mass parts of component (A)), Preferably it is 1-500 mass parts, More preferably, it is 3-300 mass parts, More preferably, it is 5-150 mass parts, More preferably Preferably it is 10-100 mass parts.

(thermosetting agent (B12))

The thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11).

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

As said functional group, a phenolic hydroxyl group, alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride, etc. are mentioned. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, a phenolic hydroxyl group and an amino group are more preferable, and an amino group is still more preferable.

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

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

You may use these thermosetting agents (B12) individually or in combination of 2 or more type.

Among these, it is preferable to contain a phenolic thermosetting agent from a viewpoint of adjusting the adhesive force ((alpha)1) and ((beta)1) of the sheet|seat for resin film formation to the said range.

The content of the phenolic thermosetting agent is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass relative to the total amount (100% by mass) of the thermosetting agent (B12). , More preferably, it is 90-100 mass %.

To [ content of a thermosetting agent (B12) / 100 mass parts of epoxy compounds (B11)), Preferably it is 0.1-500 mass parts, More preferably, it is 1-200 mass parts.

Further, in the sheet for forming a resin film of one embodiment of the present invention, from the viewpoint of adjusting the adhesive strength (α1) and (β1) of the sheet for forming a resin film to the above ranges, as the epoxy compound (B1), a biphenyl type epoxy resin It is preferable to contain and use both components in combination with a phenolic thermosetting agent as the thermosetting agent (B12).

Moreover, in this case, as a polymer component (A), it is more preferable that the acrylic polymer (A1) which has a structural unit (a2-1) derived from a nitrile-type monomer is included.

(curing accelerator (B13))

The sheet for forming a resin film of one embodiment of the present invention may contain a curing accelerator (B13) from the viewpoint of adjusting the curing rate by heating the sheet.

It is preferable to use a hardening accelerator (B13) together with an epoxy compound (B11) as a thermosetting component (B1).

Examples of the curing accelerator (B13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -imidazoles, such as hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

You may use these hardening accelerators (B13) individually or in combination of 2 or more type.

The content of the curing accelerator (B13) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12) from the viewpoint of improving the adhesiveness of the resin film formed from the sheet for forming a resin film. It is a mass part, More preferably, it is 0.1-6 mass parts, More preferably, it is 0.3-4 mass parts.

(Energy-ray-curable component (B2))

As the energy ray-curable component (B2), the compound (B21) having a functional group that reacts with energy ray irradiation may be used alone, but it is preferable to use a photopolymerization initiator (B22) in combination with the compound (B21). .

(Compound (B21) having a functional group that reacts with energy ray irradiation)

As the compound (B21) having a functional group that reacts with energy ray irradiation (hereinafter also referred to as “energy ray-reactive compound (B21)”), for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaeryth Ritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate, A urethane acrylate type oligomer, an epoxy acrylate, polyether acrylate, itaconic acid oligomer, etc. are mentioned.

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

Moreover, the mass average molecular weight (Mw) of the energy-beam reactive compound (B21) becomes like this. Preferably it is 100-30,000, More preferably, it is 300-10,000.

To [ content of an energy-beam-reactive compound (B21) / 100 mass parts of component (A)), Preferably it contains 1 1500 mass parts, More preferably, it is 3-1200 mass parts.

(Photoinitiator (B22))

By using together with the photoinitiator (B22) together with the energy-beam reactive compound (B21) mentioned above, even if it shortens polymerization hardening time and reduces the amount of light irradiation, hardening of the sheet|seat for resin film formation can be advanced.

As a photoinitiator (B22), a benzoin compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, a thioxanthone compound, a peroxide compound etc. are mentioned, for example.

As a more specific photoinitiator, For example, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azo Bisisobutyronitrile, dibenzyl, diacetyl, (beta)-chloroanthraquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, etc. are mentioned.

These photoinitiators may be used individually or in combination of 2 or more type.

Content of the photoinitiator (B22) is preferably 0.1 to 100 parts by mass of the energy-beam reactive compound (B21) from the viewpoint of sufficiently advancing the curing reaction of the sheet for forming a resin film and suppressing the production of residues. It is 10 mass parts, More preferably, it is 1-5 mass parts.

The content of the curable component (B) in the sheet for forming a resin film of one embodiment of the present invention is preferably 5 to 50 mass%, more preferably 8 to 50 mass%, based on the total amount (100 mass%) of the sheet for forming a resin film. 40 mass %, More preferably, it is 10-30 mass %, More preferably, it is 12-25 mass %.

In addition, the above "content of the curable component (B)" is a thermosetting component (B1) containing the above-mentioned epoxy compound (B11), a thermosetting agent (B12) and a curing accelerator (B13), and an energy ray reactive compound (B21) And total content of the energy-beam curable component (B2) containing a photoinitiator (B22) is pointed out.

The total content of the polymer component (A) and the curable component (B) in the sheet for forming a resin film of one embodiment of the present invention is preferably 40 mass% or more with respect to the total amount (100 mass%) of the sheet for forming a resin film. , More preferably, it is 50 mass % or more, More preferably, it is 60 mass % or more, More preferably, it is 70 mass % or more.

[Inorganic Filling Material (C)]

The sheet for resin film formation of one embodiment of the present invention may further contain an inorganic filler (C).

By including the inorganic filler (C), it becomes possible to adjust the coefficient of thermal expansion of the resin film formed from the sheet for resin film formation to an appropriate range, and by optimizing the coefficient of thermal expansion of the chip with a resin film, the semiconductor device in which the chip is assembled reliability can be improved. Moreover, it also becomes possible to reduce the moisture absorption of the resin film formed from the sheet|seat for resin film formation.

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

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

Among these, silica and alumina are preferable.

The average particle diameter of the inorganic filler (C) is preferably 400 nm or less, more preferably 300 nm or less, from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for resin film formation within the above range; More preferably, it is 200 nm or less, Even more preferably, it is 100 nm or less, On the other hand, from a viewpoint of making the reliability of the chip|tip with a resin film manufactured using the sheet|seat for resin film formation favorable, Preferably it is 10 nm or more, More preferably, it is 20 nm or more.

In the present specification, the average particle diameter of the inorganic filler (C) is a value measured using a laser diffraction scattering type particle size distribution analyzer, it means a volume median diameter (D _50).

The content of the inorganic filler (C) in the sheet for forming a resin film of one embodiment of the present invention is the sheet for forming a resin film from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film to the above range. To the total amount (100 mass %) of preferably 0 to 50 mass %, more preferably 0 to 45 mass %, still more preferably 0 to 40 mass %, still more preferably 0 to 30 mass % .

Further, when the sheet for forming a resin film of one embodiment of the present invention is a multilayer body composed of two or more layers formed of two or more kinds of compositions, in the composition which is a forming material for the layer on the surface (α) side of the sheet for forming a resin film It is preferable that the inorganic filler (C) contained makes an average particle diameter small, reduces content, and adjusts the surface roughness (Ra) of the surface (alpha).

In addition, you may mix|blend the inorganic filler (C') whose average particle diameter is 0.01 micrometer or more with the composition which is a forming material of the layer on the surface (β) side in the range which does not affect the surface roughness (Ra) of the surface (α).

As an average particle diameter of an inorganic filler (C'), it is 0.01-5 micrometers normally, Preferably it is 0.02-3 micrometers.

[Colorant (D)]

The sheet for resin film formation of one embodiment of the present invention may further contain a coloring agent (D).

By containing the colorant (D) in the sheet for forming a resin film, when a semiconductor chip having a resin film formed from the sheet for forming a resin film is assembled into an apparatus, infrared rays etc. generated from surrounding devices are shielded, thereby causing malfunction of the semiconductor chip. can prevent

As the colorant (D), an organic or inorganic pigment and dye can be used.

As the dye, for example, it is possible to use any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, or a cationic dye.

In addition, it does not restrict|limit especially as a pigment, It can select and use it suitably from well-known pigment.

Among these, a black pigment is preferable from a viewpoint of being favorable in shielding property of an electromagnetic wave or infrared rays, and improving the discrimination by a laser marking method more.

As a black pigment, although carbon black, iron oxide, manganese dioxide, aniline black, activated carbon etc. are mentioned, for example, From a viewpoint of improving the reliability of a semiconductor chip, carbon black is preferable.

In addition, you may use these coloring agents (D) individually or in combination of 2 or more type.

The average particle diameter of the colorant (D) is preferably 400 nm or less, more preferably 300 nm or less, more preferably 400 nm or less from the viewpoint of adjusting the surface roughness (Ra) of the surface (α) of the sheet for resin film formation within the above range. Preferably it is 200 nm or less, More preferably, it is 100 nm or less, More preferably, it is 10 nm or more, More preferably, it is 20 nm or more.

In the present specification, the average particle diameter of the colorant (D) is a value measured using a laser diffraction scattering type particle size distribution analyzer, it means a volume median diameter (D _50).

The content of the colorant (D) in the sheet for forming a resin film of one embodiment of the present invention is preferably 0.01 to 30 mass%, more preferably 0.05 to 25% by mass relative to the total amount (100 mass%) of the sheet for forming a resin film. It is mass %, More preferably, it is 0.1-15 mass %, More preferably, it is 0.15-5 mass %.

[Coupling agent (E)]

The sheet for resin film formation of one embodiment of the present invention may further contain a coupling agent (E).

By including a coupling agent (E), water resistance can also be improved, without impairing the heat resistance of the resin film formed from the sheet|seat for resin film formation obtained. Moreover, it contributes also to the improvement of the edge part adhesiveness after adhesion with a silicon wafer.

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

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

You may use these coupling agents (E) individually or in combination of 2 or more type.

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

The molecular weight of the coupling agent (E) including the oligomeric coupling agent is preferably 100 to 15000, more preferably 150 to 10000, still more preferably 200 to 5000, still more preferably 250 to 3000, still more preferably usually between 350 and 2000.

In addition, by including the coupling agent (E), when the inorganic filler (C) is contained in a silicon wafer as an adherend or a sheet for forming a resin film, the surface of the inorganic filler (C) is bonded, and adhesiveness and cohesiveness are improved It is considered that the adhesive force (α1) of the sheet for forming a resin film also increases.

Therefore, from a viewpoint of obtaining the sheet|seat for resin film formation excellent in rework property, it is so preferable that there is little content of the coupling agent (E) in the sheet|seat for resin film formation of one embodiment of this invention.

The content of the coupling agent (E) in the sheet for forming a resin film of one embodiment of the present invention is preferably 3.0 mass % or less, more preferably from the viewpoint of the above with respect to the total amount (100 mass %) of the sheet for forming a resin film. 1.5 mass % or less, more preferably 0.8 mass % or less, still more preferably 0.3 mass % or less, on the other hand, from the viewpoint of improving the end adhesion of the sheet for forming a resin film after attachment to a silicon wafer, and the resin From the viewpoint of adjusting the adhesive force (β1) of the surface (β) of the sheet for film formation within the above range, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.10% by mass or more.

[Leveling agent (F)]

The sheet for resin film formation of one embodiment of the present invention may further contain a leveling agent (F).

By including a leveling agent (F), the adhesive force ((alpha)1) of the surface (alpha) of the sheet|seat for resin film formation obtained can be adjusted easily in the said range.

As a leveling agent (F), the leveling agent etc. which a silicone type leveling agent, a fluorine type leveling agent, an acrylic type leveling agent, a vinyl type leveling agent, and a fluorine type and an acryl type were combined are mentioned, for example.

You may use these leveling agents (F) individually or in combination of 2 or more type.

Among these, it is preferable to contain a silicone type leveling agent from a viewpoint that the adhesive force (alpha) 1 of the surface (alpha) of the sheet|seat for resin film formation can be easily adjusted in the said range.

In addition, when the leveling agent (F) is contained in the sheet for forming a resin film, it becomes easy to adjust the adhesive force (α1) of the surface (α) to the above range, but the adhesive force (β1) of the surface (β) decreases, There exists a possibility that the rework property of the sheet|seat for resin film formation may fall. Therefore, it is so preferable that there is little content of a leveling agent in the surface (beta) side of the sheet|seat for resin film formation.

From the viewpoint of adjusting the adhesive force (α1) of the surface (α) of the sheet for forming a resin film to be obtained within the above range, the content of the leveling agent (F) is preferably based on the total amount (100% by mass) of the sheet for forming a resin film (100% by mass). is 0.010 mass% or more, more preferably 0.050 mass% or more, still more preferably 0.100 mass% or more.

In addition, from the viewpoint of adjusting the adhesive force (β1) of the surface (β) of the sheet for forming a resin film to the above range, the content of the leveling agent (F) is based on the total amount (100% by mass) of the sheet for forming a resin film, Preferably it is 0.500 mass % or less, More preferably, it is 0.300 mass % or more, More preferably, it is 0.200 mass % or more.

Further, from the viewpoint of adjusting the adhesive force (α1) and (β1) of the sheet for forming a resin film in good balance, when the sheet for forming a resin film of the present invention is a sheet containing a leveling agent, one of the sheets for forming a resin film As a form, it is preferable that it is a multilayer body which has a layer formed from the composition ((alpha)') containing a leveling agent, and the layer formed from the composition ((beta)') which does not contain a leveling agent substantially.

The composition (α′) serves as a material for forming a layer on the surface (α) side of the sheet for forming a resin film, and the composition (β′) serves as a material for forming a layer on the surface (β) side of the sheet for forming a resin film.

The content of the leveling agent (F) in the composition (α′) is the total amount (100% by mass) of the active ingredient contained in the composition (α′) from the viewpoint of adjusting the adhesive force (α1) of the surface (α) to the above range. , preferably 0.010 to 10 mass%, more preferably 0.050 to 7 mass%, still more preferably 0.100 to 5 mass%, still more preferably 0.150 to 2 mass%.

On the other hand, the content of the leveling agent (F) in the composition (β') is the total amount (100 mass %) of the active ingredient contained in the composition (β') from the viewpoint of adjusting the adhesive force (β1) of the surface (β) to the above range. ), preferably 0 to 0.500 mass%, more preferably 0 to 0.100 mass%, still more preferably 0 to 0.010 mass%, still more preferably 0 to 0.001 mass%.

[Universal Additive (G)]

The sheet for resin film formation used in one embodiment of the present invention may contain, if necessary, a general-purpose additive (G) in addition to the above components within a range that does not impair the effects of the present invention.

As a general-purpose additive (G), a crosslinking agent, a plasticizer, an antistatic agent, antioxidant, an ion trapping agent, a gettering agent, a chain transfer agent, etc. are mentioned, for example.

Among these, it is preferable to contain a crosslinking agent.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, an amine type crosslinking agent, an amino resin type crosslinking agent, etc. are mentioned, for example. You may use these crosslinking agents individually or in combination of 2 or more types.

The content of each of these general-purpose additives (G) in the sheet for forming a resin film of one embodiment of the present invention is preferably 0 to 10 mass%, more preferably 0 to 10 mass%, based on the total amount (100 mass%) of the sheet for forming a resin film. is 0 to 5 mass%, more preferably 0 to 2 mass%.

<The manufacturing method of the sheet|seat for resin film formation>

There is no restriction|limiting in particular as a manufacturing method of the sheet|seat for resin film formation of one embodiment of this invention, It can manufacture by a well-known method.

For example, after preparing the composition for resin film formation containing each component mentioned above used as the forming material of the sheet|seat for resin film formation, an organic solvent is added and diluted suitably, and the solution of the composition for resin film formation is obtained. And the sheet for resin film formation can be manufactured by apply|coating the solution of the said composition for resin film formation by a well-known coating method on a support sheet, forming a coating film, and drying this coating film.

In addition, when the sheet for resin film formation of one embodiment of the present invention is a multilayer body of two or more layers, as a manufacturing method of the sheet for resin film formation, for example, a solution of the composition for resin film formation on two or more support sheets, respectively. and a method of forming a coating film by applying a coating film, bonding the coating film together to form a coating film, and drying the coating film, and the like.

As an organic solvent used for manufacture of the solution of the composition for resin film formation, toluene, ethyl acetate, methyl ethyl ketone, etc. are mentioned, for example.

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

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

Although the thickness of the sheet|seat for resin film formation of one embodiment of this invention is suitably set according to a use, Preferably it is 3-300 micrometers, More preferably, it is 5-250 micrometers, More preferably, it is 7-200 micrometers.

Moreover, also when the sheet|seat for resin film formation is a multilayer body comprised by two or more layers, it is preferable that the total thickness of the said multilayer body is the said range.

<Use of sheet for forming a resin film>

The sheet for forming a resin film of one embodiment of the present invention can be adhered to the back surface of a work, such as a silicon wafer such as a semiconductor wafer for chips or a semiconductor chip of a face-down method, to form a resin film on the work. This resin film has a function as a protective film which protects the back surface of a workpiece|work, such as a semiconductor wafer and a semiconductor chip. For example, when attached to a semiconductor wafer, since the resin film has a function of reinforcing the wafer, damage to the wafer or the like can be prevented.

That is, it is preferable that the sheet|seat for resin film formation of one embodiment of this invention is a sheet|seat for protective film formation for forming a protective film on a silicon wafer.

Moreover, the resin film formed from the sheet|seat for resin film formation of one embodiment of this invention can also provide the function as an adhesive film. That is, when a resin film formed using the sheet for forming a resin film of one embodiment of the present invention has a function as an adhesive film, the chip having the resin film is placed on a die pad portion or another member such as a separate semiconductor chip (chip mounting portion). above), and can contribute to the improvement of productivity for manufacturing a semiconductor device.

That is, the sheet for forming a resin film of one embodiment of the present invention may be a sheet for forming an adhesive film for forming an adhesive film on a silicon wafer.

[Structure of composite sheet for resin film formation]

The composite sheet for forming a resin film of the present invention (hereinafter also simply referred to as a "composite sheet") has a structure in which the sheet for forming a resin film of the present invention capable of forming the above-described resin film is laminated on a support sheet.

In addition, there is no restriction|limiting in particular about the form of the composite sheet of one aspect of this invention, For example, the form of a long tape shape, a single-leaf label, etc. may be sufficient.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the composite sheet for resin film formation of one embodiment of this invention.

As a composite sheet of one embodiment of the present invention, a composite sheet 1a having a structure in which a sheet for forming a resin film 10 is directly laminated on a support sheet 11 as shown in Fig. 1A is mentioned. have.

The shape of the sheet 10 for forming a resin film of the composite sheet of one embodiment of the present invention may be substantially the same as that of a silicon wafer as an adherend, or a shape that can include the shape of a silicon wafer.

In addition, in the composite sheet 1a of Fig. 1 (a), the support sheet 11 and the sheet 10 for forming a resin film have substantially the same shape, but as shown in Fig. 1 (b), for forming a resin film The shape of the sheet 10 may be a composite sheet 1b smaller than the shape of the support sheet 11 .

Moreover, as shown in FIG.1(c) as a composite sheet of one embodiment of this invention, the composite sheet 1c which has the ring-shaped jig|tool adhesive layer 12 is mentioned.

The ring-shaped jig adhesive layer 12 is provided for the purpose of improving the adhesion to the jig when adhering to a jig such as a ring frame, and can be formed of a double-sided adhesive sheet having a base material (core material) or an adhesive. have.

In addition, in the composite sheet 1c shown in FIG.1(c), with respect to the composite sheet 1a of FIG.1(a), although the structure which provided the jig adhesive layer 12 further is shown, it is one form of this invention Examples of the composite sheet of FIG. 1B include a composite sheet having a configuration in which a jig adhesive layer 12 is provided on the surface of the support sheet 11 of the composite sheet 1b of FIG. 1B .

As a composite sheet of one embodiment of the present invention, as shown in Fig. 1(d), a composite sheet 1d having a configuration in which the sheet 10 for forming a resin film is sandwiched by two supporting sheets 11 and 11'. ) may be used.

Moreover, similarly to the structure of the composite sheet 1d, on the surface of the sheet|seat 10 for resin film formation which is exposed of the composite sheet 1b of FIG.1(b), a support sheet separate from the support sheet 11 may be installed.

Similarly, on the surface of the sheet 10 for forming a resin film of the composite sheet 1c shown in Fig. 1(c) and on the surface of the jig adhesive layer 12, a support sheet separate from the support sheet 11 is provided You can install it.

<Support sheet>

The support sheet included in the composite sheet of one embodiment of the present invention is a release sheet for preventing adhesion of dust or the like to the surface of the sheet for forming a resin film, or dicing for protecting the surface of the sheet for forming a resin film in a dicing step or the like It acts as a sheet.

It is preferable that the support sheet used by this invention has a structure which has a resin film.

Examples of the resin film include polyethylene films such as low-density polyethylene (LDPE) films and linear low-density polyethylene (LLDPE) films, ethylene/propylene copolymer films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene films. , polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene/vinyl acetate copolymer film, ionomer resin film, ethylene/(meth ) An acrylic acid copolymer film, an ethylene/(meth)acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, etc. are mentioned.

The support sheet used in one embodiment of the present invention may be a single layer film composed of one type of resin film, or a laminate film in which two or more types of resin films are laminated.

In addition, a crosslinked film may be sufficient as said resin film.

Moreover, the thing which colored these resin films, the thing which printed, etc. can be used.

The resin film may be a sheet formed by extrusion forming a thermoplastic resin, or may be stretched, or a resin film obtained by thinning and curing the curable resin by a predetermined means to form a sheet may be used.

Among these resin films, it is excellent in heat resistance, and since it has moderate softness|flexibility, it has expandability and a viewpoint that a pick-up ability is also easy to maintain a resin film containing a polypropylene film is preferable.

In addition, as a structure of the support sheet which has a resin film containing a polypropylene film, the single-layer structure containing only a polypropylene film may be sufficient, and the multilayer structure containing a polypropylene film and another resin film may be sufficient.

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

When the support sheet is used as a release sheet for preventing adhesion of dust or the like to the surface of the sheet for forming a resin film, the support sheet can be easily peeled off from the sheet for forming a resin film when attached to a silicon wafer or in a dicing process. A resin film that can do this is preferable.

In addition, as the said support sheet, you may use the resin film which performed peeling processing on the surface of the above-mentioned resin film.

As a method of the said peeling process, the method of providing the peeling film formed with the release agent on the surface of the above-mentioned resin film is preferable.

Examples of the release agent include a release agent containing a resin selected from an acrylic resin, an alkyd resin, a silicone resin, a fluorine resin, an unsaturated polyester resin, a polyolefin resin, a wax resin, and the like.

When the support sheet is used as a dicing sheet for protecting the surface of the sheet for forming a resin film in a dicing process or the like, the support sheet is preferably an adhesive sheet having a pressure-sensitive adhesive layer formed of an adhesive on the resin film described above.

Examples of the pressure-sensitive adhesive resin included in the pressure-sensitive adhesive include acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, vinyl ether-based resins, etc., when the structure of the pressure-sensitive adhesive resin is paid attention to. For example, energy-beam curable resin etc. are mentioned.

One aspect of this invention WHEREIN: From a viewpoint of making pick-up property favorable, the adhesive containing energy-beam curable resin is preferable.

In addition, when an adhesive layer formed of an adhesive containing an energy ray-curable resin is provided on the resin film, the adhesive layer may be an adhesive layer cured by irradiating an energy ray, or an uncured adhesive layer before irradiating an energy ray. do. In addition, when using the support sheet which has a non-hardened adhesive layer before irradiating an energy ray, before a pick-up process, you may irradiate an energy ray and harden the said adhesive layer.

The thickness of the support sheet is appropriately selected depending on the application, but is preferably 10 to 500 µm, more preferably 20 to 350 µm, still more preferably 30 to 200 µm.

In addition, in the thickness of said support sheet, not only the thickness of the resin film which comprises a support sheet, but when it has an adhesive layer or a peeling film, the thickness of the said adhesive layer or peeling film is also contained.

<Jig Adhesive Layer>

The jig adhesive layer can be formed from a double-sided adhesive sheet having a base material (core material) or an adhesive composition containing an adhesive.

As said base material (core material), the resin film which can be used as the above-mentioned support sheet is mentioned, A polypropylene film is preferable.

Moreover, as said adhesive, an acrylic resin, a urethane resin, a rubber-type resin, silicone resin, vinyl ether-type resin etc. are mentioned, for example.

The thickness of the jig adhesive layer is preferably 1 to 80 μm, more preferably 5 to 60 μm, still more preferably 10 to 40 μm.

[Silicon Wafer Regeneration Method]

The present invention also provides a method of reworking a silicon wafer by reworking the sheet for forming a resin film from a laminate in which the surface (?) of the sheet for forming a resin film of the present invention is directly adhered onto a silicon wafer.

The silicon wafer regeneration method of the present invention includes the following steps (1) to (2).

Step (1): A step of affixing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a base material and an pressure-sensitive adhesive layer on the surface (β) of the sheet for forming a resin film of the laminate

Step (2): A step of reworking the sheet for forming a resin film adhered on the silicon wafer by tensioning the pressure-sensitive adhesive sheet adhered to the surface (β) of the sheet for forming a resin film in the step (1).

The method for regenerating a silicon wafer of the present invention does not damage the silicon wafer when the need for rework occurs after attaching the sheet for forming a resin film of the present invention on a silicon wafer, and the sheet for forming a resin film adhered thereto It utilizes the property of the sheet|seat for resin film formation of this invention that it can rework while suppressing that a part adheres and remains on a silicon wafer.

In addition, in the method of regenerating a silicon wafer of one embodiment of the present invention, not only the laminate immediately after the surface (α) of the sheet for forming a resin film of the present invention is directly adhered onto the silicon wafer, but also after about 24 hours have elapsed , is applicable also to the laminated body in the state which the adhesiveness of a silicon wafer and the sheet|seat for resin film formation improved.

Hereinafter, steps (1) and (2) of the method for regenerating a silicon wafer of the present invention will be described.

<Process (1)>

In process (1), it is a process of sticking the said adhesive layer of the adhesive sheet which has a base material and an adhesive layer on the surface (beta) of the said sheet|seat for resin film formation of the said laminated body.

As an adhesive sheet used at this process, it has a base material and an adhesive layer.

As the said base material, a resin film is preferable and the resin film illustrated by the item of the above-mentioned support sheet is mentioned.

As the pressure-sensitive adhesive layer, 100 parts by mass of an acrylic resin having a structural unit derived from butyl acrylate and acrylic acid, and having a mass average molecular weight of 600,000 to 1,000,000, and 0.01 to 10 parts by mass of a crosslinking agent, as stipulated in the requirement (III) A pressure-sensitive adhesive layer having a thickness of 10 to 50 µm formed of an adhesive is preferable.

However, in one aspect of this invention, other than said adhesive, if it is an adhesive which can form the adhesive layer used as the adhesive force ((beta)1) of the surface (beta) mentioned above, it can be used.

Although there is no limitation in particular as a shape of the said adhesive sheet, From a viewpoint of operability in the following process (2), the adhesive sheet of the same shape as the sheet|seat for resin film formation, or a shape larger than the sheet|seat for resin film formation is preferable.

In this process, as a sticking method of the surface (beta) and the adhesive layer of an adhesive sheet, you may stick using a machine, and you may carry out manually.

Further, when the surface (α) of the sheet for forming a resin film included in the composite sheet of one embodiment of the present invention described above is attached to a silicon wafer, and a dicing sheet is already laminated as a support sheet on the surface (β) side In this case, the said dicing sheet can also be used as an adhesive sheet of this process.

<Process (2)>

Step (2) is a step of reworking the sheet for forming a resin film adhered on the silicon wafer by pulling the pressure-sensitive adhesive sheet attached to the surface (β) of the sheet for forming a resin film in step (1).

In this step, the sheet for forming a resin film of the present invention is used, and since the adhesive strength (α1) and (β1) of the sheet for forming a resin film are in the above-mentioned ranges, the sheet is adhered to the surface (β) in the step (1). By pulling one adhesive sheet, the sheet for forming a resin film is also pulled together, and the sheet for forming a resin film can be reworked from the silicon wafer.

There is no restriction|limiting in particular as a speed|rate and an angle at the time of tensioning an adhesive sheet, It can set suitably.

In this step, the pressure-sensitive adhesive sheet may be pulled using a machine, but from the viewpoint of operability, it is preferable to manually pull the pressure-sensitive adhesive sheet to rework the sheet for forming a resin film from a silicon wafer.

In addition, in this process, after removing the sheet|seat for resin film formation, you may wash|clean the surface of a silicon wafer with organic solvents, such as ethanol, as needed.

By passing through the above process, the silicon wafer to which the sheet|seat for resin film formation was adhered once can be regenerated.

Example

The measuring method of the mass average molecular weight (Mw) or number average molecular weight (Mn) of each component used by manufacture examples 1-8 is as follows.

<Mass Average Molecular Weight (Mw), Number Average Molecular Weight (Mn)>

It measured under the following conditions using the gel permeation chromatography apparatus (The Tosoh Corporation make, product name "HLC-8220GPC"), and the value measured by standard polystyrene conversion was used.

(Measuring conditions)

ㆍColumn: “TSK guard column HXL-H” “TSK gel GMHXL (×2)” “TSK gel G2000HXL” (all manufactured by Tosoh Corporation)

ㆍColumn temperature: 40 ℃

ㆍDeveloping solvent: tetrahydrofuran

ㆍFlow rate: 1.0mL/min

Preparation Examples 1 to 8

(Preparation of a solution of a composition for forming a resin film)

Compositions (1) to (8) for forming a resin film (in Table 1, abbreviated as “composition (1) to (8)”) were prepared by blending each component of the type and blending amount shown in Table 1, respectively, Furthermore, it diluted with methyl ethyl ketone, and the solution of the composition with a solid content concentration of 61 mass % was prepared.

In addition, the compounding quantity of each component in Table 1 is a ratio (unit: mass % (active ingredient ratio)) with respect to 100 mass % of the whole quantity (total compounding quantity of components (A)-(G)) of each composition. In addition, the detail of each component described in Table 1 is as follows.

<Polymer component (A)>

- (A-1): acrylic copolymer obtained by copolymerizing methyl acrylate (MA) and 2-hydroxyethyl acrylate (HEA) (composition ratio: MA/HEA=95/5 (mass %), Mw=80 just).

ㆍ (A-2): acrylic copolymer obtained by copolymerizing n-butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN) and glycidyl methacrylate (GMA) (composition ratio: BA/EA/AN/GMA=39/29/29/3 (% by mass), Mw=800 only).

ㆍ (A-3): acrylic copolymer obtained by copolymerizing n-butyl acrylate (BA), methyl acrylate (MA), glycidyl methacrylate (GMA) and 2-hydroxyethyl acrylate (HEA) (Composition ratio: BA/MA/GMA/HEA=55/10/20/15 (% by mass), Mw=800 only).

ㆍ (A-4): acrylic copolymer obtained by copolymerizing n-butyl acrylate (BA), ethyl acrylate (EA) and glycidyl methacrylate (GMA) (composition ratio: BA/EA/GMA=53 /44/3 (% by mass), Mw=800 only).

<Curable component (B)>

- (B-1): an acryloyl-group addition cresol novolak-type epoxy resin (The Nippon Kayaku Co., Ltd. make, brand name "CNA-147", the epoxy compound corresponding to the said component (B11)).

- (B-2): Biphenyl aralkyl type epoxy resin (The Nippon Kayaku Co., Ltd. make, brand name "NC-3000H", the epoxy compound corresponding to the said component (B11)).

- (B-3): Bisphenol A epoxy resin (The Mitsubishi Chemical Co., Ltd. make, brand name "jER828", the epoxy compound corresponding to the said component (B11)).

- (B-4): Bisphenol A epoxy resin (The Mitsubishi Chemical Co., Ltd. make, brand name "jER1055", the epoxy compound corresponding to the said component (B11)).

- (B-5): a dicyclopentadiene type epoxy resin (DIC Corporation make, trade name "Epiclon HP-7200HH", the epoxy compound corresponding to the said component (B11)).

- (B-6): a biphenylene aralkyl type phenol resin (Meiwa Chemical Co., Ltd. make, trade name "MEH-7851-H", thermosetting agent corresponding to the said component (B12)).

- (B-7): dicyandiamide (made by ADEKA Co., Ltd., brand name "adeka hardner 3636AS", thermosetting agent corresponding to the said component (B12)).

- (B-8): imidazole type hardening accelerator (Shikoku Kasei Kogyo Co., Ltd. make, brand name "Curesol 2PHZ", hardening accelerator corresponding to the said component (B13)).

<Inorganic filler (C)>

- (C-1): Silica filler (average particle diameter = 50 nm).

- (C-2): Silica filler (average particle diameter = 500 nm).

<Colorant (D)>

- (D-1): carbon black (average particle diameter = 28 nm).

<Silane coupling agent (E)>

- (E-1): Silane coupling agent (Shin-Etsu Chemical Co., Ltd. make, trade name "KBM-403").

<Leveling agent (F)>

- (F-1): Silicone-type leveling agent (Momentive Performance Materials Japan company make, brand name "XF42-334").

<General purpose additive (G)>

- (G-1): isocyanate type crosslinking agent (Toyochem Co., Ltd. make, brand name "BHS8515").

Example 1

On the release-treated surface of the first support sheet (manufactured by Lintec, trade name "SP-PET3811", thickness: 38 µm) composed of a resin film subjected to a release treatment, the composition (2) for forming a resin film prepared in Production Example 2 The solution was applied and dried to form a coating film (?').

Further, on the peeling-treated surface of the second support sheet, which is the same as that of the first support sheet, the solution of the composition (1) for forming a resin film prepared in Production Example 1 was applied and dried to form a coating film (β'). .

Then, the coating films (α′) and (β′) formed on the two supporting sheets are bonded, dried at 120° C. for 2 minutes, and the total thickness of the two layers is 25 μm. was formed, and the composite sheet for resin film formation comprised with the 1st support sheet/sheet for resin film formation/2nd support sheet was produced.

Further, in the composite sheet, when the first supporting sheet is removed, the side to which the surface of the sheet for forming a resin film exposed when the silicon wafer is adhered is the “surface (α)”, and when the second supporting sheet is removed The surface of the sheet for forming a resin film to be exposed is the “surface (β)”.

Example 2

In Example 1, instead of "the solution of the composition (2) for forming a resin film prepared in Production Example 2", "a solution of the composition (3) for forming a resin film prepared in Production Example 3" was used except that Similarly, the composite sheet for resin film formation was produced.

Example 3

In Example 1, instead of "the solution of the composition (2) for forming a resin film prepared in Production Example 2", "a solution of the composition (4) for forming a resin film prepared in Production Example 4" was used. Similarly, the composite sheet for resin film formation was produced.

Example 4

In Example 1, in place of "the solution of the composition (2) for forming a resin film prepared in Production Example 2", except that "the solution of the composition (5) for forming a resin film prepared in Production Example 5" was used. Similarly, the composite sheet for resin film formation was produced.

Example 5

On the release-treated surface of the first support sheet (manufactured by Lintec, trade name "SP-PET3811", thickness: 38 µm) composed of a resin film subjected to a release treatment, the composition (6) for forming a resin film prepared in Production Example 6 The solution was apply|coated, the coating film was formed, the drying process for 2 minutes was performed at 120 degreeC, and the sheet|seat for resin film formation with a thickness of 25 micrometers was formed.

Then, the surface of the formed sheet for forming a resin film and the peeling-treated surface of the second support sheet, which is the same as that of the first support sheet, are bonded to each other to form a first support sheet/sheet for forming a resin film/second support sheet. A composite sheet for forming a resin film was produced.

Comparative Example 1

In Example 5, in place of the "solution of the composition (6) for forming a resin film prepared in Production Example 6", except that "the solution of the composition (3) for forming a resin film prepared in Production Example 3" was used. Similarly, the composite sheet for resin film formation was produced.

Comparative Example 2

In Example 5, instead of "the solution of the composition (6) for forming a resin film prepared in Production Example 6", "a solution of the composition (7) for forming a resin film prepared in Production Example 7" was used except that Similarly, the composite sheet for resin film formation was produced.

Comparative Example 3

In Example 5, in place of "the solution of the composition (6) for forming a resin film prepared in Production Example 6", except that "the solution of the composition (8) for forming a resin film prepared in Production Example 8" was used. Similarly, the composite sheet for resin film formation was produced.

The measurement and evaluation of the following physical property values were performed as follows using the composite sheet produced by the Example and the comparative example. These results are shown in Table 2.

<Requirement (I): Measurement of the surface roughness (Ra) of the surface (α) of the sheet for forming a resin film>

The first supporting sheet included in the composite sheets produced in Examples and Comparative Examples was removed, and the exposed surface (α) of the sheet for forming a resin film was measured with a contact-type surface roughness meter (manufactured by Mitsutoyo, product name “SURFTEST SV-3000”). '), the cut-off value λc was set to 0.8 mm and the evaluation length Ln was set to 4 mm, and measurement was performed in accordance with JIS B0601:2001.

<Requirement (II): Measurement of Adhesive Force of Surface (α) of Sheet for Resin Film Formation to Silicon Wafer>

The first supporting sheet included in the composite sheets prepared in Examples and Comparative Examples was removed, and the exposed surface (α) of the sheet for forming a resin film and a #2000 polished silicon wafer (diameter: 200 mm, thickness: 600 μm) ) was affixed using a tape mounter (manufactured by Lintec Co., Ltd., product name "Adwill RAD-3600F/12"), heating at 70°C.

Then, the second supporting sheet of the composite sheet is removed, and the exposed surface (β) of the sheet for forming a resin film and a commercially available pressure-sensitive adhesive sheet used as a backing tape (manufactured by Lintec Co., Ltd., trade name “PET50(A)”) PAT1", width: 25 mm), after affixing using a 2 kg roller on a hot plate heated to 70 degreeC, in the environment of 23 degreeC, 50%RH (relative humidity), it left still for 24 hours. .

After standing still, using a universal testing machine (manufactured by Shimatsu Seisakusho Co., Ltd., product name "Autograph AG-IS"), a tensile test was performed under conditions of a peeling angle of 180° and a peeling rate of 0.3 m/min, and a silicon wafer The load at the time of peeling the sheet|seat for protective film formation and a backing tape from the surface of was measured. The value of this load was made into the adhesive force of the surface (alpha) of the sheet|seat for resin film formation with respect to a silicon wafer.

In addition, the commercially available pressure-sensitive adhesive sheet used as a backing tape does not peel at the interface between the sheet for forming a protective film and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet when subjected to a tensile test, but at the interface between the sheet for forming a protective film and the silicon wafer. It has adhesive strength enough to be able to peel stably.

<Requirement (III): Measurement of the adhesive force of the surface (β) of the sheet for forming a resin film to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet>

On the silicon wafer, the double-sided adhesive tape for fixing the sheet|seat for resin film formation (Lintech Co., Ltd. product, brand name "TL-4100S-50") was affixed at room temperature (25 degreeC) using a rubber roll. In addition, the said double-sided adhesive tape selects what can fully fix the sheet|seat for protective film formation at the time of a tensile test.

Next, the adhesive surface of this double-sided adhesive tape and the first support sheet included in the composite sheets produced in Examples and Comparative Examples were removed, and the surface (α) of the exposed sheet for forming a resin film was mounted on a tape mounter (Lintec ( Co., Ltd. product name "Adwill RAD-3600F/12") was used, and it affixed at room temperature.

Then, the second supporting sheet of the composite sheet is removed, and the exposed surface (β) of the sheet for forming a resin film and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to be described later are attached at 23° C. using a 2 kg roller, It left still for 20 minutes in 23 degreeC and the environment of 50%RH (relative humidity).

After standing still, using a universal testing machine (manufactured by Shimatsu Seisakusho Co., Ltd., product name "Autograph AG-IS"), a tensile test was performed under conditions of a peeling angle of 180° and a peeling rate of 0.3 m/min to form a protective film The load at the time of peeling an adhesive sheet from the surface (beta) of a dragon sheet was measured. The value of this load was made into the adhesive force of the surface (beta) of the sheet|seat for resin film formation with respect to the adhesive layer of an adhesive sheet.

(Details of the adhesive sheet attached to the surface (β))

On the corona-treated surface of the resin film containing the corona-treated ethylene-methyl methacrylate copolymer (composition ratio: ethylene / methyl methacrylate = 90/10 (mass ratio)), the following pressure-sensitive adhesive composition is formed with a thickness of 20 µm An adhesive sheet having an adhesive layer of was used.

ㆍAdhesive composition: tolylene diisocyanate type crosslinking agent with respect to 100 parts by mass of acrylic copolymer obtained by copolymerizing butyl acrylate (BA) and acrylic acid (AA) (BA/AA = 90/10 (mass ratio), Mw = 700 only) (Brand name "Coronate L", the Nippon Polyurethane Kogyo Co., Ltd. make) 5 mass parts was mix|blended.

<Measurement of storage elastic modulus at 23°C of the sheet for forming a resin film>

A plurality of sheets for forming a resin film formed by removing two supporting sheets of the composite sheets produced in Examples and Comparative Examples were laminated to prepare test samples having a thickness of 0.18 mm, a width of 4.5 mm, and a length of 20.0 mm.

With respect to the test sample, using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800", in tensile mode, at a frequency of 11 Hz, 23° C., and atmospheric atmosphere, the storage elastic modulus at 23° C. of the sheet for resin film formation) (unit: GPa) was measured.

<Measurement of the contact angle with respect to water on the surface (β) of the sheet for forming a resin film>

The 2nd support sheet which the composite sheet produced by the Example and the comparative example has was removed, and distilled water 10ml was dripped with respect to the surface (beta) of the exposed sheet|seat for resin film formation, and it left still for 10 minutes.

After standing still, using an automatic contact angle meter (manufactured by KRUSS, product name "DSA100S"), the angle between the surface (β) and the water drop was measured, and the angle was defined as the "contact angle with water on the surface (β)". .

<Evaluation (1): Rework property of sheet for resin film formation>

The first supporting sheet included in the composite sheets prepared in Examples and Comparative Examples was removed, and the exposed surface (α) of the sheet for forming a resin film and a #2000 polished silicon wafer (diameter: 200 mm, thickness: 600 μm) ), using a tape mounter (manufactured by Lintec Co., Ltd., product name "Adwill RAD-3600F/12"), and attached while heating to 70 ° C., in an environment of 23 ° C., 50% RH (relative humidity) , was in politics for 24 hours.

After standing still, the second support sheet of the composite sheet is removed, and the exposed surface (β) of the sheet for forming a resin film and a commercially available general-purpose dicing tape (manufactured by Lintec Co., Ltd., trade name "Adwill D-510T", The surface of the adhesive layer of the adhesive sheet which has the adhesive layer formed with the adhesive prescribed|regulated by the above-mentioned requirement (III)) was affixed at room temperature (25 degreeC), and it left still for 20 minutes.

After that, when the sheet for resin film formation is reworked from the silicon wafer by manually pulling the general-purpose dicing tape, whether or not rework can be performed and the presence or absence of adhesion of residues on the surface of the silicon wafer after rework was observed, and the following criteria evaluated the reworkability of the sheet for resin film formation.

A: The sheet for forming a protective film was completely peelable from the silicon wafer. The residue of the sheet|seat for protective film formation which can be confirmed visually on the silicon wafer after rework was not seen.

B: The sheet for forming a protective film was able to peel from the silicon wafer. On the silicon wafer after rework, some residues of the sheet for forming a protective film were seen, but wiping with ethanol was enough to completely remove it.

C: The silicon wafer was damaged during rework, or even if rework could be performed without damaging the silicon wafer, a residue of the protective film formation sheet was found on the silicon wafer after rework, to the extent that it was difficult to wipe with ethanol.

<Evaluation (2): Edge Adhesion of Sheet for Resin Film Formation>

The first supporting sheet included in the composite sheets prepared in Examples and Comparative Examples was removed, and the exposed surface (α) of the sheet for forming a resin film and a #2000 polished silicon wafer (diameter: 200 mm, thickness: 600 μm) ), using a tape mounter (manufactured by Lintec Co., Ltd., product name "Adwill RAD-3600F/12"), is attached while heating to 70° C., and thereafter, the second support sheet is also removed, and a silicon wafer and a sheet for forming a resin film were attached thereto.

And the edge part of the silicon wafer with the sheet|seat for resin film formation was observed visually, and the following criteria evaluated the edge part adhesiveness of the sheet|seat for resin film formation according to the number of burrs or cutouts of 0.5 mm or more.

A: The number of burrs or cutouts of 0.5 mm or more is 0 places.

B: The number of burrs or cuts of 0.5 mm or more is 1 to 4 places.

C: The number of burrs or cutouts of 0.5 mm or more is 5 or more.

According to Table 2, the sheet|seat for resin film formation produced in Examples 1-5 which is one embodiment of this invention brought the result excellent in both of rework property and edge part adhesiveness.

On the other hand, since the sheet for forming a resin film of Comparative Example 1 has a low value of the adhesive force (β1) of the surface (β), when the sheet for forming a resin film is reworked using the pressure-sensitive adhesive sheet, the sheet for forming a resin film A part of it remained on the silicon wafer, resulting in poor reworkability.

Further, since the sheet for forming a resin film of Comparative Example 3 has a high value of the adhesive force (α1) of the surface (α), the silicon wafer is damaged during the rework operation of the sheet for forming a resin film using the pressure-sensitive adhesive sheet. , resulting in poor reworkability.

Moreover, although the rework property of the sheet|seat for resin film formation of the comparative example 2 was favorable, the result was inferior to the edge part adhesiveness after attaching a silicon wafer.

The sheet for forming a resin film of one embodiment of the present invention is suitable as a material for forming a protective film for protecting the back surface of a semiconductor chip, or as a material for forming an adhesive film that can be adhered to a die pad portion or other site.

1a, 1b, 1c, 1d: composite sheet for forming a resin film
10: sheet for forming a resin film
11, 11' : support sheet
12: jig adhesive layer

Claims (11)

A sheet for forming a resin film attached to a silicon wafer to form a resin film on the silicon wafer, the sheet for forming a resin film satisfying the following requirements (I) to (III).
Requirement (I): The surface roughness (Ra) of the surface (α) of the sheet for forming a resin film on the side to be adhered to the silicon wafer is 50 nm or less.
Requirement (II): The adhesive force (α1) of the surface (α) of the sheet for forming a resin film to a silicon wafer is 1.0 to 7.0 N/25 mm.
Requirement (III): A pressure-sensitive adhesive comprising 100 parts by mass of an acrylic resin having a structural unit derived from butyl acrylate and acrylic acid and having a mass average molecular weight of 600,000 to 1,000,000 and 0.01 to 10 parts by mass of a crosslinking agent, a thickness of 10 to 50 The adhesive force (β1) of the surface (β) of the sheet for resin film formation on the opposite side to the side to be adhered to the silicon wafer with respect to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer of μm is 4.0 N/25 mm or more. The sheet for forming a resin film according to claim 1, wherein the storage elastic modulus at 23°C is 0.10 to 20 GPa. The sheet for forming a resin film according to claim 1, wherein a contact angle with respect to water on the surface (β) of the sheet for forming a resin film is 70 to 110°. The sheet for forming a resin film according to claim 2, wherein a contact angle with respect to water on the surface (β) of the sheet for forming a resin film is 70 to 110°. The sheet for forming a resin film according to claim 1, comprising a polymer component (A) and a curable component (B). The sheet for forming a resin film according to claim 5, wherein the polymer component (A) contains the acrylic polymer (A1). The sheet for forming a resin film according to claim 6, wherein the acrylic polymer (A1) is an acrylic copolymer having a structural unit (a1) derived from an alkyl (meth)acrylate and a structural unit (a2) derived from a nitrile-based monomer. . The sheet for forming a resin film according to claim 1, which is a sheet for forming a protective film for forming a protective film on a silicon wafer. The composite sheet for resin film formation which has a structure in which the sheet|seat for resin film formation in any one of Claims 1-8 was laminated|stacked on a support sheet. The composite sheet for forming a resin film according to claim 9, wherein the sheet for forming a resin film has a configuration in which the sheet for forming a resin film is sandwiched by two supporting sheets. A silicon wafer is regenerated by reworking the sheet for forming a resin film from a laminate in which the surface (α) of the sheet for forming a resin film according to any one of claims 1 to 8 is directly adhered on a silicon wafer. is a method,
A method of regenerating a silicon wafer, comprising the following steps (1) to (2).
Process (1): The process of affixing the said adhesive layer of the adhesive sheet which has a base material and an adhesive layer on the surface (beta) of the said sheet|seat for resin film formation of the said laminated body.
Step (2): A step of reworking the sheet for forming a resin film adhered on the silicon wafer by pulling the pressure-sensitive adhesive sheet adhered to the surface (β) of the sheet for forming a resin film in the step (1).

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