CN109791887B - First protective film-forming sheet - Google Patents

First protective film-forming sheet Download PDF

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CN109791887B
CN109791887B CN201780061254.6A CN201780061254A CN109791887B CN 109791887 B CN109791887 B CN 109791887B CN 201780061254 A CN201780061254 A CN 201780061254A CN 109791887 B CN109791887 B CN 109791887B
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resin film
curable resin
buffer layer
meth
protective film
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CN109791887A (en
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山岸正宪
安达一政
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Lintec Corp
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/02—Bonding areas ; Manufacturing methods related thereto
    • H01L24/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Investigating Strength Of Materials By Application Of Mechanical Stress (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Dicing (AREA)

Abstract

A first protective film forming sheet comprising a first base material, a buffer layer formed on the first base material, and a curable resin film formed on the buffer layer, wherein the buffer layer and the curable resin film are each produced into test pieces having a diameter of 8mm and a thickness of 1mm, the test pieces are strained under conditions of 90 ℃ and 1Hz, and when strain distribution measurement is performed for measuring shear elastic modulus G ' of the test pieces, the relationship between shear elastic modulus Gb300' of the test pieces of the buffer layer when strain of the test pieces of the buffer layer is 300% and shear elastic modulus Gc300' of the test pieces of the curable resin film when strain of the test pieces of the curable resin film is 300% is satisfied Gb300 '. Gtoreq.Gc 300 '.

Description

First protective film-forming sheet
Technical Field
The present invention relates to a first protective film forming sheet.
The present application claims priority based on Japanese patent application No. 2016-197523, filed in Japan at 10/5 of 2016, and the contents thereof are incorporated herein.
Background
Conventionally, when a multi-pin LSI package such as an MPU or a gate array is mounted on a printed wiring board, a Flip chip (Flip chip) mounting method has been employed, in which a semiconductor chip having a bump electrode (hereinafter referred to as a "bump" in this specification) formed of eutectic solder, high-temperature solder, gold or the like on a connection pad thereof is used, and these bumps are brought into opposition to and contact with corresponding terminal portions on a chip mounting board by a so-called Flip chip method to perform fusion/diffusion connection.
The semiconductor chip using this mounting method is obtained by grinding, dicing, or singulating a surface of a semiconductor wafer having bumps formed on a circuit surface, that is, a surface opposite to the circuit surface (in other words, the bump-formed surface). In such a process of obtaining a semiconductor chip, a curable resin film is generally attached to the bump formation surface for the purpose of protecting the bump formation surface and the bump of the semiconductor wafer, and the film is cured to form a protective film on the bump formation surface.
On the other hand, a semiconductor device is desired to have a higher function, and the size of a semiconductor chip tends to be enlarged. However, the semiconductor chip of which the size is enlarged is liable to be deformed by warpage occurring in a state of being mounted on the substrate, and particularly the bump located at or near the end portion of the semiconductor chip is liable to be cracked. It is also desirable that the protective film formed on the bump formation surface suppresses breakage of such bumps.
A method of forming a protective film on a bump formation surface of a semiconductor wafer will be described with reference to fig. 6.
The protective film forming sheet 8 shown in fig. 6 (a) is used for forming the protective film. The protective film forming sheet 8 is formed by sequentially laminating a buffer layer 83 and a curable resin film 82 on a base 81. The buffer layer 83 has a buffer effect on the force applied to the buffer layer 83 and the layer adjacent thereto.
First, the protective film forming sheet 8 is disposed so that the curable resin film 82 of the protective film forming sheet 8 faces the bump forming surface 9a of the semiconductor wafer 9.
Next, the protective film forming sheet 8 is pressed against the semiconductor wafer 9, and as shown in fig. 6 (b), the curable resin film 82 of the protective film forming sheet 8 is bonded to the bump forming surface 9a of the semiconductor wafer 9. The curable resin film 82 is bonded at this time while heating the curable resin film 82. Thus, the curable resin film 82 is adhered to the bump formation surface 9a of the semiconductor wafer 9 and the surface 91a of the bump 91, but if the bump 91 penetrates the curable resin film 82, the buffer layer 83 is adhered to a part of the surface 91a of the bump 91.
After the bonding of the curable resin film 82, a surface (back surface) 9b of the semiconductor wafer 9 opposite to the bump formation surface 9a is further ground as necessary, and then a protective film formation sheet (not shown) for protecting the back surface 9b is additionally attached to the back surface 9b of the semiconductor wafer 9.
Next, as shown in fig. 6 (c), the base material 81 and the buffer layer 83 are peeled from the curable resin film 82.
Next, the curable resin film 82 is cured, and as shown in fig. 6 (d), a protective film 82' is formed.
In such a method of forming the protective film, the upper portion 910 of the bump 91 must be protruded while penetrating the protective film 82'. For this reason, in the stage of peeling the base material 81 and the buffer layer 83, it is important to form the state in which the upper portion 910 of the bump 91 penetrates the curable resin film 82 and protrudes as described above, and the curable resin film 82 does not remain on the upper portion 910 of the bump 91. In contrast, fig. 7 shows an example of a state in which the curable resin film 82 remains on the upper portion 910 of the bump 91. Here, although an example is shown in which the entire surface 91a of the bump 91 is covered with the curable resin film 82, this is an example of a residual state of the curable resin film 82, and for example, in the upper portion 910 of the bump 91, a part of the surface 91a may not be covered with the curable resin film 82 and may be exposed.
As described above, as the protective film forming sheets which are capable of forming a protective film without leaving a curable resin film on the bump, the following protective film forming sheets are disclosed, respectively: the protective film forming sheet in which the elastic ratio of the shear storage modulus of the curable resin film to the shear storage modulus of the buffer layer at the attachment temperature for attaching the sheet to the semiconductor wafer is defined within a specific range (refer to patent document 1), and the protective film forming sheet in which the melt viscosity of the curable resin film at the attachment temperature for attaching the sheet to the semiconductor wafer is defined within a specific range (refer to patent document 2).
The protective film forming sheets disclosed in patent documents 1 and 2 each define physical properties of a curable resin film at a temperature at which the sheet is attached to a semiconductor wafer. However, the degree of strain of the buffer layer and the curable resin film constituting the sheet is greatly different between the initial stage of attachment to the semiconductor wafer and the stage after the intermediate stage. This is apparent from fig. 6 (a) and 6 (b). Further, if the degree of strain is so different, physical properties of the buffer layer and a part of the curable resin film are greatly changed. The inventors of the present application have studied with this point in mind, and as a result, have obtained the following findings: in order to suppress the residue of the curable resin film on the bump upper portion, it is important to appropriately adjust the physical properties of the curable resin film and the like in the attaching stage, particularly in a stage after the middle of attaching in which the bump upper portion is protruded while penetrating the curable resin film. In contrast, the protective film forming sheets disclosed in patent documents 1 and 2 are not configured in consideration of such points, and there is a possibility that the effect of suppressing the residual of the curable resin film on the bump is insufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-206006
Patent document 2: japanese patent No. 5666335
Disclosure of Invention
Technical problem to be solved by the invention
The present invention provides a novel protective film forming sheet comprising a curable resin film, wherein the curable resin film is applied to a surface of a semiconductor wafer having bumps and cured to form a protective film on the surface, and the curable resin film is applied to the surface so that the residue of the curable resin film on the upper portions of the bumps can be suppressed.
Technical means for solving the technical problems
A first protective film forming sheet comprising a first base material, a buffer layer formed on the first base material, and a curable resin film formed on the buffer layer, wherein the curable resin film is applied to a surface of a semiconductor wafer having bumps and cured to form a first protective film on the surface, and the test piece of the buffer layer having a diameter of 8mm and a thickness of 1mm is strained under the conditions of a temperature of 90 ℃ and a frequency of 1Hz to measure a strain distribution of a shear elastic modulus G 'of the test piece of the buffer layer, the shear modulus of the test piece of the buffer layer is Gb300' when the test piece of the buffer layer has a strain of 300%, the test piece of the curable resin film having a diameter of 8mm and a thickness of 1mm is strained under the conditions of a temperature of 90 ℃ and a frequency of 1Hz, when the strain distribution measurement is performed to measure the shear modulus G 'of the test piece of the curable resin film, the shear modulus of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 300% is Gc300', the Gb300 'and the Gc300' satisfy the following relationship,
Gb300 '. Gtoreq.Gc300'.
In the first protective film forming sheet of the present invention, the shear elastic modulus Gb200 'of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 200% and the shear elastic modulus Gc200' of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 200% may satisfy the following relationship,
gb200 '. Gtoreq.Gc200'.
In the first protective film forming sheet of the present invention, the shear elastic modulus Gb400 'of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 400% and the shear elastic modulus Gc400' of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 400% may satisfy the following relationship,
gb400 '. Gtoreq.Gc400'.
In the first protective film forming sheet according to the present invention, a region where the shear elastic modulus Gb ' is not constant may be present in a function of the strain of the test piece of the buffer layer and the shear elastic modulus Gb ' of the test piece of the buffer layer obtained by the strain distribution measurement, and the shear elastic modulus Gb ' when the strain of the test piece of the buffer layer is 300% may be included in the region.
In the first protective film-forming sheet of the present invention, a region where the shear elastic modulus Gc ' is not constant may be present in a function of the strain of the test piece of the curable resin film and the shear elastic modulus Gc ' of the test piece of the curable resin film obtained by the strain distribution measurement, and the shear elastic modulus Gc ' when the strain of the test piece of the curable resin film is 300% may be included in the region.
In the first protective film-forming sheet of the present invention, the curable resin film contains a resin component, the filler content of the curable resin film is 45 mass% or less, and the weight average molecular weight of the resin component may be 30000 or less.
Effects of the invention
The first protective film forming sheet of the present invention is attached to the surface of the semiconductor wafer having the bumps, and the curable resin film is cured, whereby the first protective film can be formed on the surface. Further, when the curable resin film is attached to the surface, the curable resin film can be prevented from remaining on the bump.
Drawings
Fig. 1 is a cross-sectional view schematically showing an embodiment of a first protective film-forming sheet according to the present invention.
Fig. 2 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention.
Fig. 3 is a cross-sectional view schematically showing an example of a method of using the first protective film forming sheet shown in fig. 1.
Fig. 4 is a cross-sectional view schematically showing an example of a method of using the first protective film forming sheet shown in fig. 2.
FIG. 5 is a graph showing the measurement results of the shear elastic modulus G' of test pieces of the buffer layers and the thermosetting resin films of examples and comparative examples.
Fig. 6 is a cross-sectional view schematically illustrating a method of forming a protective film on a bump formation surface of a semiconductor wafer.
Fig. 7 is a cross-sectional view schematically showing an example of a state in which a curable resin film remains on the bump.
Detailed Description
First protective film-forming sheet
The first protective film-forming sheet of the present invention includes a first base material, a buffer layer formed on the first base material, and a curable resin film formed on the buffer layer.
The curable resin film is applied to the surface of the semiconductor wafer having the bumps and cured to form a first protective film on the surface.
The first protective film-forming sheet of the present invention satisfies the following expression (w 1).
Gb300’≥Gc300’····(w1)
Here, gb300' is the shear elastic modulus of the test piece of the buffer layer when the strain distribution of the test piece of the buffer layer is measured and the strain of the test piece of the buffer layer is 300%. The strain distribution measurement at this time is performed by: a test piece of the buffer layer having a diameter of 8mm and a thickness of 1mm was strained at a temperature of 90℃and a frequency of 1Hz, and the shear elastic modulus G' of the test piece of the buffer layer was measured.
Further, gc300' is the shear elastic modulus of the test piece of the curable resin film when the strain distribution of the test piece of the curable resin film is measured and the strain of the test piece of the curable resin film is 300%. The strain distribution measurement at this time was performed in the same manner as in the case of the test piece of the buffer layer. That is, strain distribution was measured by measuring the shear modulus G' of a test piece of the curable resin film by applying strain to the test piece of the curable resin film having a diameter of 8mm and a thickness of 1mm at a temperature of 90℃and a frequency of 1 Hz.
As described above, the test pieces for strain distribution measurement are each in the form of a circular film.
The first protective film forming sheet of the present invention is used by attaching the curable resin film to the surface having the bump (in this specification, sometimes referred to as "bump forming surface") of the semiconductor wafer. At this time, the softened curable resin film spreads between the bumps so as to cover the bumps by adhering to the bump formation surface while heating the curable resin film, and the softened curable resin film is adhered to the bump formation surface while covering the surface of the bumps, particularly the surface of the vicinity of the bump formation surface, thereby filling the bumps. Thereafter, the curable resin film in this state is cured to finally form a first protective film. The first protective film protects the bump formation surface and the bump while being in close contact with the bump formation surface and the surface of the bump. The semiconductor wafer to which the first protective film forming sheet is attached is mounted in a semiconductor device in a state in which, for example, the first substrate and the buffer layer are removed after grinding a surface opposite to the bump forming surface, and further, the first protective film is formed, and then, the semiconductor wafer is finally mounted in the semiconductor device in a state in which the semiconductor chip is provided with the first protective film.
When the curable resin film is attached to the bump forming surface of the semiconductor wafer by using the first protective film forming sheet of the present invention, the residue of the curable resin film on the bump can be suppressed. This is because the curable resin film and the buffer layer satisfy the relationship of the above formula (w 1). After the intermediate stage of attaching the first protective film forming sheet to the semiconductor wafer, the upper portions of the bumps can easily penetrate the curable resin film and protrude by bringing the shear elastic moduli of the curable resin film and the buffer layer into the specific relationship described above in the stage where the degree of strain of the curable resin film and the buffer layer is greatly different from the initial stage of attachment.
The first protective film forming sheet satisfies the relationship of the formula (w 1). That is, the buffer layer and the curable resin film constituting the first protective film-forming sheet were each fabricated into test pieces having a diameter of 8mm and a thickness of 1mm, and the test pieces were subjected to strain at a temperature of 90℃and a frequency of 1Hz, and strain distribution measurement was performed to measure the shear elastic modulus G' of the test pieces. In this case, in the present invention, the shear elastic modulus Gb300 'of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 300% and the shear elastic modulus Gc300' of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 300% satisfy the relationship of Gb300 '. Gtoreq.Gc300'.
When the first protective film forming sheet is attached to the bump forming surface of the semiconductor wafer, the degree of strain of the buffer layer constituting the sheet is greatly different from the degree of strain of the curable resin film in the initial stage and the stages after the intermediate stage of the attachment. The reason why the values (Gb 300', gc300 ') at which the strain of the test pieces is 300% are employed as the shear modulus G ' of the test pieces of the buffer layer and the curable resin film in order to define the present invention is described here. If the degree of strain of the buffer layer is different, some physical properties of the buffer layer are greatly changed. Similarly, when the degree of strain of the curable resin film varies, some physical properties of the curable resin film also vary greatly. In order to suppress the residual of the curable resin film on the bump upper portion when the curable resin film is attached to the bump formation surface, it is important to define the relationship between the shear elastic modulus G' of the buffer layer and the curable resin film in the attachment stage of the curable resin film, particularly in the stage in which the bump upper portion protrudes through the curable resin film (in other words, the stage after the middle of attachment, or the stage in which the degree of strain of the buffer layer and the curable resin film increases to some extent). Accordingly, the present invention satisfies the relationship of the formula (w 1). The Gb300' and Gc300' are shear elastic moduli G ' at which the degree of strain of the buffer layer and the curable resin film has been increased, respectively.
The first protective film-forming sheet may satisfy the relationship of the formula (w 1), in other words, the value of Gb300'/Gc300' may be 1 or more. The value of Gb300'/Gc300' is preferably greater than 1, more preferably 10 or more, still more preferably 100 or more, and may be 1000 or more, for example, from the point of further improving the above-mentioned effects of the present invention.
In the first protective film-forming sheet, the shear elastic modulus G 'of the buffer layer and the shear elastic modulus G' of the test piece of the buffer layer can be easily adjusted by adjusting the type or content of the component contained in the buffer layer. Therefore, the kind or content of the component contained in the buffer layer forming composition to be described later for forming the buffer layer may be adjusted, and for example, the kind or content of the main component contained in the buffer layer forming composition (V) to be described later, such as the poly- α -olefin, is preferably adjusted.
In the first protective film-forming sheet, the shear elastic modulus G 'of the curable resin film and the shear elastic modulus G' of the test piece of the curable resin film can be easily adjusted by adjusting the type or content of the component contained in the curable resin film. Therefore, the type or content of the component contained in the curable resin film-forming composition to be described later for forming the curable resin film may be adjusted. For example, when the resin layer-forming composition (III) described later is used, the type or content of the main component such as the polymer component (a), the thermosetting component (B), the curing accelerator (C), or the filler (D) in the composition is preferably adjusted.
In the case of performing the strain distribution measurement, it is further preferable that the first protective film forming sheet satisfies the following expression (w 2).
Gb200’≥Gc200’····(w2)
Here, gb200' is the shear elastic modulus of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 200%. Further, gc200' is the shear elastic modulus of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 200%.
When the curable resin film of the first protective film-forming sheet satisfying the relation of the formula (w 2) is attached to the bump-forming surface, the effect of suppressing the residue of the curable resin film on the bump is further improved.
The first protective film-forming sheet preferably satisfies the relationship of the formula (w 2), in other words, the value of Gb200'/Gc200' is preferably 1 or more. The value of Gb200'/Gc200' is more preferably greater than 1, still more preferably 10 or more, particularly preferably 100 or more, and may be 1000 or more, for example, from the point of further improving the above-mentioned effects of the present invention.
In the case of performing the strain distribution measurement, it is further preferable that the first protective film forming sheet satisfies the following expression (w 3).
Gb400’≥Gc400’····(w3)
Here, gb400' is the shear elastic modulus of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 400%. Further, gc400' is the shear elastic modulus of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 400%.
When the curable resin film of the first protective film-forming sheet satisfying the relation of the formula (w 3) is attached to the bump-forming surface, the effect of suppressing the residue of the curable resin film on the bump is further improved.
The first protective film-forming sheet preferably satisfies the relationship of the formula (w 3), in other words, the value of Gb400'/Gc400' is preferably 1 or more. The value of Gb400'/Gc400' is more preferably greater than 1, still more preferably 10 or more, particularly preferably 100 or more, and may be 1000 or more, for example, from the point of further improving the above-mentioned effects of the present invention.
From the viewpoint of further improving the above-described effects of the present invention, it is preferable that the first protective film-forming sheet satisfies the relationship of the formula (w 1), and satisfies the relationship of at least one of the formulas (w 2) and (w 3), and more preferably satisfies the relationship of the formulas (w 1), (w 2) and (w 3) at the same time.
In the first protective film forming sheet, it is preferable that a region (in this specification, referred to as "fluctuation region Rb") where the shear elastic modulus Gb ' is not constant is present in a function (in this specification, referred to as "function Fb") of the strain of the test piece of the buffer layer obtained by the strain distribution measurement and the shear elastic modulus Gb ' of the test piece of the buffer layer, and it is more preferable that the shear elastic modulus Gb ' when the strain of the test piece of the buffer layer is 300% is included in the region (fluctuation region Rb). When the curable resin film of the first protective film-forming sheet is attached to the bump-forming surface, the effect of suppressing the residue of the curable resin film on the bump is further improved.
In the first protective film-forming sheet, a region where the shear elastic modulus Gc ' is not constant (in this specification, this may be referred to as "fluctuation region Rc") is preferably present in a function (in this specification, this may be referred to as "function Fc") of the strain of the test piece of the curable resin film obtained by the strain distribution measurement and the shear elastic modulus Gc ' of the test piece of the curable resin film, and more preferably, the shear elastic modulus Gc ' when the strain of the test piece of the curable resin film is 300% is included in the region (fluctuation region Rc). When the curable resin film of the first protective film-forming sheet is attached to the bump-forming surface, the effect of suppressing the residue of the curable resin film on the bump is further improved.
From the point of further improving the above-described effects of the present invention, it is preferable that the first protective film-forming sheet has a fluctuation range Rb in the function Fb and a fluctuation range Rc in the function Fc, and more preferable that the shear elastic modulus Gb 'when the strain of the test piece of the buffer layer is 300% is included in the fluctuation range Rb and the shear elastic modulus Gc' when the strain of the test piece of the curable resin film is 300% is included in the fluctuation range Rc.
In addition, in the present specification, "the shear elastic modulus is not constant" means that "the minimum value (Pa) of the shear elastic modulus is smaller than 90% of the maximum value (Pa) of the shear elastic modulus in the target region ([ the minimum value (Pa) of the shear elastic modulus ]/[ the maximum value (Pa) of the shear elastic modulus ] ×100 is smaller than 90)". In other words, the term "constant shear elastic modulus" means that the minimum value (Pa) of the shear elastic modulus is 90% or more of the maximum value (Pa) of the shear elastic modulus in the target region.
In the function Fb of the first protective film-forming sheet, as in the case of the shear modulus G', the presence or absence of the fluctuation region Rb can be easily adjusted by adjusting the type or content of the component contained in the buffer layer.
In the function Fc of the first protective film-forming sheet, as in the case of the shear elastic modulus G', the presence or absence of the fluctuation region Rb can be easily adjusted by adjusting the type or content of the component contained in the curable resin film.
Fig. 1 is a cross-sectional view schematically showing an embodiment of a first protective film-forming sheet according to the present invention. In order to facilitate understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged and displayed, and the dimensional ratios of the components and the like are not necessarily the same as those of the actual ones.
The first protective film forming sheet shown in fig. 1 includes a first base material 11, a buffer layer 13 formed on the first base material 11, and a curable resin film 12 formed on the buffer layer 13.
More specifically, in the first protective film forming sheet 1, the buffer layer 13 is laminated on the surface (hereinafter, sometimes referred to as "first surface") 11a of the first substrate 11, and the curable resin film 12 is laminated on the surface (hereinafter, sometimes referred to as "first surface") 13a of the buffer layer 13 opposite to the side on which the first substrate 11 is provided. As described above, the first protective film forming sheet 1 is formed by stacking the first base material 11, the buffer layer 13, and the curable resin film 12 in this order in the thickness direction thereof. In fig. 1, reference numeral 12a denotes a surface (hereinafter, sometimes referred to as "first surface") of the curable resin film 12 opposite to the side where the buffer layer 13 is provided.
Fig. 2 is a cross-sectional view schematically showing another embodiment of the first protective film forming sheet of the present invention.
In the drawings subsequent to fig. 2, the same components as those shown in the already described drawings are denoted by the same reference numerals as those in the already described drawings, and detailed description thereof is omitted.
The first protective film forming sheet 2 shown in fig. 2 is the same as the first protective film forming sheet 1 shown in fig. 1 except that an adhesive layer 14 (including the adhesive layer 14 formed on the first substrate 11 and the buffer layer 13 formed on the adhesive layer 14) is provided between the first substrate 11 and the buffer layer 13.
That is, in the first protective film forming sheet 2, the adhesive layer 14 is laminated on the first surface 11a of the first base material 11, the buffer layer 13 is laminated on the surface (hereinafter, sometimes referred to as "first surface") 14a of the adhesive layer 14 opposite to the side on which the first base material 11 is provided, and the first protective film forming sheet 2 is formed by laminating the first base material 11, the adhesive layer 14, the buffer layer 13, and the curable resin film 12 in this order in the thickness direction thereof.
The first protective film forming sheet of the present invention is not limited to the forming sheet shown in fig. 1 and 2, and a part of the configuration of the forming sheet shown in fig. 1 and 2 may be changed, deleted, or added within a range that does not impair the effects of the present invention.
For example, the first protective film-forming sheet of the present invention may include a release film on the outermost layer (the curable resin film 12 in the first protective film-forming sheet shown in fig. 1 and 2) on the opposite side from the base material.
Next, each layer constituting the first protective film forming sheet of the present invention will be described.
Very good first substrate
The first base material is in the form of a sheet or film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylene such as Low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins (resins obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; a polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters each having an aromatic ring group in its constituent unit; copolymers of two or more of the polyesters; poly (meth) acrylates; polyurethane; a urethane acrylate; polyimide; a polyamide; a polycarbonate; a fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyetherketone, and the like.
The resin may be, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester. Preferably, the amount of resin other than polyester in the polymer alloy of the polyester and resin other than polyester is a small amount.
Examples of the resin include crosslinked resins obtained by crosslinking one or more of the above resins; modified resins such as ionomers of one or two or more of the above resins exemplified above are used.
In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Similar terms to (meth) acrylic acid are also used, for example, "(meth) acrylate" is a concept that includes both "acrylate" and "methacrylate", and "(meth) acryl" is a concept that includes both "acryl" and "methacryl".
The resin constituting the first base material may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The first substrate may be a single layer or a plurality of layers of two or more layers, and when the layers are a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
In the present specification, not limited to the case of the first base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or different from each other or only a part of layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent materials and thicknesses of the respective layers is different from each other".
The thickness of the first substrate is preferably 5 to 1000. Mu.m, more preferably 10 to 500. Mu.m, still more preferably 15 to 300. Mu.m, particularly preferably 20 to 150. Mu.m.
Here, the "thickness of the first substrate" refers to the thickness of the entire first substrate, and for example, the thickness of the first substrate composed of a plurality of layers refers to the total thickness of all layers constituting the first substrate.
The first substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which variation in thickness is suppressed at any position. Examples of the material that can be used as the material constituting the first base material having such high thickness accuracy include polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer.
The first base material may contain, in addition to the main constituent materials such as the resin, various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer).
The first substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited with another layer.
When the curable resin film is energy ray curable, the first substrate preferably transmits energy rays.
The first substrate can be produced by a known method. For example, the first substrate containing a resin can be produced by molding a resin composition containing the resin.
Very good buffer layer
The buffer layer has a buffering effect on forces applied to the buffer layer and the layers adjacent thereto. Here, "layer adjacent to the buffer layer" mainly means a curable resin film and a first protective film corresponding to the cured product thereof.
The buffer layer is sheet-like or film-like, and the constituent material thereof is not particularly limited as long as the relationship of the above formula (w 1) is satisfied.
Examples of the preferred buffer layer include buffer layers containing various resins such as poly- α -olefin.
The buffer layer may be one layer (single layer), or a plurality of layers of two or more layers, and when the buffer layer is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the buffer layer is preferably 150 to 1000. Mu.m, more preferably 150 to 800. Mu.m, still more preferably 200 to 600. Mu.m, particularly preferably 250 to 500. Mu.m.
Here, the "thickness of the buffer layer" refers to the thickness of the entire buffer layer, and for example, the thickness of the buffer layer composed of a plurality of layers refers to the total thickness of all the layers constituting the buffer layer.
Buffer layer forming composition
The buffer layer can be formed using a composition for forming a buffer layer containing a constituent material of the buffer layer such as the resin. For example, the buffer layer can be formed at the target site by extrusion molding the buffer layer forming composition onto the surface to be formed of the buffer layer. A more specific method of forming the buffer layer will be described in detail later together with a method of forming other layers. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming a buffer layer is generally the same as the content ratio of the components of the buffer layer. In the present specification, the term "normal temperature" refers to a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ℃.
Composition (V) for forming buffer layer
Examples of the composition for forming a buffer layer include a composition (V) for forming a buffer layer containing a polyalphaolefin.
The polyalphaolefin may be a polyalphaolefin having structural units derived from an alpha-olefin.
The structural units of the poly- α -olefin may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected. That is, the poly- α -olefin may be a homopolymer obtained by polymerizing 1 monomer, or may be a copolymer obtained by copolymerizing 2 or more monomers.
Preferably the polyalphaolefin is an ethylene-alpha-olefin copolymer.
The density of the polyalphaolefins is preferably 890kg/m 3 Hereinafter, 830 to 890kg/m is more preferable 3 Particularly preferably 850 to 875kg/m 3 . In addition, in the present specification, unless otherwise indicated, "density of a polyalphaolefin" refers to a value determined based on ASTM D1505.
The melting point of the poly-alpha-olefin is preferably 55℃or less, more preferably 50℃or less.
The Melt Flow Rate (MFR) of the poly-alpha-olefin at 190℃is preferably 1 to 6g/10 min, more preferably 2.5 to 4.5g/10 min.
Further, the Melt Flow Rate (MFR) of the poly-alpha-olefin at 230℃is preferably 2 to 12g/10 min, more preferably 4 to 9g/10 min.
In addition, in the present specification, unless otherwise indicated, "melt flow rate of a polyalphaolefin" refers to a value determined based on ASTM D1238.
The composition (V) for forming a buffer layer preferably contains 80 to 100% by mass of the poly-alpha-olefin in the buffer layer.
[ other Components ]
The buffer layer-forming composition (V) and the buffer layer may contain other components than the polyalphaolefin as long as the effects of the present invention are not impaired.
The other components are not particularly limited and may be appropriately selected according to the purpose.
The buffer layer-forming composition (V) and the other components contained in the buffer layer may be one kind only, or may be two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The buffer layer forming composition (V) and the content of the other components of the buffer layer are not particularly limited, and may be appropriately selected according to the purpose.
Excellent curable resin film
The curable resin film is a layer for protecting a bump formation surface (in other words, a circuit surface) of a semiconductor wafer and a bump provided on the bump formation surface, and is a thermosetting resin film in the first embodiment and an energy ray curable resin film in the second embodiment. The curable resin film is cured to form a first protective film.
The curable resin film is in the form of a sheet or film, and the constituent material is not particularly limited as long as the relationship of the above formula (w 1) is satisfied.
The curable resin may be any of thermosetting or energy ray-curable, but is preferably thermosetting.
In the present specification, the term "energy ray" refers to a ray having energy in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation rays, and electron beams.
The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp (fusion H lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet source. The electron beam can irradiate an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray curability" refers to a property that is cured by irradiation with energy rays, and "non-energy ray curability" refers to a property that is not cured even when energy rays are irradiated.
The curable resin film contains a resin component, may contain a filler other than the resin component, and may not contain a filler other than the resin component, and the content of the filler is preferably 45 mass% or less.
In the curable resin film, the weight average molecular weight of the resin component is preferably 1000000 or less, and may be, for example, any one of 800000 or less, 500000 or less, 300000 or less, 200000 or less, 100000 or less, 50000 or 30000 or less.
On the other hand, in the curable resin film, the lower limit value of the weight average molecular weight of the resin component is not particularly limited, and may be any one of 5000 and 8000, for example.
By making the resin component satisfy these respective conditions, the effect of the first protective film forming sheet in suppressing the residue of the curable resin film on the bump upper portion is further improved.
In the present specification, unless otherwise indicated, the weight average molecular weight is a polystyrene equivalent measured by Gel Permeation Chromatography (GPC).
The weight average molecular weight of the resin component can be appropriately adjusted so that the weight average molecular weight of the resin component is within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value.
Preferable examples of the weight average molecular weight include 5000 to 1000000, 5000 to 800000, 5000 to 500000, 5000 to 300000, 5000 to 200000, 5000 to 100000, 5000 to 50000, and 5000 to 30000.
Examples of preferable weight average molecular weights include 8000 to 1000000, 8000 to 800000, 8000 to 500000, 8000 to 300000, 8000 to 200000, 8000 to 100000, 8000 to 50000, and 8000 to 30000.
However, the weight average molecular weight is not limited thereto.
The content of the filler in the curable resin film is more preferably 40 mass% or less, and particularly preferably 30 mass% or less.
On the other hand, the lower limit of the filler content of the curable resin film is not particularly limited. For example, the filler content of the curable resin film may be any one of 0 mass% or more, 5 mass% or more, 10 mass% or more, and the like.
The content of the filler of the curable resin film can be appropriately adjusted so that the content of the filler of the curable resin film is within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value.
Preferable examples of the content of the filler in the curable resin film include 0 to 45 mass%, 0 to 40 mass%, 0 to 30 mass%, and the like.
However, the content of the filler of the curable resin film is not limited thereto.
The curable resin film particularly preferably contains a resin component having a weight average molecular weight of 30000 or less, and the filler content is 45 mass% or less. By satisfying such a condition, the effect of the first protective film forming sheet in suppressing the residue of the curable resin film on the bump is further enhanced.
The type of the resin component and the filler is not particularly limited.
Examples of such a curable resin film include a curable resin film containing a resin component having a weight average molecular weight of 30000 or less (for example, 5000 to 30000, 8000 to 30000, etc.), and the filler content is preferably 0 to 45 mass%, more preferably 0 to 40 mass%, and still more preferably 0 to 30 mass%.
The curable resin film can be formed using a curable resin film-forming composition containing the constituent materials thereof. For example, the resin component is contained in the total amount of components corresponding to the resin in the thermosetting resin film-forming composition described later.
Thermosetting resin film
As a preferable thermosetting resin film, for example, a thermosetting resin film containing a polymer component (a) as the resin component and further containing a thermosetting component (B) can be cited.
The thermosetting resin film may be a single layer (single layer) or a plurality of layers of two or more layers, and when the layers are a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
The thickness of the thermosetting resin film is preferably 1 to 100. Mu.m, more preferably 5 to 75. Mu.m, particularly preferably 5 to 50. Mu.m. By setting the thickness of the thermosetting resin film to the lower limit value or more, a first protective film having a higher protective ability can be formed. Further, by setting the thickness of the thermosetting resin film to the above upper limit value or less, the thickness can be suppressed from becoming excessive.
Here, the "thickness of the thermosetting resin film" refers to the thickness of the entire thermosetting resin film, and for example, the thickness of the thermosetting resin film composed of a plurality of layers refers to the total thickness of all the layers constituting the thermosetting resin film.
Composition for forming thermosetting resin film
The thermosetting resin film can be formed using a thermosetting resin film-forming composition containing the constituent materials thereof. For example, the thermosetting resin film-forming composition is applied to the surface to be formed of the thermosetting resin film and dried as necessary, whereby the thermosetting resin film can be formed at the target site. A more specific method of forming the thermosetting resin film will be described in detail later together with a method of forming other layers. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming a thermosetting resin film is generally the same as the content ratio of the components of the thermosetting resin film.
The thermosetting resin film-forming composition may be applied by a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater (screen coater), a meyer bar coater, and a kiss coater.
The drying conditions of the thermosetting resin film-forming composition are not particularly limited, but when the thermosetting resin film-forming composition contains a solvent described later, it is preferable to perform heat drying. The solvent-containing thermosetting resin film-forming composition is preferably dried at a temperature of 70 to 130℃for 10 seconds to 5 minutes, for example.
Composition (III) for forming resin layer
Examples of the thermosetting resin film-forming composition include a thermosetting resin film-forming composition (III) containing a polymer component (a) and a thermosetting component (B) (in this specification, the term "resin layer-forming composition (III)" may be abbreviated as "in some cases).
[ Polymer component (A) ]
The polymer component (a) is a polymer compound for imparting film-forming property, flexibility, and the like to a thermosetting resin film, and is considered to be a component formed by polymerizing a polymerizable compound. The polymerization reaction in the present specification also includes a polycondensation reaction.
The polymer component (a) contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include an acrylic resin (a resin having a (meth) acryloyl group), and a polyvinyl acetal.
The acrylic resin in the polymer component (a) may be a known acrylic polymer.
The weight average molecular weight (Mw) of the acrylic resin is preferably 5000 to 1000000, more preferably 8000 to 800000. When the weight average molecular weight of the acrylic resin is in such a range, the effect of suppressing the residue of the curable resin film on the bump upper portion is further improved when the curable resin film is attached to the bump formation surface.
The glass transition temperature (Tg) of the acrylic resin is preferably-50 to 70℃and more preferably-30 to 60 ℃. When the Tg of the acrylic resin is in such a range, the effect of suppressing the residue of the curable resin film on the bump is further improved when the curable resin film is attached to the bump-forming surface.
The monomers constituting the acrylic resin may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic resin include polymers of one or more (meth) acrylic esters;
copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like;
copolymers of two or more (meth) acrylates with one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like.
Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and the like Alkyl (meth) acrylate having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms;
Cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyl oxyalkyl (meth) acrylates such as dicyclopentenoxyethyl (meth) acrylate;
(meth) acrylimide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxy group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate, and the like. Here, "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may have a functional group that can be bonded to other compounds, such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. The functional group of the acrylic resin may be bonded to other compounds via a crosslinking agent (F) described later, or may be directly bonded to other compounds without via the crosslinking agent (F). The acrylic resin is bonded to other compounds through the functional group, and thus the reliability of the package obtained by using the first protective film-forming sheet tends to be improved.
The polyvinyl acetal in the polymer component (a) includes known polyvinyl acetals.
Among them, preferable polyvinyl acetals include, for example, polyvinyl formal and polyvinyl butyral, and more preferable polyvinyl butyral.
The polyvinyl butyral includes polyvinyl butyrals having structural units represented by the following formulas (i) -1, (i) -2 and (i) -3.
[ chemical formula 1]
Figure BDA0002015437460000211
Wherein l, m and n are each independently an integer of 1 or more.
The weight average molecular weight (Mw) of the polyvinyl acetal is preferably 5000 to 200000, more preferably 8000 to 100000. When the weight average molecular weight of the polyvinyl acetal is in such a range, the effect of suppressing the residue of the curable resin film on the bump upper portion is further improved when the curable resin film is attached to the bump formation surface.
The glass transition temperature (Tg) of the polyvinyl acetal is preferably 40 to 80℃and more preferably 50 to 70 ℃. When the Tg of the polyvinyl acetal is in such a range, the effect of suppressing the residue of the curable resin film on the bump upper portion is further improved when the curable resin film is attached to the bump formation surface.
The ratio of the three or more monomers constituting the polyvinyl acetal may be arbitrarily selected.
In the composition (III) for forming a resin layer, the proportion of the content of the polymer component (a) (i.e., the content of the polymer component (a) of the thermosetting resin film) relative to the total content of all components except the solvent is preferably 5 to 25% by mass, more preferably 5 to 15% by mass, regardless of the kind of the polymer component (a).
[ thermosetting component (B) ]
The thermosetting component (B) is a component for forming a hard first protective film by curing a thermosetting resin film using heat as a trigger (trigger) of reaction.
The thermosetting component (B) contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Preferably, the thermosetting component (B) is an epoxy thermosetting resin.
(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
The epoxy resin (B1) includes known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, and epoxy compounds having a double function or more such as phenylene skeleton type epoxy resins.
The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. The epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained using the first protective film-forming sheet is improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy groups of a multifunctional epoxy resin is converted into groups having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting (meth) acrylic acid or a derivative thereof to an addition reaction with an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene (vinyl) group, a 2-propenyl (allyl) group, a (meth) acryl group, a (meth) acrylamide group, and the like, and acryl groups are preferable.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000, from the viewpoint of curability of the thermosetting resin film and strength and heat resistance of the first protective film.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 300 to 800g/eq.
The epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used at the same time, the combination and ratio thereof may be arbitrarily selected.
Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group, and the functional group is preferably a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (B2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-phenol resins.
Examples of amine curing agents having an amino group in the thermosetting agent (B2) include dicyandiamide (hereinafter, abbreviated as "dic") and the like.
The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenol resin, and the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as that in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.
The number average molecular weight of the resin component of the thermosetting agent (B2), for example, a polyfunctional phenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, an aralkyl phenol resin or the like is preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol or dicyandiamide in the thermosetting agent (B2) is not particularly limited, and is preferably 60 to 500, for example.
The thermosetting agent (B2) may be used alone or in combination of two or more kinds, and when two or more kinds are used at the same time, the combination and ratio thereof may be arbitrarily selected.
In the resin layer-forming composition (III) and the thermosetting resin film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and for example, may be any one of 1 to 150 parts by mass, 1 to 100 parts by mass, and 1 to 75 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the lower limit value or more, curing of the thermosetting resin film becomes easier. Further, by setting the content of the thermosetting agent (B2) to the upper limit value or less, the moisture absorption rate of the thermosetting resin film is reduced, and the reliability of the package obtained by using the first protective film forming sheet is further improved.
In the resin layer-forming composition (III) and the thermosetting resin film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 600 to 1000 parts by mass per 100 parts by mass of the content of the polymer component (a). By setting the content of the thermosetting component (B) to such a range, the effect of suppressing the residue of the curable resin film on the bump can be further improved, and a hard first protective film can be formed.
Further, from the point that such an effect can be more remarkably obtained, it is preferable to appropriately adjust the content of the thermosetting component (B) according to the kind of the polymer component (a).
For example, when the polymer component (a) is the acrylic resin, the content of the thermosetting component (B) is preferably 700 to 1000 parts by mass, more preferably 750 to 1000 parts by mass, and particularly preferably 750 to 900 parts by mass, relative to 100 parts by mass of the content of the polymer component (a) in the resin layer-forming composition (iii) and the thermosetting resin film.
For example, when the polymer component (a) is the polyvinyl acetal, the content of the thermosetting component (B) is preferably 600 to 1000 parts by mass, more preferably 650 to 1000 parts by mass, and particularly preferably 650 to 950 parts by mass, per 100 parts by mass of the content of the polymer component (a) in the resin layer-forming composition (iii) and the thermosetting resin film.
[ curing accelerator (C) ]
The resin layer-forming composition (III) and the thermosetting resin film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the resin layer-forming composition (III).
Examples of the preferable curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which 1 or more hydrogen atoms are substituted with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphine in which 1 or more hydrogen atoms are replaced with an organic group); tetraphenylboron salts such as tetraphenylboron tetraphenylphosphine and triphenylphosphine tetraphenylborate.
The curing accelerator (C) contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the content of the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film. By setting the content of the curing accelerator (C) to the above lower limit value or more, the effect of using the curing accelerator (C) can be more significantly obtained. Further, by setting the content of the curing accelerator (C) to the above-described upper limit value or less, for example, the effect of inhibiting the high-polarity curing accelerator (C) from moving to the adhesion interface side with the adherend in the thermosetting resin film under the conditions of high temperature and high humidity and segregation is improved, and the reliability of the package obtained by using the first protective film forming sheet is further improved.
[ Filler (D) ]
The resin layer-forming composition (III) and the thermosetting resin film may contain a filler (D). By containing the filler (D) in the thermosetting resin film, the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin film can be easily adjusted. For example, by optimizing the coefficient of thermal expansion of the first protective film with respect to the object to be formed of the first protective film, the reliability of the package obtained by using the first protective film forming sheet is further improved. Further, by containing the filler (D) in the thermosetting resin film, the moisture absorption rate of the first protective film can be reduced or the heat radiation property can be improved.
The filler (D) may be any of an organic filler and an inorganic filler, but is preferably an inorganic filler.
Preferable examples of the inorganic filler include powders such as silica, alumina, talc, calcium carbonate, titanium white, red lead, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fiber, and the like.
Among them, the inorganic filler is preferably silica or alumina.
The filler (D) contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the resin layer-forming composition (III), the proportion of the content of the filler (D) relative to the total content of all components except the solvent (i.e., the content of the filler (D) of the thermosetting resin film) is preferably 45 mass% or less (0 to 45 mass%). By setting the content of the filler (D) to such a range, the effect of suppressing the residue of the curable resin film on the bump can be further improved.
On the other hand, when the filler (D) is used, the proportion of the content of the filler (D) relative to the total content of all components except the solvent (i.e., the content of the filler (D) of the thermosetting resin film) in the resin layer-forming composition (III) is more preferably 5 to 45% by mass, still more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. By setting the content of the filler (D) to such a range, the effect of suppressing the residue of the curable resin film on the bump can be further improved, and the adjustment of the coefficient of thermal expansion can be facilitated.
[ coupling agent (E) ]
The resin layer-forming composition (III) and the thermosetting resin film may contain a coupling agent (E). By using a substance having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (E), the adhesion and the adhesiveness of the thermosetting resin film to an adherend can be improved. Further, by using the coupling agent (E), the water resistance of the first protective film obtained by curing the thermosetting resin film is improved without impairing the heat resistance.
The coupling agent (E) is preferably a compound having a functional group reactive with the functional groups of the polymer component (a), the thermosetting component (B), and the like, and more preferably a silane coupling agent.
Preferable examples of the silane coupling agent include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3- (2-aminoethylamino) propyl methyl diethoxysilane, 3- (phenylamino) propyl trimethoxysilane, 3-anilinopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazole silane.
The resin layer-forming composition (III) and the thermosetting resin film may contain only one kind of coupling agent (E), or two or more kinds of coupling agent (E), and when two or more kinds of coupling agent (E) are used, the combination and ratio of these may be arbitrarily selected.
When the coupling agent (E) is used, the content of the coupling agent (E) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (B) in the resin layer-forming composition (III) and the thermosetting resin film. By setting the content of the coupling agent (E) to the lower limit value or more, the effect of using the coupling agent (E) such as an improvement in dispersibility of the filler (D) in the resin, an improvement in adhesion of the thermosetting resin film to the adherend, and the like can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of degassing can be further suppressed.
[ Cross-linker (F) ]
When a substance having a functional group such as a vinyl group, (meth) acryl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which can be bonded to other compounds, is used as the polymer component (a), the resin layer-forming composition (III) and the thermosetting resin film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by crosslinking in this manner, the initial adhesion and cohesive force of the thermosetting resin film can be adjusted.
Examples of the crosslinking agent (F) include an organic polyisocyanate compound, an organic polyimide compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively abbreviated as "aromatic polyisocyanate compounds and the like"); a trimer, isocyanurate, or adduct of the aromatic polyisocyanate compound; and a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound. The "adduct" refers to a reactant of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Examples of the adduct include a xylylene diisocyanate adduct of trimethylolpropane, which will be described later. In addition, the "terminal isocyanate urethane prepolymer" is the same as that described hereinabove.
More specifically, examples of the organic polyisocyanate compound include 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; any one or two or more compounds selected from toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or a part of hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyimine compound include N, N ' -diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinyl propionate, tetramethylolmethane-tris- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridinyl carboxamide) triethylenemelamine.
When an organic polyisocyanate compound is used as the crosslinking agent (F), a hydroxyl group-containing polymer is preferably used as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (a) has a hydroxyl group, the crosslinked structure can be easily introduced into the thermosetting resin film by the reaction of the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the resin layer-forming composition (III) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the crosslinking agent (F) to the lower limit value or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. Further, by setting the content of the crosslinking agent (F) to the upper limit value or less, excessive use of the crosslinking agent (F) can be suppressed.
[ other Components ]
The resin layer-forming composition (III) and the thermosetting resin film may contain components other than the polymer component (a), the thermosetting component (B), the curing accelerator (C), the filler (D), the coupling agent (E) and the crosslinking agent (F) as far as the effects of the present invention are not impaired.
Examples of the other components include an energy ray curable resin, a photopolymerization initiator, and general-purpose additives. The general-purpose additive is a known additive, and may be arbitrarily selected according to the purpose, but is not particularly limited, and examples of preferable additives include plasticizers, antistatic agents, antioxidants, colorants (dyes and pigments), capturing agents (coloring agents), and the like.
The other components contained in the resin layer-forming composition (III) and the thermosetting resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The content of the other components of the resin layer-forming composition (III) and the thermosetting resin film is not particularly limited, and may be appropriately selected according to the purpose.
[ solvent ]
The resin layer-forming composition (III) preferably further contains a solvent. The solvent-containing resin layer-forming composition (III) is excellent in handleability.
The solvent is not particularly limited, but examples of the preferable solvent include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the resin layer-forming composition (III) may be one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
The solvent contained in the resin layer-forming composition (III) is preferably methyl ethyl ketone or the like, since the components contained in the resin layer-forming composition (III) can be mixed more uniformly.
The content of the solvent in the resin layer-forming composition (III) is not particularly limited, and may be appropriately selected according to the kind of the component other than the solvent, for example.
Process for producing composition for forming thermosetting resin film
The thermosetting resin film-forming composition such as the resin layer-forming composition (III) can be obtained by blending the components constituting the composition.
The order of addition in blending the components is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any blend component other than the solvent to dilute the blend component in advance, or the solvent may be mixed with any blend component other than the solvent without diluting the blend component in advance.
The method of mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, stirring blades, or the like; a method of mixing using a stirrer; and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of adding and mixing the components are not particularly limited as long as the components to be blended are not degraded, and the temperature is preferably 15 to 30 ℃.
Energy ray-curable resin film
The energy ray-curable resin film contains an energy ray-curable component (a).
In the energy ray-curable resin film, the energy ray-curable component (a) is preferably uncured, preferably has tackiness, more preferably uncured and has tackiness.
The energy ray-curable resin film may be a single layer (single layer) or a plurality of layers of two or more layers, and when the layers are a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
The thickness of the energy ray-curable resin film is preferably 1 to 100. Mu.m, more preferably 5 to 75. Mu.m, particularly preferably 5 to 50. Mu.m. By setting the thickness of the energy ray-curable resin film to the lower limit value or more, a first protective film having higher protective ability can be formed. Further, by setting the thickness of the energy ray-curable resin film to the above-described upper limit value or less, the thickness can be suppressed from becoming excessive.
Here, the "thickness of the energy ray-curable resin film" refers to the thickness of the entire energy ray-curable resin film, and for example, the thickness of the energy ray-curable resin film composed of a plurality of layers refers to the total thickness of all layers constituting the energy ray-curable resin film.
The curing condition for forming the first protective film by attaching the energy ray-curable resin film to the bump-forming surface of the semiconductor wafer and curing the energy ray-curable resin film is not particularly limited as long as the first protective film has a degree of curing sufficient to perform its function, and may be appropriately selected depending on the type of the thermosetting resin film.
For example, the illuminance of the energy ray at the time of curing the energy ray-curable resin film is preferably 180 to 280mW/cm 2 . The amount of energy rays at the time of curing is preferably 450 to 1000mJ/cm 2 。
Composition for forming energy ray-curable resin film
The energy ray-curable resin film can be formed using an energy ray-curable resin film-forming composition containing the constituent materials thereof. For example, the energy ray-curable resin film-forming composition can be applied to the surface of the energy ray-curable resin film to be formed and dried as necessary, whereby the energy ray-curable resin film can be formed at the target site. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming an energy ray-curable resin film is generally the same as the content ratio of the components of the energy ray-curable resin film.
The composition for forming an energy ray-curable resin film may be applied by a known method, and examples thereof include methods using various coaters such as an air knife coater, a doctor blade coater, a bar coater, a gravure coater, a roll knife coater, a curtain coater, a die coater, a blade coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the composition for forming an energy ray-curable resin film are not particularly limited, but when the composition for forming an energy ray-curable resin film contains a solvent described later, it is preferable to perform heat drying. The composition for forming an energy ray-curable resin film containing a solvent is preferably dried at a temperature of 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
Composition (IV) for forming resin layer
Examples of the composition for forming an energy ray-curable resin film include a composition (IV) for forming an energy ray-curable resin film containing the energy ray-curable component (a) (in this specification, the composition (IV) for forming a resin layer may be abbreviated as "composition (IV)").
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming properties, flexibility, and the like to the energy ray-curable resin film.
Examples of the energy ray-curable component (a) include a polymer (a 1) having an energy ray-curable group and having a weight average molecular weight of 80000 ～ 2000000 and a compound (a 2) having an energy ray-curable group and having a molecular weight of 100 to 80000. The polymer (a 1) may be a crosslinked material at least a part of which is crosslinked by a crosslinking agent, or may be an uncrosslinked material.
(Polymer (a 1) having an energy ray-curable group and having a weight-average molecular weight of 80000 ～ 2000000)
Examples of the polymer (a 1) having an energy ray-curable group and a weight average molecular weight of 80000 ～ 2000000 include an acrylic resin (a 1-1) obtained by polymerizing an acrylic polymer (a 11) and an energy ray-curable compound (a 12), wherein the acrylic polymer (a 11) has a functional group capable of reacting with a group of another compound, and the energy ray-curable compound (a 12) has a group capable of reacting with the functional group and an energy ray-curable group such as an energy ray-curable double bond.
Examples of the functional group that can react with a group of another compound include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of the amino group are replaced with groups other than hydrogen atoms), an epoxy group, and the like. However, from the point of preventing corrosion of circuits of a semiconductor wafer, a semiconductor chip, or the like, it is preferable that the functional group is a group other than a carboxyl group.
Wherein preferably the functional group is a hydroxyl group.
Acrylic Polymer having functional group (a 11)
Examples of the acrylic polymer (a 11) having a functional group include a polymer obtained by copolymerizing an acrylic monomer having a functional group with an acrylic monomer having no functional group, and a polymer obtained by copolymerizing a monomer other than an acrylic monomer (a non-acrylic monomer) other than these monomers.
The acrylic polymer (a 11) may be a random copolymer or a block copolymer.
Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols (unsaturated alcohols having no (meth) acryl skeleton) such as vinyl alcohol and allyl alcohol.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
Preferably, the acrylic monomer having the functional group is a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a 11) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and stearyl (meth) acrylate The alkyl group constituting the alkyl ester is a chain-structured alkyl (meth) acrylate having 1 to 18 carbon atoms, or the like.
Examples of the acrylic monomer having no functional group include alkoxyalkyl group-containing (meth) acrylates such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like; (meth) acrylic esters having an aromatic group, including aryl (meth) acrylates such as phenyl (meth) acrylate; non-crosslinking (meth) acrylamides and derivatives thereof; non-crosslinkable (meth) acrylic acid esters having tertiary amino groups such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer not having the functional group constituting the acrylic polymer (a 11) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a 11) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a 11), the proportion (content) of the amount of the structural unit derived from the acrylic monomer having the functional group is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass, relative to the total amount of the structural units constituting it. By setting the ratio to such a range, the content of the energy ray-curable group in the acrylic resin (a 1-1) obtained by copolymerizing the acrylic polymer (a 11) with the energy ray-curable compound (a 12) can easily adjust the curing degree of the first protective film to a preferable range.
The acrylic polymer (a 11) constituting the acrylic resin (a 1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The content of the acrylic resin (a 1-1) in the resin layer-forming composition (IV) is preferably 1 to 40, more preferably 2 to 30, particularly preferably 3 to 20.
Energy ray-curable Compound (a 12)
The energy ray-curable compound (a 12) preferably has one or more groups selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as groups that can react with functional groups of the acrylic polymer (a 11), and more preferably has isocyanate groups as the groups. For example, when the energy ray-curable compound (a 12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a 11) having a hydroxyl group as the functional group.
The energy ray-curable compound (a 12) preferably has 1 to 5 energy ray-curable groups in 1 molecule, more preferably 1 to 2 energy ray-curable groups.
Examples of the energy ray-curable compound (a 12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate;
an acryl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and acryl monoisocyanate compounds obtained by reacting a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among them, the energy ray-curable compound (a 12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a 12) constituting the acrylic resin (a 1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a 1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a 12) to the content of the functional group derived from the acrylic polymer (a 11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. By making the ratio of the content in such a range, the adhesive force of the first protective film becomes larger. In addition, when the energy ray-curable compound (a 12) is a monofunctional (1 molecule having 1 of the groups), the upper limit of the content ratio is 100 mol%, and when the energy ray-curable compound (a 12) is a polyfunctional (1 molecule having 2 or more of the groups), the upper limit of the content ratio is sometimes more than 100 mol%.
The weight average molecular weight (Mw) of the polymer (a 1) is preferably 100000 ～ 2000000, more preferably 300000 ～ 1500000.
Here, the "weight average molecular weight" is the same as that described hereinabove.
When the polymer (a 1) is a substance in which at least a part thereof is crosslinked by a crosslinking agent, the polymer (a 1) may be a polymer in which a monomer having a group reactive with the crosslinking agent is copolymerized and crosslinked at a group reactive with the crosslinking agent, or a polymer in which a group reactive with the functional group is derived from the energy ray-curable compound (a 12), not being any of the above monomers described as monomers constituting the acrylic polymer (a 11).
The polymer (a 1) contained in the resin layer-forming composition (IV) and the energy ray-curable resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a 2) having an energy ray-curable group and having a molecular weight of 100 to 80000)
The energy ray-curable group in the compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000 includes a group containing an energy ray-curable double bond, and preferable groups include a (meth) acryloyl group, a vinyl group, and the like.
The compound (a 2) is not particularly limited as long as the above conditions are satisfied, and examples thereof include low molecular weight compounds having an energy ray-curable group, epoxy resins having an energy ray-curable group, phenol resins having an energy ray-curable group, and the like.
The low molecular weight compound having an energy ray-curable group in the compound (a 2) includes, for example, a polyfunctional monomer or oligomer, and the like, and an acrylic compound having a (meth) acryloyl group is preferable.
As the above-mentioned acrylic acid ester-based compound, examples thereof include 2-hydroxy-3- (meth) acryloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloxypolypropoxy) phenyl ] propane tricyclodecane dimethanol di (meth) acrylate, 1, 10-decane diol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, difunctional (meth) acrylates such as neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acryloxypropane;
Polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like;
multifunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers, and the like.
As the epoxy resin having an energy ray-curable group or the phenol resin having an energy ray-curable group in the compound (a 2), for example, the resin described in paragraph 0043 or the like of "japanese patent application laid-open No. 2013-194102" can be used. Such a resin also corresponds to a resin constituting a thermosetting component described later, but is regarded as the compound (a 2) in the present invention.
The weight average molecular weight of the compound (a 2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a 2) contained in the resin layer-forming composition (IV) and the energy ray-curable resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the resin layer-forming composition (IV) and the energy ray-curable resin film contain the compound (a 2) as the energy ray-curable component (a), it is preferable that the composition further contain a polymer (b) having no energy ray-curable group.
The polymer (b) may be a substance crosslinked at least partially with a crosslinking agent, or may be a substance not crosslinked.
Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, polyurethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known acrylic polymer, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, glycidyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, and substituted amino group-containing (meth) acrylates. Here, "substituted amino group" is the same as that described hereinabove.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and stearyl (meth) acrylate The alkyl group constituting the alkyl ester is a chain-structured alkyl (meth) acrylate having 1 to 18 carbon atoms, or the like.
Examples of the (meth) acrylic acid ester having a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
and cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate and the like.
Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the polymer (b) having no energy ray-curable group and crosslinked at least partially with a crosslinking agent include polymers obtained by reacting a reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group is not particularly limited, as long as it is appropriately selected according to the kind of the crosslinking agent and the like. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, a hydroxyl group having high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, and the like, and among these, a carboxyl group having high reactivity with an epoxy group is preferable. However, from the point of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip, it is preferable that the reactive functional group is a group other than a carboxyl group.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include a polymer obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer may be used as the monomer constituting the acrylic polymer (b-1). Examples of the polymer (b) having a hydroxyl group as a reactive functional group include a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and other examples of the polymer (b) include a polymer obtained by polymerizing a monomer obtained by substituting the reactive functional group with one or more hydrogen atoms in the acrylic monomer or the non-acrylic monomer listed above.
In the polymer (b) having a reactive functional group, the proportion (content) of the amount of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, relative to the total amount of the structural units constituting it. By setting the ratio to such a range, the degree of crosslinking in the polymer (b) becomes a more preferable range.
The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 ～ 2000000, more preferably 100000 ～ 1500000, from the viewpoint of better film-forming property of the resin layer-forming composition (IV). Here, the "weight average molecular weight" is the same as that described hereinabove.
The polymer (b) having no energy ray-curable group contained in the resin layer-forming composition (IV) and the energy ray-curable resin film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The resin layer-forming composition (IV) includes a resin layer-forming composition containing one or both of the polymer (a 1) and the compound (a 2). When the resin layer-forming composition (IV) contains the compound (a 2), it preferably further contains the polymer (b) having no energy ray-curable group, and in this case, it further preferably further contains the compound (a 1). The resin layer-forming composition (IV) may not contain the compound (a 2) but may contain the polymer (a 1) and the polymer (b) having no energy ray-curable group.
When the resin layer-forming composition (IV) contains the polymer (a 1), the compound (a 2), and the polymer (b) having no energy ray-curable group, the content of the compound (a 2) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a 1) and the polymer (b) having no energy ray-curable group in the resin layer-forming composition (IV).
In the resin layer-forming composition (IV), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group (i.e., the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) of the energy ray-curable resin film) to the total content of the components other than the solvent is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray-curability of the energy ray-curable resin film is further improved.
In addition to the energy ray-curable component, the resin layer-forming composition (IV) may contain one or more selected from the group consisting of a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, and a general-purpose additive, depending on the purpose. For example, by using the composition (IV) for forming a resin layer containing the energy ray-curable component and the thermosetting component, the adhesion of the formed energy ray-curable resin film to an adherend is improved by heating, and the strength of the first protective film formed of the energy ray-curable resin film is also improved.
The thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, and general-purpose additive in the resin layer-forming composition (IV) are the same as the thermosetting component (B), photopolymerization initiator, filler (D), coupling agent (E), crosslinking agent (F), and general-purpose additive in the resin layer-forming composition (III), respectively.
In the resin layer-forming composition (IV), one of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, and the general-purpose additive may be used alone, or two or more of them may be used at the same time, and when two or more of them are used at the same time, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, and general-purpose additive in the resin layer-forming composition (IV) is not particularly limited as long as it is appropriately adjusted according to the purpose.
Since the workability of the resin layer forming composition (IV) is improved by dilution, it is preferable to further contain a solvent.
Examples of the solvent contained in the resin layer-forming composition (IV) include the same solvents as those in the resin layer-forming composition (III).
The solvent contained in the resin layer-forming composition (IV) may be one or two or more.
Method for producing composition for forming energy ray-curable resin film
The composition for forming an energy ray-curable resin film such as the composition (IV) for forming a resin layer can be obtained by blending the components for constituting the composition.
The order of addition in blending the components is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any blend component other than the solvent to dilute the blend component in advance, or the solvent may be mixed with any blend component other than the solvent without diluting the blend component in advance.
The method of mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, stirring blades, or the like; a method of mixing using a stirrer; and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of adding and mixing the components are not particularly limited as long as the components to be blended are not degraded, and the temperature is preferably 15 to 30 ℃.
Sealing layer of very good material
The adhesion layer improves adhesion between the first base material and the buffer layer, and highly suppresses peeling of the first base material and the buffer layer in the first protective film forming sheet. Therefore, when the first protective film forming sheet having the adhesive layer is used, the laminated structure of the first base material, the adhesive layer, and the buffer layer can be maintained more stably.
The sealing layer is in the form of a sheet or film.
Preferable examples of the adhesive layer include adhesive layers containing ethylene-vinyl acetate copolymer resin (EVA) and the like.
The sealing layer may be a single layer (single layer) or a plurality of layers of two or more layers, and when the layers are a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
The thickness of the sealing layer is preferably 10 to 100. Mu.m, more preferably 25 to 85. Mu.m, particularly preferably 40 to 70. Mu.m.
Here, the "thickness of the adhesion layer" refers to the thickness of the entire adhesion layer, and for example, the thickness of the adhesion layer composed of a plurality of layers refers to the total thickness of all layers constituting the adhesion layer.
Composition for forming adhesion layer
The adhesive layer can be formed using an adhesive layer forming composition containing the constituent material thereof. For example, the adhesive layer can be formed at the target site by extrusion molding the adhesive layer forming composition onto the surface to be formed of the adhesive layer. A more specific method of forming the sealing layer will be described in detail later together with a method of forming other layers. The content ratio of the components in the composition for forming an adhesive layer, which do not vaporize at ordinary temperature, is generally the same as the content ratio of the components in the adhesive layer.
Composition (VI) for forming adhesive layer
Examples of the composition for forming an adhesive layer include a composition (VI) for forming an adhesive layer containing an ethylene-vinyl acetate copolymer resin (EVA).
The ethylene-vinyl acetate copolymer resin preferably has a density of 1100kg/m 3 Hereinafter, it is more preferably 850 to 1100kg/m 3 Particularly preferably 900 to 1000kg/m 3 . In addition, in the present specification, unless otherwise indicated, "density of ethylene-vinyl acetate copolymer resin" means a value measured based on JIS K7112:1999.
The melting point of the ethylene-vinyl acetate copolymer resin is preferably 50 to 95℃and more preferably 65 to 85 ℃.
The Melt Flow Rate (MFR) of the ethylene-vinyl acetate copolymer resin at 190℃is preferably 1 to 10g/10 min, more preferably 3 to 8g/10 min.
In addition, in the present specification, unless otherwise indicated, "melt flow rate of an ethylene-vinyl acetate copolymer resin" means a value measured based on JIS K7210:1999.
The content of the composition (VI) for forming an adhesive layer and the ethylene-vinyl acetate copolymer resin of the adhesive layer is preferably 80 to 100% by mass.
[ other Components ]
The adhesive layer-forming composition (VI) and the adhesive layer may contain other components than the ethylene-vinyl acetate copolymer resin within a range that does not impair the effects of the present invention.
The other components are not particularly limited and may be appropriately selected according to the purpose.
The composition (VI) for forming the adhesive layer and the other components contained in the adhesive layer may be one kind only, or may be two or more kinds, and when two or more kinds are used, the combination and the ratio thereof may be arbitrarily selected.
The content of the composition (VI) for forming an adhesive layer and the other components of the adhesive layer is not particularly limited, and may be appropriately selected according to the purpose.
Method for producing first protective film-forming sheet
The first protective film forming sheet can be manufactured by sequentially laminating the layers so that the layers have a corresponding positional relationship. The method of forming each layer is the same as described hereinabove.
For example, a first protective film-forming sheet formed by stacking a first base material, a buffer layer, and a curable resin film in this order in the thickness direction can be produced by the following method. That is, the buffer layer is laminated on the first substrate by extrusion molding the buffer layer forming composition on the first substrate. The curable resin film-forming composition is applied to the release treated surface of the release film, and dried as necessary, thereby laminating the curable resin film. Then, the curable resin film on the release film is bonded to the buffer layer on the first substrate, whereby a first protective film-forming sheet is obtained in which the buffer layer, the curable resin film, and the release film are laminated in this order on the first substrate. The release film may be removed when the first protective film forming sheet is used.
In the above-described manufacturing method, the first protective film forming sheet including the layers other than the above-described layers can be manufactured by appropriately adding one or both of the other layer forming step and the lamination step so that the lamination position of the other layers is an appropriate position.
For example, a first protective film-forming sheet in which a first base material, an adhesive layer, a buffer layer, and a curable resin film are laminated in this order in the thickness direction can be produced by the following method. Specifically, the adhesive layer and the buffer layer are laminated in this order on the first substrate by coextrusion molding the adhesive layer forming composition and the buffer layer forming composition on the first substrate. The curable resin film is further laminated on the release film by the same method as described above. Then, the curable resin film on the release film is bonded to the first substrate and the buffer layer on the adhesive layer, whereby a first protective film-forming sheet is obtained in which the adhesive layer, the buffer layer, the curable resin film, and the release film are laminated in this order on the first substrate. When the first protective film forming sheet is used, the release film on the curable resin film may be removed.
(method for using first protective film-forming sheet)
The first protective film-forming sheet of the present invention can be used in the following manner, for example.
That is, first, the first protective film forming sheet is bonded to the bump forming surface of the semiconductor wafer through the curable resin film. At this time, the curable resin film is softened by bonding while heating the curable resin film, so that the curable resin film adheres to the bump formation surface.
Next, if necessary, a protective film forming sheet (referred to as a "second protective film forming sheet" in this specification) for protecting the back surface is attached to the back surface of the semiconductor wafer after grinding the surface (i.e., the back surface) opposite to the bump forming surface. Examples of the second protective film forming sheet include a second protective film forming sheet having a second protective film forming film capable of forming a second protective film for protecting the back surface of the semiconductor wafer and the semiconductor chip by curing. The second protective film forming sheet may be a forming sheet including a dicing sheet in addition to the second protective film forming film.
Then, only the curable resin film in the first protective film forming sheet bonded to the bump forming surface of the semiconductor wafer is left on the bump forming surface, and the other layer is peeled from the curable resin film. Here, for example, in the case of the first protective film forming sheet 1 shown in fig. 1, "other layers to be peeled" means the first base material 11 and the buffer layer 13, and in the case of the first protective film forming sheet 2 shown in fig. 2, "other layers to be peeled" means the first base material 11, the adhesion layer 14 and the buffer layer 13.
Next, the curable resin film is cured to form a first protective film on the bump formation surface of the semiconductor wafer.
Thereafter, the process can be performed until the semiconductor device is manufactured by the same method as the conventional process. That is, the semiconductor wafer having the first protective film is diced to form semiconductor chips, and the semiconductor chips having the first protective film are picked up. The second protective film-forming film may be cured at an appropriate timing according to the kind thereof, and the second protective film may be formed. The picked-up semiconductor chip is flip-chip mounted on the wiring substrate, and the semiconductor device is finally formed.
By using the first protective film forming sheet of the present invention, at least the upper portion of the bump penetrates the curable resin film and protrudes in the stage of bonding the sheet to the bump forming surface of the semiconductor wafer, and the residue of the curable resin film on the upper portion of the bump is suppressed. As a result, at least the upper portion of the bump penetrates the first protective film and protrudes. When the semiconductor chip including the first protective film and the bump is flip-chip mounted on the wiring substrate, the electrical connection between the semiconductor chip and the wiring substrate is improved.
Hereinafter, a process from attaching the first protective film forming sheet of the present invention to the bump forming surface of the semiconductor wafer until the first protective film is formed will be described in further detail with reference to the accompanying drawings.
Fig. 3 is a cross-sectional view schematically showing an example of a method of using the first protective film forming sheet 1 shown in fig. 1.
When the first protective film forming sheet 1 is used, first, as shown in fig. 3 (a), the first protective film forming sheet 1 is disposed so that the curable resin film 12 of the first protective film forming sheet 1 faces the bump forming surface 9a of the semiconductor wafer 9.
The height of the bump 91 is not particularly limited, but is preferably 120 to 300. Mu.m, more preferably 150 to 270. Mu.m, particularly preferably 180 to 240. Mu.m. By setting the height of the bump 91 to the above lower limit value or more, the function of the bump 91 can be further improved. Further, by setting the height of the bump 91 to the above-described upper limit value or less, the effect of suppressing the residue of the curable resin film 12 on the bump 91 is further improved.
In the present specification, the "bump height" refers to a height from a bump formation surface to a position located at the highest position in the bump.
The width of the bump 91 is not particularly limited, but is preferably 170 to 350 μm, more preferably 200 to 320 μm, and particularly preferably 230 to 290 μm. By setting the width of the bump 91 to the lower limit value or more, the function of the bump 91 can be further improved. Further, by setting the height of the bump 91 to the above-described upper limit value or less, the effect of suppressing the residue of the curable resin film 12 on the bump 91 is further improved.
In the present specification, the term "bump width" refers to the maximum value of a line segment obtained by connecting 2 different points on the bump surface in a straight line when the bump is viewed from top to bottom in a direction perpendicular to the bump formation surface.
The distance between the adjacent bumps 91 is not particularly limited, but is preferably 250 to 800 μm, more preferably 300 to 600 μm, and particularly preferably 350 to 500 μm. By setting the distance to the lower limit value or more, the function of the bump 91 can be further improved. Further, by setting the distance to the upper limit value or less, the effect of suppressing the residue of the curable resin film 12 on the bump 91 is further improved.
In addition, in the present specification, the "distance between adjacent bumps" refers to the minimum value of the distance between the surfaces of adjacent bumps.
Next, the curable resin film 12 is brought into contact with the bumps 91 on the semiconductor wafer 9, and the first protective film forming sheet 1 is pressed against the semiconductor wafer 9. Thereby, the first surface 12a of the curable resin film 12 is sequentially pressed against the surface 91a of the bump 91 and the bump formation surface 9a of the semiconductor wafer 9. At this time, the curable resin film 12 is softened by heating the curable resin film 12, spreads between the bumps 91 so as to cover the bumps 91, adheres to the bump formation surface 9a, and covers the surface 91a of the bumps 91, particularly the surface 91a in the vicinity of the bump formation surface 9a, thereby filling the bumps 91.
In the above manner, as shown in fig. 3 (b), the curable resin film 12 of the first protective film-forming sheet 1 is bonded to the bump-forming surface 9a of the semiconductor wafer 9.
As a method of pressing the first protective film forming sheet 1 against the semiconductor wafer 9 as described above, a known method of pressing and attaching various sheets to an object can be applied, and examples thereof include a method using a lamination roller (lamination roller).
The heating temperature of the first protective film forming sheet 1 at the time of pressure bonding to the semiconductor wafer 9 may be a temperature at which the curable resin film 12 is not cured at all or a temperature at which the curing is not excessively performed, and is preferably 80 to 100 ℃, more preferably 85 to 95 ℃.
The pressure at which the first protective film forming sheet 1 is pressed against the semiconductor wafer 9 is not particularly limited, but is preferably 0.1 to 1.5MPa, more preferably 0.3 to 1MPa.
When the first protective film forming sheet 1 is pressed against the semiconductor wafer 9 as described above, the pressure from the bumps 91 is applied to the curable resin film 12 and the buffer layer 13 in the first protective film forming sheet 1, and the first surface 12a of the curable resin film 12 and the first surface 13a of the buffer layer 13 are deformed into concave shapes in the initial stage. Further, cracking occurs in the curable resin film 12 to which pressure from the bump 91 is always applied. Finally, at the stage where the first surface 12a of the curable resin film 12 is pressed against the bump formation surface 9a of the semiconductor wafer 9, the upper portion 910 of the bump 91 is in a state of penetrating and protruding through the curable resin film 12. In addition, in this final stage, generally, the upper portion 910 of the bump 91 does not penetrate the buffer layer 13. This is because the buffer layer 13 has a buffer effect against the pressure applied by the bump 91.
As shown in fig. 3 (b), in the stage of attaching the first protective film forming sheet 1 to the bump forming surface 9a of the semiconductor wafer 9, the curable resin film 12 is not left at all or substantially at the upper portion 910 of the bump 91. In the present specification, unless otherwise specified, "a curable resin film hardly remains on the upper portion of the bump" means that a curable resin film slightly remains on the upper portion of the bump, but the remaining amount is such that electrical connection between the semiconductor chip and the wiring substrate is not hindered when the semiconductor chip provided with the bump is flip-chip mounted on the wiring substrate.
As described above, the reason why the curable resin film 12 can be prevented from remaining on the upper portion 910 of the bump 91 is that, as described above, the curable resin film 12 is designed to be particularly liable to break when the curable resin film 12 is deformed by applying pressure from the bump 91 thereto. That is, in the first protective film forming sheet 1, when the curable resin film 12 and the buffer layer 13 satisfy the relationship of the above formula (w 1) and these (the curable resin film 12 and the buffer layer 13) undergo a large strain, the buffer layer 13 exhibits an appropriate buffer action, and the curable resin film 12 is broken into an appropriate state.
After the first protective film forming sheet 1 is attached to the bump forming surface 9a of the semiconductor wafer 9, if necessary, a surface (back surface) 9b of the semiconductor wafer 9 opposite to the bump forming surface 9a is ground, and then a second protective film forming sheet (not shown) is attached to the back surface 9b.
Next, as shown in fig. 3 (c), the first base material 11 and the buffer layer 13 are peeled from the curable resin film 12.
Next, by curing the curable resin film 12, as shown in fig. 3 (d), a first protective film 12' is formed on the bump formation surface 9 a.
Here, the case where the first protective film forming sheet 1 shown in fig. 1 is used will be described, and when the first protective film forming sheet of another embodiment such as the first protective film forming sheet 2 shown in fig. 2 is used, the first protective film forming sheet exhibits the same effects as when the first protective film forming sheet 1 is used.
Fig. 4 is a cross-sectional view schematically showing an example of a method of using the first protective film forming sheet 2 shown in fig. 2.
When the first protective film forming sheet 2 is used, first, as shown in fig. 4 (a), the first protective film forming sheet 2 is also arranged so that the curable resin film 12 of the first protective film forming sheet 2 faces the bump forming surface 9a of the semiconductor wafer 9.
Next, the first protective film forming sheet 2 is pressed against the semiconductor wafer 9 by bringing the curable resin film 12 into contact with the bumps 91 on the semiconductor wafer 9 while heating the curable resin film. Thereby, the first surface 12a of the curable resin film 12 is sequentially pressed against the surface 91a of the bump 91 and the bump formation surface 9a of the semiconductor wafer 9. As shown in fig. 4 (b), the curable resin film 12 of the first protective film-forming sheet 2 is bonded to the bump-forming surface 9a of the semiconductor wafer 9 in the manner described above.
At this time, the first protective film forming sheet 2 can be pressure-bonded to the semiconductor wafer 9 by the same method as that when the first protective film forming sheet 1 is used.
When the first protective film forming sheet 2 is pressed against the semiconductor wafer 9 as described above, the pressure from the bumps 91 is applied to the curable resin film 12 and the buffer layer 13 in the first protective film forming sheet 2, and the first surface 12a of the curable resin film 12 and the first surface 13a of the buffer layer 13 are deformed into concave shapes in the initial stage. Further, cracking occurs in the curable resin film 12 to which pressure from the bump 91 is always applied. Finally, at the stage where the first surface 12a of the curable resin film 12 is pressed against the bump formation surface 9a of the semiconductor wafer 9, the upper portion 910 of the bump 91 is in a state of penetrating and protruding through the curable resin film 12. In this final stage, generally, the upper portion 910 of the bump 91 does not penetrate the buffer layer 13.
In addition, by using the first protective film forming sheet 2, as described above, the adhesion layer 14 highly suppresses peeling of the first base material 11 and the buffer layer 13 in the process of bonding the curable resin film 12 to the bump forming surface 9a of the semiconductor wafer 9, and the laminated structure of the first base material 11, the adhesion layer 14, and the buffer layer 13 is maintained more stably.
As shown in fig. 4 (b), in the stage of attaching the first protective film forming sheet 2 to the bump forming surface 9a of the semiconductor wafer 9, the curable resin film 12 is completely or hardly left on the upper portion 910 of the bump 91 by the same action as in the case of the first protective film forming sheet 1.
After the first protective film forming sheet 2 is attached to the bump forming surface 9a of the semiconductor wafer 9, if necessary, a surface (back surface) 9b of the semiconductor wafer 9 opposite to the bump forming surface 9a is ground, and then a 2 nd protective film forming sheet (not shown) is attached to the back surface 9b.
Next, as shown in fig. 4 (c), the first base material 11, the adhesive layer 14, and the buffer layer 13 are peeled off from the curable resin film 12.
Next, by curing the curable resin film 12, as shown in fig. 4 (d), a first protective film 12' is formed on the bump formation surface 9 a.
For example, by obtaining the image data of SEM of the bump, it can be confirmed whether or not a curable resin film or a protective film remains on the upper portion of the bump.
Examples
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.
The components used in the preparation of the composition for forming a thermosetting resin film are shown below.
Polymer component
Polymer component (a) -1: polyvinyl butyral having structural units represented by the following formulae (i) -1, (i) -2 and (i) -3 (sekisuicical co., ltd. Manufactured "S-LEC BL-10", weight average molecular weight 25000, glass transition temperature 59 ℃)
Polymer component (a) -2: an acrylic resin (weight average molecular weight 800000, glass transition temperature-28 ℃) obtained by copolymerizing butyl acrylate (hereinafter abbreviated as "BA") (55 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (10 parts by mass), glycidyl methacrylate (hereinafter abbreviated as "GMA") (20 parts by mass), and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass).
[ chemical formula 1]
Figure BDA0002015437460000511
Wherein, I 1 About 28, m 1 Is 1 to 3, n 1 Is an integer of 68 to 74.
Epoxy resin
Epoxy resin (B1) -1: liquid bisphenol F type epoxy resin (Mitsubishi Chemical Corporation manufactured "YL 983U")
Epoxy resin (B1) -2: multifunctional aromatic epoxy resin (Nippon Kayaku Co., ltd., "EPPN-502H")
Epoxy resin (B1) -3: dicyclopentadiene type epoxy resin (EPICLON HP-7200 manufactured by DIC CORPORATION)
Thermosetting agent
Thermosetting agent (B2) -1: novolak type phenol resin (SHOWA DENKO K.K. "BRG-556")
Curing accelerator
Curing accelerator (C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole (SHIKOKU CHEMICALS CORPORATION manufactured by CUREZOL 2 PHZ-PW)
Filler material
Filler (D) -1: spherical silica modified with epoxy group (manufactured by Admatechs company, "ADMANANOYA 050C-MKK")
Example 1
< manufacturing of first protective film Forming sheet >
(preparation of composition for Forming thermosetting resin film)
The polymer components (A) -1, the epoxy resin (B1) -2, the epoxy resin (B1) -3, the thermosetting agent (B2) -1 and the curing accelerator (C) -1 were dissolved or dispersed in methyl ethyl ketone in such a manner that the ratio of the contents thereof became the values shown in Table 1, and the mixture was stirred at 23℃to obtain a resin layer-forming composition (III) having a solid content concentration of 55% by mass as a thermosetting resin film-forming composition. Note that the "-" in the column containing the component in table 1 indicates that the thermosetting resin film-forming composition does not contain the component.
(production of first protective film-forming sheet)
Ethylene-vinyl acetate copolymer resin (DU PONT-MITSU POLYCHEMICALS manufactured by "EVAFLEX (registered trademark) EV260", density 950 kg/m) was produced by using a small-sized T-die head extruder (TOYO SEIKICO., ltd., "Labo Plato Mill") 3 Melting point less than 72℃and melt flow rate (190 ℃) of 6g/10 min), ethylene-alpha-olefin copolymer (manufactured by Mitsui Chemicals company "TAFMER DF640", density 864 kg/m) 3 A film of polyethylene terephthalate (PET) (manufactured by tolay INDUSTRIES, INC., "lumirror (registered trademark)", thickness 100 μm) was co-extrusion molded with a melting point of less than 50 ℃, a melt flow rate (190 ℃) of 3.6g/10 minutes, and a melt flow rate (230 ℃) of 6.7g/10 minutes, whereby an adhesive layer composed of an ethylene-vinyl acetate copolymer resin and a buffer layer composed of an ethylene- α -olefin copolymer (thickness 400 μm) were laminated in this order on a first substrate composed of the PET film.
The thermosetting resin film-forming composition obtained above was further applied to the release treated surface of a release film (produced by Lintec corporation, "SP-PET381031", 38 μm thick) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and heated and dried at 120℃for 2 minutes to form a thermosetting resin film having a thickness of 30. Mu.m.
Next, the thermosetting resin film on the release film was bonded to the buffer layer formed on the first substrate, and a first protective film-forming sheet having a structure shown in fig. 2 was obtained in which the adhesive layer, the buffer layer, the thermosetting resin film, and the release film were laminated in this order on the first substrate.
< evaluation of first protective film Forming sheet >
(measurement of shear elastic modulus G' of buffer layer and thermosetting resin film)
A buffer layer having a thickness of 1000 μm was formed by the same method as described above, except that the coating amount of the buffer layer forming composition was changed. Then, the buffer layer was cut into a disk shape having a diameter of 8mm, and a test piece of the buffer layer was obtained.
A thermosetting resin film having a thickness of 1000 μm was formed by the same method as described above, except that the coating amount of the thermosetting resin film-forming composition was changed. Next, the thermosetting resin film was cut into a disk shape having a diameter of 8mm, and a test piece of the thermosetting resin film was obtained.
The test piece of the shear viscosity measuring device was held at 90℃in advance at the set position, the test piece of the buffer layer and the thermosetting resin film obtained above was placed at the set position, and the measurement jig was pressed against the upper surface of the test piece, whereby the test piece was fixed and set at the set position.
Then, the shear modulus G' of the test piece was measured at a temperature of 90℃and a measurement frequency of 1Hz until the strain was gradually increased to 0.01% to 1000%. The results are shown in FIG. 5. In fig. 5, the measurement value indicated as "example 1" is the measurement value of the test piece of the thermosetting resin film.
(confirmation of the presence or absence of the remaining thermosetting resin film on the bump)
The thermosetting resin film of the first protective film forming sheet obtained as described above is brought into contact with the bumps of the semiconductor wafer, and the first protective film forming sheet is bonded to the semiconductor wafer by pressure while being heated. As the semiconductor wafer, a semiconductor wafer having a bump height of 210 μm, a bump width of 250 μm, and a bump-to-bump distance of 400 μm was used. The heating temperature of the first protective film-forming sheet was set to 90℃and the pressure was set to 0.5MPa. Thus, the thermosetting resin film is bonded to the bump forming surface of the semiconductor wafer.
Then, the first base material, the adhesive layer, and the buffer layer are peeled off from the thermosetting resin film, exposing the thermosetting resin film.
Next, the surface of the bump of the semiconductor wafer was observed from a direction at an angle of 60 ° to a direction perpendicular to the bump formation surface of the semiconductor wafer using a scanning electron microscope (SEM, KEYENCE corporation, manufactured "VE-9700"), and the presence or absence of the thermosetting resin film remaining on the bump upper portion was confirmed. The results are shown in Table 1.
Examples 2 to 3 and comparative examples 1 to 2
< manufacturing and evaluation of first protective film Forming sheet >
A first protective film-forming sheet was produced and evaluated in the same manner as in example 1, except that either one or both of the types and the content ratios of the respective components were set as shown in table 1, and the shear modulus G' of the test piece of the buffer layer was not measured. The results are shown in FIG. 5 and Table 1. In fig. 5, the measurement values indicated as "example 2", "example 3", "comparative example 1" and "comparative example 2" are the measurement values of the test pieces of the thermosetting resin films in these examples and comparative examples, respectively.
TABLE 1
Figure BDA0002015437460000551
As is clear from fig. 5, in examples 1 to 3, the buffer layer and the thermosetting resin film satisfy the relationship of formula (w 1). In examples 1 and 2, gc300' was not directly measured, but the relationship of Gb300' > Gc300' was satisfied.
Further, in examples 1 and 2, although Gc200 'and Gc400' were not directly measured, it is apparent that the relationship of Gb200 '> Gc200', gb400 '> Gc400' was satisfied, and the relationships of formulae (w 2) and (w 3) were also satisfied. On the other hand, in example 3, the relationship of the formula (w 2) is satisfied, but the relationship of the formula (w 3) is not satisfied.
As is clear from fig. 5, in examples 1 to 3, a region (fluctuation region Rb) where the shear elastic modulus Gb 'is not constant exists in the function (function Fb) of the strain of the buffer layer and the shear elastic modulus G' (Gb '), and the shear elastic modulus Gb' when the strain of the buffer layer is 300% is included in the region (fluctuation region Rb).
Further, in examples 1 to 3, a region (variable region Rc) where the shear elastic modulus Gc ' is not constant was present in the function (function Fc) of the strain of the thermosetting resin film and the shear elastic modulus G ' (Gc '). In examples 1 and 2, the strain of the thermosetting resin film, such as 300%, was not observed directly, but in example 3, the shear elastic modulus Gc' at 300% strain of the thermosetting resin film was included in the region (variation region Rc).
When the first protective film forming sheet of examples 1 to 3 was used, it was confirmed from SEM imaging data that no thermosetting resin film remained on the bump upper portion of the semiconductor wafer.
In contrast, as is clear from fig. 5, in comparative examples 1 to 2, the buffer layer and the thermosetting resin film do not satisfy the relationship of formula (w 1). In comparative examples 1 and 2, the relationship of the formula (w 2) was satisfied, but the relationship of the formula (w 3) was not satisfied.
When the first protective film forming sheet of comparative examples 1 and 2 was used, it was confirmed that the thermosetting resin film remained on the bump upper portion of the semiconductor wafer. In the SEM imaging data of these comparative examples, a striped pattern was present in the entire region including the surface of the upper portion of the bump, and further, the bump size was significantly larger than that of the example from an apparent point of view, whereby it was clearly confirmed that the thermosetting resin film remained on the surface of the bump. The thickness of the thermosetting resin film remaining on the upper portion of the bump was calculated from the SEM image data, and as a result, comparative example 1 was about 9.4. Mu.m, and comparative example 2 was about 4.8. Mu.m.
Industrial applicability
The present invention can be used for manufacturing a semiconductor chip or the like having bumps at connection pad portions, which is used in a flip-chip mounting method.
Description of the reference numerals
1. 2: first protective film forming sheet, 11: first substrate, 11a: first side of first substrate, 12: curable resin film, 12a: first surface of curable resin film, 12': first protective film, 13: buffer layer, 13a: first side of buffer layer, 14: sealing layer, 14a: first surface of sealing layer, 9: semiconductor wafer, 9a: bump formation face of semiconductor wafer, 91: bumps, 91a: surface of bump, 910: the upper part of the bump.

Claims (6)

1. A first protective film-forming sheet comprising a first base material, a buffer layer formed on the first base material, and a curable resin film formed on the buffer layer,
the curable resin film is applied to the surface of the semiconductor wafer having the bumps and cured to form a first protective film on the surface,
when a test piece of the buffer layer having a diameter of 8mm and a thickness of 1mm is strained under conditions of a temperature of 90 ℃ and a frequency of 1Hz and a strain distribution measurement for measuring a shear modulus G 'of the test piece of the buffer layer is performed, the shear modulus Gb300' of the test piece of the buffer layer at a strain of 300% of the test piece of the buffer layer,
when a test piece of the curable resin film having a diameter of 8mm and a thickness of 1mm is strained under conditions of a temperature of 90 ℃ and a frequency of 1Hz and a strain distribution measurement for measuring a shear modulus G 'of the test piece of the curable resin film is performed, the shear modulus of the test piece of the curable resin film at 300% strain is Gc300',
the Gb300 'and the Gc300' satisfy the following relationship,
Gb300 '. Gtoreq.Gc300'.
2. The first protective film-forming sheet according to claim 1, wherein a shear elastic modulus Gb200 'of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 200% and a shear elastic modulus Gc200' of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 200% satisfy the following relationship,
gb200 '. Gtoreq.Gc200'.
3. The first protective film forming sheet according to claim 1 or 2, wherein a shear elastic modulus Gb400 'of the test piece of the buffer layer when the strain of the test piece of the buffer layer is 400% and a shear elastic modulus Gc400' of the test piece of the curable resin film when the strain of the test piece of the curable resin film is 400% satisfy the following relationship,
gb400 '. Gtoreq.Gc400'.
4. The first protective film forming sheet according to claim 1 or 2, wherein, in a function of the strain of the test piece of the buffer layer and the shear elastic modulus Gb 'of the test piece of the buffer layer obtained by the strain distribution measurement, there is a region where the shear elastic modulus Gb' is not constant, the region where the shear elastic modulus Gb 'is not constant is a region where the minimum value of the shear elastic modulus Gb' is less than 90% of the maximum value of the shear elastic modulus Gb ', and the shear elastic modulus Gb' when the strain of the test piece of the buffer layer is 300% is included in the region.
5. The first protective film forming sheet according to claim 1 or 2, wherein, in a function of the strain of the test piece of the curable resin film obtained by the strain distribution measurement and the shear elastic modulus Gc 'of the test piece of the curable resin film, there is a region where the shear elastic modulus Gc' is not constant, the region where the shear elastic modulus Gc 'is not constant is a region where the minimum value of the shear elastic modulus Gc' is less than 90% of the maximum value of the shear elastic modulus Gc ', and the shear elastic modulus Gc' when the strain of the test piece of the curable resin film is 300% is included in the region.
6. The first protective film-forming sheet according to claim 1 or 2, wherein the curable resin film contains a resin component,
the filler content of the curable resin film is 45 mass% or less,
the weight average molecular weight of the resin component is 30000 or less.
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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108821231B (en) * 2018-06-26 2019-08-09 清华大学 A kind of surface based on mechanics principle has the high resiliency matrix and method of micro-structure
JP2020063362A (en) * 2018-10-17 2020-04-23 住友ベークライト株式会社 Adhesive composition for wet friction material
JP6859376B2 (en) * 2019-01-22 2021-04-14 グンゼ株式会社 Cover film
JP6697603B1 (en) * 2019-03-27 2020-05-20 グンゼ株式会社 Cover film
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JP7323734B1 (en) * 2022-01-12 2023-08-08 リンテック株式会社 Sheet for forming first protective film, method for manufacturing semiconductor device, and use of sheet

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012169484A (en) * 2011-02-15 2012-09-06 Nitto Denko Corp Semiconductor device manufacturing method
JP2013004872A (en) * 2011-06-20 2013-01-07 Hitachi Chem Co Ltd Method of manufacturing semiconductor device, film glue, and adhesive sheet
JP2013123003A (en) * 2011-12-12 2013-06-20 Nitto Denko Corp Laminated sheet and method for manufacturing semiconductor device using laminated sheet
KR20140044758A (en) * 2012-10-05 2014-04-15 린텍 가부시키가이샤 Surface protective sheet
KR20140069508A (en) * 2012-11-29 2014-06-10 제일모직주식회사 Adhesive film for protecting surface of semiconductor wafer
JP2015005598A (en) * 2013-06-20 2015-01-08 古河電気工業株式会社 Adhesive tape for semiconductor wafer surface protection
JP2015084352A (en) * 2013-10-25 2015-04-30 東レ株式会社 Multilayered sheet for gluing circuit member, and method for manufacturing semiconductor device
CN104797423A (en) * 2012-11-30 2015-07-22 琳得科株式会社 Sheet provided with curable resin film-forming layer and method for manufacturing semiconductor device using sheet
JP2015183008A (en) * 2014-03-20 2015-10-22 リンテック株式会社 adhesive sheet
CN105452408A (en) * 2013-09-30 2016-03-30 琳得科株式会社 Composite sheet for resin film formation
CN105765699A (en) * 2013-11-22 2016-07-13 琳得科株式会社 Dicing-sheet base film and base-film manufacturing method
KR20160111385A (en) * 2014-01-21 2016-09-26 린텍 가부시키가이샤 Adhesive sheet for wafer protection

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5666335B2 (en) 2011-02-15 2015-02-12 日東電工株式会社 Protective layer forming film
JP6347657B2 (en) * 2014-04-22 2018-06-27 デクセリアルズ株式会社 Protective tape and method of manufacturing semiconductor device using the same

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012169484A (en) * 2011-02-15 2012-09-06 Nitto Denko Corp Semiconductor device manufacturing method
JP2013004872A (en) * 2011-06-20 2013-01-07 Hitachi Chem Co Ltd Method of manufacturing semiconductor device, film glue, and adhesive sheet
JP2013123003A (en) * 2011-12-12 2013-06-20 Nitto Denko Corp Laminated sheet and method for manufacturing semiconductor device using laminated sheet
KR20140044758A (en) * 2012-10-05 2014-04-15 린텍 가부시키가이샤 Surface protective sheet
KR20140069508A (en) * 2012-11-29 2014-06-10 제일모직주식회사 Adhesive film for protecting surface of semiconductor wafer
CN104797423A (en) * 2012-11-30 2015-07-22 琳得科株式会社 Sheet provided with curable resin film-forming layer and method for manufacturing semiconductor device using sheet
JP2015005598A (en) * 2013-06-20 2015-01-08 古河電気工業株式会社 Adhesive tape for semiconductor wafer surface protection
CN105452408A (en) * 2013-09-30 2016-03-30 琳得科株式会社 Composite sheet for resin film formation
JP2015084352A (en) * 2013-10-25 2015-04-30 東レ株式会社 Multilayered sheet for gluing circuit member, and method for manufacturing semiconductor device
CN105765699A (en) * 2013-11-22 2016-07-13 琳得科株式会社 Dicing-sheet base film and base-film manufacturing method
KR20160111385A (en) * 2014-01-21 2016-09-26 린텍 가부시키가이샤 Adhesive sheet for wafer protection
JP2015183008A (en) * 2014-03-20 2015-10-22 リンテック株式会社 adhesive sheet

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