CN108966671B - Support sheet and composite sheet for forming protective film - Google Patents

Support sheet and composite sheet for forming protective film Download PDF

Info

Publication number
CN108966671B
CN108966671B CN201780016815.0A CN201780016815A CN108966671B CN 108966671 B CN108966671 B CN 108966671B CN 201780016815 A CN201780016815 A CN 201780016815A CN 108966671 B CN108966671 B CN 108966671B
Authority
CN
China
Prior art keywords
protective film
forming
adhesive layer
film
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780016815.0A
Other languages
Chinese (zh)
Other versions
CN108966671A (en
Inventor
小桥力也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of CN108966671A publication Critical patent/CN108966671A/en
Application granted granted Critical
Publication of CN108966671B publication Critical patent/CN108966671B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/145—Variation across the thickness of the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The support sheet of the present application comprises a substrate and an adhesive layer laminated on the substrate, wherein the surface roughness (Ra) of the surface of the substrate on the side on which the adhesive layer is provided is 0.4 [ mu ] m or less, and the surface roughness (Ra) of the surface of the substrate on the opposite side from the side on which the adhesive layer is provided is greater than the surface roughness of the surface on the side on which the adhesive layer is provided and is 0.053 to 0.48 [ mu ] m. The composite sheet for forming a protective film of the present application comprises the support sheet, and the adhesive layer in the support sheet further comprises a film for forming a protective film.

Description

Support sheet and composite sheet for forming protective film
Technical Field
The present application relates to a support sheet and a composite sheet for forming a protective film.
The present application is based on the priority of Japanese patent application No. 2016-060577 filed in Japan at 3/24 of 2016, and the content of which is incorporated herein by reference.
Background
In recent years, a so-called flip-chip (face down) mounting method has been used for manufacturing semiconductor devices. In the flip-chip method, a semiconductor chip having electrodes such as bumps on a circuit surface, the electrodes being bonded to a substrate, may be used. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.
A semiconductor chip with a protective film obtained by forming a resin film made of an organic material as a protective film on the back surface of the exposed semiconductor chip in this way may be mounted in a semiconductor device. The protective film is used for preventing so-called chipping, such as cracking or chipping, from occurring on the semiconductor chip in the steps subsequent to the dicing step.
In forming such a protective film, a protective film forming composite sheet including a protective film forming film (protective film forming layer) on a support sheet is used. As the support sheet, for example, a laminate sheet obtained by laminating an adhesive layer or the like on a resin substrate can be used. In the composite sheet for forming a protective film, the protective film forming film has a protective film forming ability, and the support sheet can function as a dicing sheet, and the protective film forming film and the dicing sheet can be formed integrally.
The substrate before processing used for the support sheet generally has a concave-convex shape on one or both surfaces thereof. When a substrate before processing, a support sheet obtained by using the substrate, or a composite sheet for forming a protective film is wound up to form a roll, if the substrate does not have the surface (concave-convex surface) having the concave-convex shape described above, the contact surfaces of the roll adhere to each other to cause blocking, which makes use difficult. In the case of the base material roll, the contact surface is the surface of each base material, and in the case of the support sheet and the composite sheet for forming the protective film, the contact surface is the exposed surface of the base material as the lowermost layer and the exposed surface of the uppermost layer such as the release film. In particular, if the protective film forming composite sheet sticks, the composite sheet may be wrinkled or the like, and when the composite sheet is pulled out from the roll, the uppermost layer (typically, a release film) may be peeled from the composite sheet.
In contrast, if one of the contact surfaces of the roll is the uneven surface of the base material, the area of the contact surface of the roll is reduced, and thus blocking can be suppressed.
On the other hand, in the process of manufacturing a semiconductor device, a surface of a protective film attached to a semiconductor wafer or a semiconductor chip on a support sheet side may be printed by laser irradiation (in this specification, it may be referred to as "laser printing"). At this time, laser light is irradiated from the side of the support sheet (substrate) opposite to the side on which the protective film is formed, through the support sheet. That is, the laser light enters the support sheet from the exposed surface side of the base material and reaches the protective film. Therefore, when the exposed surface of the base material is a concave-convex surface, there is a problem that laser light is diffusely reflected on the concave-convex surface, and laser printing may become unclear.
In addition, in the manufacturing process of the semiconductor device, the state of the semiconductor wafer or the semiconductor chip provided with the composite sheet for forming the protective film or the protective film may be inspected by an infrared camera or the like through the sheet or the like. However, when the laser light is diffusely reflected on the exposed surface of the base material as described above, there is a problem that a clear inspection image cannot be obtained.
As a composite sheet for forming a protective film capable of preventing such diffuse reflection of light such as laser light, for example, there is disclosed: a composite sheet (dicing tape-integrated semiconductor back surface protective film) is used in which a substrate having an uneven surface on only one side is disposed on the protective film forming film side without using the uneven surface as an exposed surface (see patent document 1). In the protective film-forming film, the haze of a laminate (dicing tape) formed by laminating the base material and the adhesive layer is 45% or less.
However, the composite sheet for forming a protective film disclosed in patent document 1 has a problem that the above-described blocking cannot be suppressed when the composite sheet is wound into a roll because the exposed surface of the base material is a smooth surface.
In addition, in the case where an adhesive layer is provided on the uneven surface of a substrate, there is a problem in that the adhesive layer needs to be made soft and sufficiently thick in order to reduce the influence of the uneven surface on the adhesive layer. If the adhesive layer is hard, the adhesive layer may not be filled in the bottom portion of the convex portion on the surface of the substrate, and a void portion may be generated. In addition, if the pressure-sensitive adhesive layer is thin, the uneven shape of the substrate surface is reflected, and the surface (back surface) of the protective film-forming film on the substrate side becomes uneven. In this way, when the protective film is formed from the protective film forming film in which the uneven shape on the surface of the substrate is not sufficiently buried, the laser printing is performed on the surface of the support sheet side, which may cause the printing to become unclear. In addition, a clear inspection image of the semiconductor wafer or the semiconductor chip cannot be obtained. On the other hand, when the pressure-sensitive adhesive layer is too thick, the pressure-sensitive adhesive layer tends to vibrate during the dicing process, for example, and therefore the semiconductor chip or the semiconductor wafer during the dicing process to form the semiconductor chip tends to vibrate, and when an excessive force is applied to the semiconductor chip or the semiconductor wafer, breakage or chipping (chipping) tends to occur on the semiconductor chip as a result.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-033741
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a composite sheet for forming a protective film, which is capable of suppressing defects such as insufficient embedding of an adhesive layer into a substrate surface and generation of chipping, and which is capable of suppressing blocking, performing clear laser printing on a protective film, and acquiring clear inspection images of a semiconductor wafer or a semiconductor chip, and a support sheet used for manufacturing the composite sheet for forming a protective film.
Means for solving the problems
The invention provides a support sheet, which comprises a substrate and an adhesive layer laminated on the substrate, wherein the surface roughness (Ra) of one side surface of the substrate, which is provided with the adhesive layer, is less than 0.4 mu m, and the surface roughness (Ra) of the surface of the substrate, which is opposite to the side surface provided with the adhesive layer, is greater than the surface roughness of the side surface provided with the adhesive layer and is 0.053-0.48 mu m.
In the support sheet of the present invention, the thickness of the pressure-sensitive adhesive layer may be 15 μm or less.
In the support sheet of the present invention, the pressure-sensitive adhesive layer may be non-energy-ray curable.
The present invention also provides a composite sheet for forming a protective film, comprising the support sheet, and a protective film formed on the adhesive layer in the support sheet.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the support sheet and the composite sheet for forming a protective film of the present invention, it is possible to prevent defects such as insufficient embedding of the adhesive layer into the surface of the substrate and chipping, to suppress blocking, to perform clear laser printing on the protective film, and to obtain a clear inspection image of the semiconductor wafer or the semiconductor chip.
Drawings
Fig. 1 is a cross-sectional view schematically showing one embodiment of the support sheet of the present invention.
Fig. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
Symbol description
1 … support piece
11 … substrate
11a … substrate (first side 1)
11b … substrate (face 2)
12 … adhesive layer
13. 23 … protective film forming film
101. 102, 103, … protective film forming composite sheet
Detailed Description
Support sheet and composite sheet for forming protective film
The support sheet of the present invention comprises a base material and an adhesive layer laminated on the base material, wherein the surface roughness (Ra) of the surface of the base material on the side where the adhesive layer is provided (hereinafter, sometimes referred to as "1 st surface") is 0.4 [ mu ] m or less, and the surface roughness (Ra) of the surface of the base material on the opposite side to the side where the adhesive layer is provided (hereinafter, sometimes referred to as "2 nd surface") is greater than the surface roughness of the surface of the base material on the side where the adhesive layer is provided (1 st surface) and is 0.053 to 0.48 [ mu ] m.
The support sheet is a member for constituting a composite sheet for forming a protective film described below, and can be used as a processing sheet for a semiconductor wafer such as a dicing sheet.
In the present specification, for convenience, a surface having a small surface roughness (for example, a surface having a surface roughness of 0.4 μm or less or a 1 st surface) is referred to as a smooth surface, and a surface having a large surface roughness (for example, a surface having a surface roughness of 0.053 to 0.48 μm or a 2 nd surface) is referred to as a concave-convex surface. That is, the terms "smooth surface" and "uneven surface" of the base material do not necessarily mean absolute smoothness of these surfaces, but mean a relative magnitude relation of smoothness of these surfaces.
The composite sheet for forming a protective film of the present invention is provided with the support sheet, and the adhesive layer in the support sheet is further provided with a film for forming a protective film.
The composite sheet for forming a protective film can prevent sticking, perform clear laser printing on the protective film, and obtain a clear inspection image of a semiconductor wafer or a semiconductor chip by providing the base material having the surface roughness of the 1 st and 2 nd surfaces within a specific range and the surface roughness of the 2 nd surface being larger than the surface roughness of the 1 st surface. In the composite sheet for forming a protective film, the surface roughness of the 1 st surface of the substrate is set within a specific range (small value) and the roughness is low, so that it is not necessary to make the adhesive layer soft and thick enough, and it is also possible to suppress the occurrence of defects such as insufficient embedding of the adhesive layer into the 1 st surface of the substrate and generation of chipping.
The overall structure of the support sheet and the protective film-forming composite sheet according to the present invention will be described below with reference to the drawings. For the sake of easier understanding of the features of the present invention, the drawings used in the following description may be enlarged for the portions to be described, and are not limited to the case where the dimensional ratios of the respective constituent elements are the same as the actual ones.
Fig. 1 is a cross-sectional view schematically showing one embodiment of the support sheet of the present invention.
The support sheet 1 shown here is formed by providing the pressure-sensitive adhesive layer 12 on the base material 11, and further providing the release film 15 on the pressure-sensitive adhesive layer 12.
The pressure-sensitive adhesive layer 12 is laminated on one surface (1 st surface) 11a of the base material 11, and the other surface (2 nd surface) 11b of the base material 11, which is the surface opposite to the side provided with the pressure-sensitive adhesive layer 12, becomes an exposed surface.
In the substrate 11, the surface roughness of the 1 st surface 11a is 0.4 μm or less, and the surface roughness of the 2 nd surface 11b is greater than the surface roughness of the 1 st surface 11a and is 0.053 to 0.48 μm.
In the present specification, unless otherwise specified, "surface roughness" refers to the so-called arithmetic average roughness obtained based on JIS B0601:2001, and may be abbreviated as "Ra".
In this case, a release film 15 is provided on one surface of the pressure-sensitive adhesive layer 12, that is, on the surface (hereinafter, sometimes referred to as "the 1 st surface") 12a opposite to the side on which the base material 11 is provided, but when the support sheet 1 is used, the release film 15 is removed, for example, a protective film forming film is laminated instead of the release film 15, so that a protective film forming composite sheet is constituted. The symbol 12b refers to the other surface of the adhesive layer 12, i.e., the surface on the side where the base material 11 is provided (hereinafter, sometimes referred to as "the 2 nd surface").
Fig. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film 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 in the case of the already described drawings, and detailed description thereof is omitted.
The composite sheet 101 for forming a protective film shown here is formed by providing an adhesive layer 12 on a base material 11, and providing a film 13 for forming a protective film on the adhesive layer 12. The composite sheet 101 for forming a protective film may be formed using the support sheet 1, or may be formed by further providing the protective film 13 on the adhesive layer 12 in the support sheet 1.
The protective film forming film 13 is laminated on the entire 1 st surface 12a of the adhesive layer 12.
The adhesive layer 14 for jigs is laminated on a part of the surface 13a of the protective film forming film 13 (hereinafter, sometimes referred to as "1 st surface") opposite to the side where the adhesive layer 12 is provided, that is, a region near the peripheral portion.
In the 1 st surface 13a of the protective film 13, a release film 15 is laminated on the surface on which the adhesive layer 14 for jigs is not laminated and the surface (1 st surface 14a and side surface 14 c) of the adhesive layer 14 for jigs which is not in contact with the protective film 13. Here, the 1 st surface 14a of the jig adhesive layer 14 is a surface of the jig adhesive layer 14 opposite to the side thereof in contact with the protective film forming film 13, and there are cases where the boundary between the 1 st surface 14a and the side surface 14c of the jig adhesive layer 14 cannot be clearly distinguished. In addition, the release film 15 may not contact the side surface 14c of the adhesive layer 14 for jigs. The protective film forming composite sheet 1 is usually stored in such a state that the release film 15 is provided. In fig. 2, a symbol 15a denotes a surface of the release film 15 opposite to the side in contact with the protective film forming film 13 (hereinafter, sometimes referred to as "1 st surface").
The composite sheet 101 for forming a protective film is used by adhering the 1 st surface 13a of the film 13 for forming a protective film to a surface (in this specification, may be simply referred to as "circuit forming surface") opposite to the surface on which a circuit is formed (in this specification, may be simply referred to as "circuit forming surface") of a semiconductor wafer (not shown) in a state where the release film 15 is removed, and adhering the 1 st surface 14a of the adhesive layer 14 for a jig to a jig such as a ring frame.
In the composite sheet 101 for forming a protective film, the 2 nd surface 11b of the base material 11 has a surface roughness of 0.053 to 0.48 μm, which is larger than the 1 st surface 11a of the base material 11, and has a moderate uneven shape. Thus, when the protective film forming composite sheet 101 is wound up to form a roll, adhesion between the contact surfaces of the rolls, that is, between the 2 nd surface 11b of one base material 11 and the 1 st surface 15a of the other release film 15 in the laminated protective film forming composite sheet 101 can be suppressed, and blocking can be suppressed.
In the process of manufacturing a semiconductor device, the protective film forming film 13 may be formed into a protective film by curing in a state of being attached to a surface (back surface) of a semiconductor wafer or a semiconductor chip opposite to a circuit forming surface, and then printing (laser printing) may be performed by irradiating laser light from the 2 nd surface 11b side of the base material 11. At this time, the laser light enters the support sheet 1 from the 2 nd surface 11b side of the base material 11 and reaches the protective film. Therefore, as described above, since the 2 nd surface 11b of the base material 11 has a moderate uneven shape and a low uneven degree, diffuse reflection of laser light on the 2 nd surface 11b of the base material 11 is suppressed, and clear laser printing can be performed on the protective film.
In addition, in the manufacturing process of the semiconductor device, a semiconductor wafer or a semiconductor chip provided with the composite sheet 101 for forming a protective film or the protective film may be inspected with the composite sheet 101 for forming a protective film or the protective film interposed therebetween by an infrared camera or the like. At this time, as described above, since the 2 nd surface 11b of the base material 11 has a moderate uneven shape and a low uneven degree, diffuse reflection of infrared rays at the 2 nd surface 11b of the base material 11 is suppressed, and a clear inspection image can be obtained.
In addition, in the case where an adhesive layer is provided on the uneven surface of a base material as in the conventional composite sheet for forming a protective film, the adhesive layer needs to be soft and sufficiently thick in order to reduce the influence of the uneven surface on the adhesive layer. This is because if the pressure-sensitive adhesive layer is hard, the pressure-sensitive adhesive layer may not be filled in the bottom portion of the convex portion on the surface of the substrate to generate a void portion, and if the pressure-sensitive adhesive layer is thin, the concave-convex shape of the surface of the substrate is reflected, and the surface (back surface) on the substrate side of the film for forming the protective film becomes a concave-convex surface. If the embedding of the adhesive layer into the concave-convex shape of the substrate surface becomes insufficient, the laser printing of the protective film as described above causes unclear printing, and a clear inspection image of the semiconductor wafer or semiconductor chip cannot be obtained. However, when the pressure-sensitive adhesive layer is too thick, the pressure-sensitive adhesive layer tends to vibrate during the dicing process, for example, and therefore the semiconductor chip or the semiconductor wafer during the dicing process to form the semiconductor chip tends to vibrate, and when an excessive force is applied to the semiconductor chip or the semiconductor wafer, breakage or chipping tends to occur. Therefore, when the pressure-sensitive adhesive layer is provided on the uneven surface of the substrate, various problems are likely to occur.
However, in the composite sheet 101 for forming a protective film of the present invention, the 1 st surface 11a of the base material 11 provided with the adhesive layer 12 has a surface roughness of 0.4 μm or less and a high smoothness (low roughness), and thus the above-described drawbacks can be avoided. That is, in the composite sheet 101 for forming a protective film, the 1 st surface 11a of the base material 11 can be sufficiently embedded by the adhesive layer 12, and the thick adhesive layer 12 does not need to be formed, so chipping can be suppressed.
Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
The composite sheet 102 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in fig. 2 except that the shape of the film for forming a protective film is different and there is no adhesive layer for a jig. That is, the composite sheet 102 for forming a protective film includes the adhesive layer 12 on the base material 11, the protective film forming film 23 on the adhesive layer 12, and the release film 15 on the protective film forming film 23.
The protective film forming film 23 is laminated on a part of the 1 st surface 12a of the pressure-sensitive adhesive layer 12, that is, a region on the center side in the width direction (left-right direction in fig. 3) of the support sheet 1.
The release film 15 is laminated on the 1 st surface 12a of the adhesive layer 12, the surface on which the protective film forming film 23 is not laminated, and the surface (1 st surface 23a and side surface 23 c) of the protective film forming film 23 which is not in contact with the adhesive layer 12. Here, the 1 st surface 23a of the protective film 23 is a surface of the protective film 23 opposite to the side in contact with the adhesive layer 12, and there are cases where the boundary between the 1 st surface 23a and the side surface 23c of the protective film 23 cannot be clearly distinguished. The side surface 23c of the protective film forming film 23 may not contact the release film 15. The protective film forming composite sheet 102 is usually stored in a state where the release film 15 is provided in this way.
The protective film forming composite sheet 102 is used by adhering the 1 st surface 23a of the protective film forming film 23 to the back surface of a semiconductor wafer (not shown) with the release film 15 removed, and adhering the surface of the 1 st surface 12a of the adhesive layer 12, on which the protective film forming film 23 is not laminated, to a jig such as a ring frame.
In the composite sheet 102 for forming a protective film, the 1 st surface 11a of the base material 11 has a surface roughness of 0.4 μm or less, and the 2 nd surface 11b has a surface roughness greater than the 1 st surface 11a and is
0.053-0.48 mu m. As a result, the protective film forming composite sheet 102 can prevent the adhesive layer 12 from being buried insufficiently in the 1 st surface 11a of the substrate 11 and from generating chipping, and can prevent blocking, clearly print the protective film by laser, and obtain a clear inspection image of the semiconductor wafer or the semiconductor chip, as in the case of the protective film forming composite sheet 101.
Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
The protective film forming composite sheet 103 shown here is the same as the protective film forming composite sheet 102 shown in fig. 3 except that the adhesive layer 14 for a jig is further laminated on the 1 st surface 12a of the adhesive layer 12, that is, on the surface where the protective film forming film 23 is not laminated, that is, in the region near the peripheral portion.
The protective film forming composite sheet 103 is used by attaching the 1 st surface 23a of the protective film forming film 23 to the back surface of a semiconductor wafer (not shown) and attaching the 1 st surface 14a of the jig adhesive layer 14 to a jig such as a ring frame in a state where the release film 15 is removed.
In the composite sheet 103 for forming a protective film, the surface roughness of the 1 st surface 11a of the base material 11 is 0.4 μm or less, and the surface roughness of the 2 nd surface 11b is 0.053 to 0.48 μm larger than the surface roughness of the 1 st surface 11 a. As a result, the protective film forming composite sheet 103 can prevent defects such as insufficient embedding of the adhesive layer 12 into the 1 st surface 11a of the substrate 11 and chipping, prevent blocking, clear laser printing of the protective film, and obtain clear inspection images of the semiconductor wafer or the semiconductor chip, as in the case of the protective film forming composite sheet 101.
The composite sheet for forming a protective film of the present invention is not limited to the examples shown in fig. 2 to 4, and may be modified or deleted in a part of the composition of the composite sheet for forming a protective film shown in fig. 2 to 4, or may be further added with other compositions in the above-described examples, within a range not impairing the effects of the present invention.
Next, the structure of each layer of the support sheet and the protective film-forming composite sheet of the present invention will be described.
Very good substrate
The surface roughness of the side surface (1 st surface) of the substrate having the pressure-sensitive adhesive layer may be in any range of, for example, 0.37 μm or less, 0.3 μm or less, 0.2 μm or less, 0.1 μm or less, 0.09 μm or less, 0.08 μm or less, 0.07 μm or less, and 0.06 μm or less, although these are only examples.
The lower limit of the surface roughness of the 1 st surface of the substrate is not particularly limited, and may be, for example, 0.01 μm or the like, but this is only an example.
Preferable examples of the surface roughness of the 1 st surface include 0.01 to 0.4. Mu.m, 0.01 to 0.37. Mu.m, 0.01 to 0.3. Mu.m, 0.01 to 0.2. Mu.m, 0.01 to 0.1. Mu.m, 0.01 to 0.09. Mu.m, 0.01 to 0.08. Mu.m, 0.01 to 0.07. Mu.m, and 0.01 to 0.06. Mu.m.
The surface roughness of the surface (the 2 nd surface) of the substrate on the opposite side to the side provided with the pressure-sensitive adhesive layer may be, for example, 0.055 μm or more, 0.08 μm or more, 0.15 μm or more, 0.25 μm or more, 0.35 μm or more, or 0.47 μm or less, 0.45 μm or less, 0.35 μm or less, 0.25 μm or less, 0.15 μm or less, or the like within the above range.
Preferable examples of the surface roughness of the 2 nd surface include 0.053 to 0.47. Mu.m, 0.053 to 0.45. Mu.m, 0.053 to 0.35. Mu.m, 0.053 to 0.25. Mu.m, and 0.053 to 0.15. Mu.m.
As other preferable examples of the surface roughness of the 2 nd side, 0.055 to 0.48. Mu.m, 0.08 to 0.48. Mu.m, 0.15 to 0.48. Mu.m, 0.25 to 0.48. Mu.m, and 0.35 to 0.48. Mu.m can be given.
Wherein the surface roughness of the 2 nd surface is larger than the surface roughness of the 1 st surface.
The substrate may be produced, for example, by using a substrate as a raw material (hereinafter, may be simply referred to as a "raw material substrate"), by a method of forming a smooth surface and an uneven surface simultaneously, or by a method of forming a smooth surface and an uneven surface separately.
Examples of a method for producing a substrate having a smooth surface and an uneven surface formed simultaneously include the following methods: by sandwiching a raw material substrate between a pair of rolls having different smoothness of roll surfaces, and passing the raw material substrate between the roll surfaces while rotating the rolls, a smooth surface is formed on the raw material substrate by a roll surface having a large smoothness (smooth surface of the roll) and a concave-convex surface is formed on the roll surface having a small smoothness (concave-convex surface of the roll), thereby producing a substrate.
On the other hand, as a method for producing a substrate having a smooth surface and an uneven surface, for example, the following methods are given: a substrate is produced by using a raw material substrate having a surface roughness of 0.4 [ mu ] m or less on one surface or both surfaces, determining one surface which is a smooth surface (surface having a surface roughness of 0.4 [ mu ] m or less), and subjecting the other surface different from the one surface to a smoothing treatment or a concavity-convexity treatment to form a concavity-convexity surface (surface having a surface roughness of 0.053 to 0.48 [ mu ] m) having a surface roughness larger than that of the smooth surface. Examples of the method of smoothing or embossing at this time include a so-called press molding method in which the raw material base material is pressed against the smooth surface or the uneven surface of the roll as described above.
In the case where the smooth surface or the uneven surface is formed on the raw material substrate by the shape of the transfer roller surface or the like as described above, the surface roughness of the substrate can be adjusted by adjusting the smoothness of the smooth surface of the roller surface or the like or the uneven surface.
In the above method, one surface of the raw material base material, which is finally a smooth surface (surface having a surface roughness of 0.4 μm or less), may be subjected to a smoothing treatment or a concavity-convexity treatment as needed, and the surface roughness thereof may be adjusted within a range of 0.4 μm or less.
The method of using the smooth surface or the uneven surface of the roller to make the surface roughness of one surface of the substrate 0.053 to 0.48 μm is described here, but the template used for transfer of the smooth surface or the uneven surface is not limited to the roller and may be a template of another shape such as a plate or a block.
The surface roughness treatment method of the raw material base material includes, for example, a sand blast treatment method, a solvent treatment method, and the like, in addition to the press molding method described above.
The method of producing a substrate having surface roughness of both surfaces satisfying the above conditions using a raw material substrate having surface roughness of 0.4 μm or less on one surface or both surfaces has been described above, but the substrate may be produced by, for example, the following method.
That is, a base material having a surface roughness of 0.053 μm or more on one surface or both surfaces is used, one surface which is to be finally formed into an uneven surface (surface having a surface roughness of 0.053 to 0.48 μm) is determined, and the other surface which is different from the one surface is subjected to a smoothing treatment or an uneven treatment to be formed into a smooth surface (surface having a surface roughness of 0.4 μm or less) having a surface roughness smaller than that of the uneven surface, thereby producing the base material.
In this method, one surface of the raw material base material, which is eventually formed into a concave-convex surface (surface having a surface roughness of 0.053 to 0.48 μm), may be subjected to a smoothing treatment or a concavity-convexity treatment as needed, and the surface roughness may be adjusted in the range of 0.053 to 0.48 μm.
Among them, as a method for producing the above-mentioned substrate, a method of forming a smooth surface and a concave-convex surface simultaneously using a raw material substrate is preferable.
The constituent material of the base material is preferably various resins, and the resin may be any known resin.
Among them, a substrate having a transmittance for light having a wavelength of 532nm and a transmittance for light having a wavelength of 1600nm is preferable. Light having a wavelength of 532nm is suitable for laser printing of the protective film, and light having a wavelength of 1600nm is suitable for infrared inspection of the semiconductor wafer or the semiconductor chip.
In the case where the adhesive layer to be described later is energy ray curable, a substrate having a transmittance to light in the ultraviolet region is preferable.
Specific constituent materials of the base material will be described later.
The constituent materials of the 1-layer base material may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily adjusted.
The tensile elastic modulus of the base material is not particularly limited, but is preferably 240 to 700MPa, more preferably 280 to 650MPa, and particularly preferably 320 to 600MPa.
The substrate may be composed of 1 layer (single layer) or 2 or more layers. In the case where the substrate is composed of a plurality of layers, the plurality of layers may be the same or different from each other. That is, all layers may be the same, all layers may be different, or only part of layers may be the same. In addition, when the layers are different from each other, the combination of the layers is not particularly limited. In the present specification, the term "a plurality of layers are different from each other" means that at least one of the material and the thickness of each layer is different from each other, and this is not limited to the case of the base material.
The thickness of the base material may be appropriately selected depending on the purpose, and is preferably 15 to 300. Mu.m, more preferably 20 to 200. Mu.m, and may be any thickness such as 30 to 160. Mu.m, 40 to 120. Mu.m, and the like. By setting the thickness of the base material to such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or a semiconductor chip are further improved.
Here, "thickness of the substrate" refers to thickness of the entire substrate, for example, thickness of the substrate composed of a plurality of layers refers to total thickness of all layers constituting the substrate.
The surface roughness of at least one surface of the substrate is 0.053 μm or more, and the substrate has a non-smooth surface having a concave-convex shape, and the thickness of the substrate can be calculated with higher accuracy at a portion of the substrate including the convex portion with the tip of the convex portion as a starting point.
Adhesive layer of very good quality
The pressure-sensitive adhesive layer may be a known pressure-sensitive adhesive layer, and is not particularly limited. For example, the adhesive layer may be any of energy ray curability and non-energy ray curability.
In the present invention, "energy ray curability" refers to a property of curing by irradiation with energy rays. In contrast, the property of not curing even when the energy ray is irradiated is referred to as "non-energy ray curability".
In the present invention, the "energy line" refers to a ray having energy in an electromagnetic wave or a charged ion 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, a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet source. The electron beam may radiate rays generated by an electron beam accelerator or the like.
Examples of the constituent material of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive such as an adhesive resin, a crosslinking agent, and the like.
Among them, an adhesive layer having a transmittance for light having a wavelength of 532nm and a transmittance for light having a wavelength of 1600nm is preferable. Light having a wavelength of 532nm is suitable for laser printing of the protective film, and light having a wavelength of 1600nm is suitable for infrared inspection of the semiconductor wafer or the semiconductor chip.
The pressure-sensitive adhesive layer is preferably either of energy ray curability and non-energy ray curability, and more preferably is non-energy ray curability.
The storage modulus of the pressure-sensitive adhesive layer is not particularly limited, but is usually preferably 0.01 to 1000MPa, more preferably 0.01 to 500MPa, and particularly preferably 0.01 to 300MPa.
The storage modulus of the adhesive layer can be adjusted by adjusting the kind or amount of the component containing the adhesive layer.
In the present specification, unless otherwise specified, when the adhesive layer is curable, "storage modulus of the adhesive layer" means "storage modulus of the adhesive layer before curing".
The storage modulus of the adhesive layer was determined by the following method.
Specifically, the adhesive layers were bonded to each other, a laminate of adhesive layers having a thickness of 800 μm was produced, the laminate was punched out into a circular shape having a diameter of 10mm, a test piece was produced, a strain with a frequency of 1Hz was applied to the test piece by a measuring device such as a viscoelasticity measuring device, a storage modulus at-50 to 150℃was measured, and a value of the storage modulus at 23℃was used as the storage modulus of the adhesive layer.
The adhesive layer may be formed of 1 layer (single layer) or 2 or more layers. In the case where the adhesive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other. Here, "the layers may be the same as or different from each other" means the same as in the case of the above-described base material. In addition, when the layers are different from each other, the combination of the layers is not particularly limited.
The thickness of the pressure-sensitive adhesive layer may be appropriately selected depending on the purpose, and is preferably 1 to 50. Mu.m, more preferably 1 to 40. Mu.m, particularly preferably 1 to 30. Mu.m. By setting the thickness of the pressure-sensitive adhesive layer to the lower limit value or more, the adhesive force of the pressure-sensitive adhesive layer to the protective film-forming film is further improved. Further, the effect of the concave-convex shape of the 1 st surface of the embedded substrate is further improved, and the influence of the concave-convex shape on the adhesive layer can be further reduced. On the other hand, by setting the thickness of the adhesive layer to the above upper limit value or less, the chip suppressing effect is further improved, and the dicing process is more stabilized.
Here, the "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer, and for example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer.
As described above, the surface roughness of the 1 st surface of the base material is 0.4 μm or less, and the side surface (2 nd surface) of the pressure-sensitive adhesive layer on which the base material is provided may be a non-smooth surface having a concave-convex shape having a surface roughness of 0.1 μm or more or the like, corresponding to such a concave-convex shape. In this case, the thickness of the adhesive layer can be calculated with higher accuracy at the portion of the adhesive layer including the convex portion, with the tip of the convex portion as a starting point.
The adhesive layer preferably adjusts hardness according to its thickness. Examples of the index for determining the hardness of the pressure-sensitive adhesive layer include the storage modulus described above.
For example, when the thickness of the pressure-sensitive adhesive layer is preferably greater than 15 μm (thicker than 15 μm), more preferably 18 μm or more, the storage modulus of the pressure-sensitive adhesive layer is preferably 30kPa or more, more preferably 40kPa or more, particularly preferably 50kPa or more. The upper limit of the storage modulus of the adhesive layer in this case may be, for example, the upper limit of the storage modulus at the usual value as set forth above. Thus, if the adhesive layer is hard, vibration of the adhesive layer is less likely to occur even when the adhesive layer is thick, for example, during cutting in a dicing step. Therefore, the semiconductor chip and the semiconductor wafer during cutting in the process of forming the semiconductor chip are not likely to vibrate, and the occurrence of so-called chipping, such as cracking and chipping of the semiconductor chip due to the application of excessive force to the semiconductor chip and the semiconductor wafer, can be suppressed.
On the other hand, in the case where the thickness of the adhesive layer is preferably a relatively small thickness of 15 μm or less, more preferably 10 μm or less, the storage modulus of the adhesive layer is not particularly limited. In this case, even if the adhesive layer is soft, for example, vibration is less likely to occur in the adhesive layer when the adhesive layer is cut in the dicing step, and therefore the same effect as in the case of the adhesive layer being hard and thick as described above can be obtained.
In this case (in the case where the pressure-sensitive adhesive layer is thin), the storage modulus of the pressure-sensitive adhesive layer may be set to the usual range as described above, for example, but this is only an example. In this case, too, the storage modulus of the adhesive layer is preferably set to the same range as in the case of the thicker adhesive layer described above, in order to further improve the chip suppressing effect.
That is, in the support sheet, by making the thickness of the adhesive layer preferably 15 μm or less, more preferably 10 μm or less, a higher chipping-suppressing effect can be obtained without being affected by the storage modulus of the adhesive layer.
The adhesive layer may be formed using an adhesive composition containing an adhesive. For example, the pressure-sensitive adhesive layer may be formed on the target site by applying the pressure-sensitive adhesive composition to the surface to be formed of the pressure-sensitive adhesive layer and drying the composition as necessary. A more specific method of forming the adhesive layer is described in detail later together with a method of forming other layers. The content ratio of the components in the adhesive composition, which do not vaporize at ordinary temperature, is generally the same as the content ratio of the above components in the adhesive layer. In the present specification, the term "normal temperature" means a temperature at which cooling is not particularly performed nor heating is performed, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ℃.
The adhesive composition can be obtained by blending the adhesive, and components other than the adhesive, which are used as needed, with the adhesive composition.
The order of addition in the mixing of the components is not particularly limited, and two or more components may be added simultaneously.
The method of mixing the components at the time of blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a paddle, a method of mixing by using a mixer, 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 deteriorated, and the temperature is preferably 15 to 30 ℃.
The application of the adhesive composition can be performed by a known method, and examples thereof include a method 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 blade coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying condition of the adhesive composition is not particularly limited, and when the adhesive composition contains a solvent described later, it is preferable to heat-dry it. The solvent-containing adhesive composition is preferably dried, for example, at 70 to 130℃for 10 seconds to 5 minutes.
Examples of the support sheet having the base material and the pressure-sensitive adhesive layer formed of the above-mentioned constituent materials include: an adhesive sheet comprising a base film and an adhesive layer formed on the base film as described in japanese patent No. 4805549; an adhesive sheet comprising a base film and an adhesive layer formed on the base film as described in japanese patent No. 4781633; a dicing sheet described in japanese patent No. 5414953, which includes a base material and an adhesive layer laminated on at least one surface thereof; a sheet for work processing having a pressure-sensitive adhesive resin layer (pressure-sensitive adhesive layer) on at least one surface of a base material as described in japanese patent application laid-open No. 2013-199562, and the like.
The support sheet of the present invention is preferably one having the same constituent material as the sheet and having the surface roughness of the 1 st and 2 nd surfaces adjusted to the above numerical range.
Film for forming protective film
The protective film forming film has curability, and is cured to form a protective film.
The protective film-forming film may be any of thermosetting and energy ray-curable films.
Film for forming thermosetting protective film
Preferable examples of the film for forming a thermosetting protective film include a film for forming a thermosetting protective film containing a polymer component (a) and a thermosetting component (B). The polymer component (a) is a component which can be considered as a component formed by polymerizing a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as an initiator of the reaction. In the present embodiment, the polymerization reaction also includes a polycondensation reaction.
The thermosetting protective film-forming film may be formed of 1 layer (single layer) or 2 or more layers. When the thermosetting protective film forming film is composed of a plurality of layers, the plurality of layers may be the same or different from each other. Here, "the layers may be the same as or different from each other" means the same as in the case of the above-described base material. In addition, when the layers are different from each other, the combination of the layers is not particularly limited.
The thickness of the thermosetting protective film-forming 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 protective film forming film to the above lower limit or more, a protective film having higher protective ability can be formed. Further, by setting the thickness of the thermosetting protective film forming film to the above upper limit or less, the formation of excessive thickness can be suppressed.
Here, the "thickness of the thermosetting protective film forming film" refers to the thickness of the entire thermosetting protective film forming film, and for example, the thickness of the thermosetting protective film forming film composed of a plurality of layers refers to the total thickness of all layers constituting the thermosetting protective film forming film.
The curing condition for forming the protective film by adhering the thermosetting protective film to the back surface of the semiconductor wafer and curing the film is not particularly limited as long as the curing condition is such that the protective film can sufficiently function.
For example, the heating temperature at the time of curing the thermosetting protective film-forming film is preferably 100 to 200 ℃, more preferably 110 to 180 ℃, and particularly preferably 120 to 170 ℃. The heating time during curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.
Composition for forming thermosetting protective film
The thermosetting protective film-forming film can be formed using a thermosetting protective film-forming composition containing the constituent materials thereof. For example, the thermosetting protective film-forming composition may be applied to the surface to be formed of the thermosetting protective film-forming film, and dried as necessary, thereby forming the thermosetting protective film-forming film at the target site. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming a thermosetting protective film is generally the same as the content ratio of the above components in the film for forming a thermosetting protective film. Here, "normal temperature" is as described above.
The thermosetting protective film-forming composition may be applied, for example, in the same manner as in the case of the adhesive composition.
The drying condition of the thermosetting protective film-forming composition is not particularly limited, and when the thermosetting protective film-forming composition contains a solvent described later, it is preferably dried by heating. The solvent-containing thermosetting protective film-forming composition is preferably dried at a temperature of 70 to 130℃for 10 seconds to 5 minutes, for example.
Composition (III-1) for forming thermosetting protective film
Examples of the composition for forming a thermosetting protective film include a composition (III-1) for forming a thermosetting protective film containing a polymer component (a) and a thermosetting component (B) (in this specification, the composition may be simply referred to as "composition (III-1)").
[ Polymer component (A) ]
The polymer component (a) is a polymer compound for imparting film formability, flexibility, and the like to the film for forming a thermosetting protective film.
The polymer component (a) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include: acrylic resin (resin having a (meth) acryl), polyester, urethane resin (resin having a urethane bond), acrylic urethane resin, silicone resin (resin having a siloxane bond), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide, and the like, acrylic resin being preferred.
In the present specification, the term "(meth) acryl" includes both "acryl" and "methacryl". Similar terms to the (meth) acryl group are also used, and for example, "(meth) acrylic acid" includes both "acrylic acid" and "methacrylic acid", and "(meth) acrylate" includes both "acrylate" and "methacrylate".
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 10000 ～ 2000000, more preferably 100000 ～ 1500000. By setting the weight average molecular weight of the acrylic resin to the above lower limit or more, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. In addition, by setting the weight average molecular weight of the acrylic resin to the above upper limit or less, the thermosetting protective film-forming film can easily follow the uneven surface of the adherend, and generation of voids or the like between the adherend and the thermosetting protective film-forming film can be further suppressed.
In the present specification, unless otherwise specified, the weight average molecular weight is a polystyrene equivalent measured by Gel Permeation Chromatography (GPC).
The glass transition temperature (Tg) of the acrylic resin is preferably-60 to 70℃and more preferably-30 to 50 ℃. By setting the Tg of the acrylic resin to the lower limit or more, the adhesion between the protective film and the support sheet (pressure-sensitive adhesive layer) can be suppressed, and the peelability of the support sheet can be improved. In addition, by setting Tg of the acrylic resin to the above upper limit value or less, the thermosetting protective film forming film and the adhesion between the protective film and the adherend are improved.
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.
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, 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 the like are each a chain of 1 to 18 alkyl groups constituting alkyl esters;
Cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (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;
and substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate. The term "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of the amino group are replaced with groups other than hydrogen atoms.
The acrylic resin may be, for example, an acrylic resin obtained by copolymerizing one or more monomers selected from the group consisting of (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide, in addition to the (meth) acrylic acid ester.
The acrylic resin may be composed of only one kind, or two or more kinds, and in the case where the acrylic resin is composed of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The acrylic resin may have a functional group capable of bonding with 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 by the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). When the acrylic resin is bonded to other compounds through the functional group, the reliability of the package obtained by using the composite sheet for forming a protective film tends to be improved.
In the present invention, a thermoplastic resin other than an acrylic resin (hereinafter, may be simply referred to as "thermoplastic resin") may be used alone instead of the acrylic resin as the polymer component (a), or may be used in combination with the acrylic resin. By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, or the thermosetting protective film forming film is likely to follow the uneven surface of the adherend, and the occurrence of voids or the like between the adherend and the thermosetting protective film forming film may be further suppressed.
The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, more preferably 3000 to 80000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150℃and more preferably-20 to 120 ℃.
Examples of the thermoplastic resin include: polyesters, polyurethanes, phenoxy resins, polybutenes, polybutadiene, polystyrene, and the like.
The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and the ratio thereof may be arbitrarily selected.
In the composition (III-1), the ratio of the content of the polymer component (a) to the total content of all the components other than the solvent (i.e., the content of the polymer component (a) of the film for forming a thermosetting protective film) is not dependent on the kind of the polymer component (a), but is preferably in the range of 5 to 85 mass%, more preferably 5 to 80 mass%, and may be in any range of 10 to 70 mass%, 20 to 60 mass%, and 30 to 50 mass%, for example.
The polymer component (A) may correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) can be regarded as containing the polymer component (A) and the thermosetting component (B).
[ thermosetting component (B) ]
The thermosetting component (B) is a component for curing the thermosetting protective film-forming film to form a hard protective film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and the ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and epoxy thermosetting resins are preferable.
(epoxy thermosetting resin)
The epoxy thermosetting resin contains an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and the ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
The epoxy resin (B1) may be a known epoxy resin, and examples thereof include: polyfunctional epoxy resins, biphenyl compounds, bisphenol A glycidyl ethers, hydrogenated products thereof, o-cresol novolak epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and epoxy compounds having 2 or more functions.
As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can be used. 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, the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming the protective film is improved by using the epoxy resin having the unsaturated hydrocarbon group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of epoxy groups of a polyfunctional 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 constituting the epoxy resin.
The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples thereof include vinyl group (vinyl group), 2-propenyl group (allyl group), a (meth) acryl group, a (meth) acrylamide group, and the like, and acryl group is preferable.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, particularly preferably 300 to 3000, from the viewpoints of curability of the film for forming a thermosetting protective film, and strength and heat resistance of the protective film after curing.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 150 to 950g/eq.
The epoxy resin (B1) may be used alone or in combination of two or more, and in the case of using two or more in combination, 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: a compound having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include: the group obtained by acid anhydride treatment of a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an acid group is preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (B2) include: polyfunctional phenol resins, diphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl-type phenol resins, and the like.
Examples of amine curing agents having an amino group in the heat curing agent (B2) include: dicyandiamide (hereinafter also referred to simply as "dic") and the like.
The thermosetting agent (B2) may be a thermosetting agent having 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 the phenolic 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 the phenolic resin, or the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as that in the epoxy resin having an unsaturated hydrocarbon group.
When a phenol curing agent is used as the thermosetting agent (B2), the thermosetting agent (B2) is preferably a thermosetting agent having a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet.
In the thermosetting agent (B2), for example, the resin component such as a polyfunctional phenol resin, a novolak phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin has a number average molecular weight of preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000.
In the thermosetting agent (B2), the molecular weight of the non-resin component such as bisphenol and dicyandiamide 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, and in the case of using two or more in combination, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1) and the film for forming a thermosetting protective 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 may be, for example, any of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass, based on 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the above lower limit value or more, the film for forming a thermosetting protective film is more easily cured. In addition, by setting the content of the thermosetting agent (B2) to the above upper limit value or less, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.
In the composition (III-1) and the film for forming a thermosetting protective 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 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, particularly preferably 40 to 150 parts by mass, and for example, may be in any range of 40 to 125 parts by mass, 40 to 100 parts by mass, and 40 to 75 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). When the content of the thermosetting component (B) is in such a range, the adhesion between the protective film and the support sheet can be suppressed, and the peelability of the support sheet can be improved.
[ curing accelerator (C) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).
Preferable curing accelerators (C) include, for example: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the likeImidazoles (imidazoles in which 1 or more hydrogen atoms are replaced with groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphine obtained by substituting 1 or more hydrogen atoms with an organic group); tetraphenyl groupTetraphenylborates such as tetraphenylborates and triphenylphosphine tetraphenylborates.
The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and the 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 7 parts by mass, per 100 parts by mass of the content of the thermosetting component (B) in the composition (III-1) and the film for forming a thermosetting protective 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. In addition, by setting the content of the curing accelerator (C) to the above-described upper limit value or less, for example, the effect of suppressing segregation caused by movement of the curing accelerator (C) having a high polarity to the adhesive interface side with the adherend in the film for forming a thermosetting protective film under high temperature/high humidity conditions is improved, and the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming a protective film is further improved.
[ Filler (D) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By containing the filler (D) in the thermosetting protective film-forming film, the thermal expansion coefficient of the protective film obtained by curing the thermosetting protective film-forming film can be easily adjusted. Further, by optimizing the coefficient of thermal expansion for the object to be protected, the reliability of the semiconductor chip with the protective film obtained by using the film for forming a thermosetting protective film is further improved. In addition, by incorporating the filler (D) in the thermosetting protective film-forming film, the moisture absorption rate of the protective film can be reduced and the heat release 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 inorganic filler include, for example: powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride, and the like; beads formed by making these inorganic fillers into spheres; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fiber, and the like.
Of these, the inorganic filler material is preferably silica or alumina.
The filler (D) contained in the composition (III-1) and the thermosetting protective film-forming film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the filler (D) is used, the proportion of the filler (D) (i.e., the content of the filler (D) of the thermosetting protective film-forming film) in the composition (III-1) is preferably 5 to 80% by mass, more preferably 7 to 60% by mass, and may be, for example, any of 10 to 50% by mass, 15 to 45% by mass, and 20 to 40% by mass, based on the total content of all the components other than the solvent. By making the content of the filler (D) within such a range, the adjustment of the thermal expansion coefficient becomes easier.
[ coupling agent (E) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and the adhesiveness of the thermosetting protective film-forming film to an adherend can be improved. In addition, by using the coupling agent (E), the heat resistance of the protective film obtained by curing the thermosetting protective film-forming film is not impaired, and the water resistance can be improved.
The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (a), the thermosetting component (B), or 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, 3-glycidoxypropyl diethoxysilane, 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 dimethoxy silane, bis (3-triethoxysilylpropyl) tetrasulfide, methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxy silane, imidazole silane, and the like.
The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof 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, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (B), in the composition (III-1) and the film for forming a thermosetting protective film. When the content of the coupling agent (E) is not less than the lower limit, the effect of using the coupling agent (E) such as an improvement in dispersibility of the filler (D) in the resin, an improvement in adhesiveness between the thermosetting protective film-forming film and the adherend, and the like can be more significantly obtained. Further, by setting the content of the coupling agent (E) to the above upper limit or less, the occurrence of degassing (outgas) can be further suppressed.
[ Cross-linker (F) ]
When the polymer component (a) is a component having a functional group such as a vinyl group, (meth) acryl group, amino group, hydroxyl group, carboxyl group, isocyanate group, or the like capable of bonding to other compounds, such as the acrylic resin, the composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking the functional group in the polymer component (a) by bonding with other compounds, and by crosslinking in this manner, the initial adhesion and cohesive force of the thermosetting protective film-forming film can be adjusted.
Examples of the crosslinking agent (F) include: an organic polyisocyanate compound, an organic polyimine compound, a metal chelate-based crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine-based crosslinking agent (a crosslinking agent having an aziridine group), and the like.
Examples of the organic polyisocyanate compound include: an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds are collectively referred to simply as "aromatic polyisocyanate compound and the like"); trimers, isocyanurate bodies and adducts of the above aromatic polyisocyanate compounds; and a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound and the polyol compound. The "adduct" refers to a reaction product 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 adducts include xylylene diisocyanate adducts of trimethylolpropane, which will be described later. In addition, the "terminal isocyanate urethane prepolymer" is as described previously.
As the organic polyisocyanate compound, more specifically, for example, there may be mentioned: 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; a compound in which any one or two or more of toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or 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-tri-beta-aziridinyl propionate, tetramethylolmethane-tri-beta-aziridinylpropionate, N ' -toluene-2, 4-bis (1-aziridincarboxamide) triethylenemelamine, and the like.
In the case of using an organic polyisocyanate compound 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 crosslinking structure can be easily introduced into the thermosetting protective film-forming film by the reaction of the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where 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 composition (III-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, based on 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 or more, the effect of using the crosslinking agent (F) can be more significantly obtained. In addition, by setting the content of the crosslinking agent (F) to the above upper limit value or less, excessive use of the crosslinking agent (F) can be suppressed.
Energy ray-curable resin (G)
The composition (III-1) may contain an energy ray curable resin (G). The thermosetting protective film-forming film contains the energy ray-curable resin (G) and can be changed in characteristics by irradiation with energy rays.
The energy ray curable resin (G) is a resin obtained by polymerizing (curing) an energy ray curable compound.
Examples of the energy ray-curable compound include: the compound having at least 1 polymerizable double bond in the molecule is preferably an acrylic compound having a (meth) acryloyl group.
Examples of the acrylic acid ester compound include: (meth) acrylates having a chain aliphatic skeleton such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; (meth) acrylic esters having a cyclic aliphatic skeleton such as dicyclopentanyl (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; urethane (meth) acrylate oligomers; epoxy modified (meth) acrylates; polyether (meth) acrylates other than the polyalkylene glycol (meth) acrylates described above; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray curable compound is preferably 100 to 30000, more preferably 300 to 10000.
The energy ray curable compound used for polymerization may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The energy ray curable resin (G) contained in the composition (III-1) may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
[ photopolymerization initiator (H) ]
When the composition (III-1) contains the energy ray curable resin (G), a photopolymerization initiator (H) may be contained in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G).
Examples of the photopolymerization initiator (H) in the composition (III-1) include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ether, etc.; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one; acyl phosphine oxide compounds such as bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethyl thiuram monosulfide; alpha-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; a titanocene compound such as titanocene; thioxanthone compounds such as thioxanthone; a peroxy compound; diketone compounds such as butanedione; dibenzoyl; bibenzyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.
Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; amine and the like.
The photopolymerization initiator (H) contained in the composition (III-1) may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, based on 100 parts by mass of the content of the energy ray-curable resin (G).
[ colorant (I) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I).
Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.
Examples of the organic pigment and the organic dye include: ammonium-based dye, cyanine-based dye, merocyanine-based dye, croconic acid-based dye, and squaric acidPigment system, azulenium pigment system, polymethine pigment system, naphthoquinone pigment system, pyran->Pigments of the series, phthalocyanine series, naphthalocyanine series, naphthalimide series, azo series, condensed azo series, indigo series, viologen series, perylene series, di- >Oxazine-based pigments, quinacridone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, pyrrole-based pigments, thioindigo-based pigments (metal complex salt-based pigments), dithiol metal complex-based pigments, indophenol-based pigments, triallylmethane-based pigments, anthraquinone-based pigments, di->Oxazine pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments, and petrolatum pigments.
Examples of the inorganic pigment include: carbon black, cobalt-based pigment, iron-based pigment, chromium-based pigment, titanium-based pigment, vanadium-based pigment, zirconium-based pigment, molybdenum-based pigment, ruthenium-based pigment, platinum-based pigment, ITO (indium tin oxide) -based pigment, ATO (antimony tin oxide) -based pigment, and the like.
The colorant (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and the ratio thereof may be arbitrarily selected.
In the case of using the colorant (I), the content of the colorant (I) of the film for forming a thermosetting protective film can be appropriately adjusted according to the purpose. For example, the printing visibility when laser printing is performed on the protective film can be adjusted by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film and adjusting the light transmittance of the protective film. In addition, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, the designability of the protective film can be improved and the grinding marks on the back surface of the semiconductor wafer can be made less visible. In view of these, in the composition (III-1), the proportion of the content of the colorant (I) relative to the total content of all the components other than the solvent (i.e., the content of the colorant (I) of the film for forming a thermosetting protective film) is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass. By setting the content of the colorant (I) to the above lower limit value or more, the effect of using the colorant (I) can be more remarkably obtained. Further, by setting the content of the colorant (I) to the above upper limit value or less, excessive decrease in light transmittance of the film for forming a thermosetting protective film can be suppressed.
General purpose additive (J)
The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range not impairing the effect of the present invention.
The general-purpose additive (J) may be a known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples of preferable general-purpose additives include: plasticizers, antistatic agents, antioxidants, getters, and the like.
The general-purpose additive (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The content of the general-purpose additive (I) for the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.
[ solvent ]
The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) is excellent in handleability.
The solvent is not particularly limited, and 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 composition (III-1) may be one or two or more, and in the case where the solvent is two or more, the combination and the ratio thereof may be arbitrarily selected.
The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like, from the viewpoint of more uniformly mixing the components contained in the composition (III-1).
Method for producing composition for forming thermosetting protective film
The composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending the components constituting the composition.
The order of addition of the components is not particularly limited, and two or more components may be added simultaneously.
In the case of using a solvent, the solvent may be mixed with any component other than the solvent to dilute the component in advance, or the solvent may be mixed with the component without diluting the component other than the solvent in advance.
The method of mixing the components at the time of mixing is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a paddle, a method of mixing by using a mixer, 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 are not degraded, and the temperature is preferably 15 to 30 ℃.
Film for forming energy ray-curable protective film
The film for forming an energy ray-curable protective film contains an energy ray-curable component (a).
In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably has adhesiveness, more preferably is uncured and has adhesiveness. Here, "energy ray" and "energy ray curability" are described as above.
The energy ray-curable protective film-forming film may be formed of only 1 layer (single layer), or may be formed of at least 2 layers, and in the case of multiple layers, the multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.
The thickness of the film for forming an energy ray-curable protective 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 protective film-forming film to the above lower limit or more, a protective film having higher protective ability can be formed. Further, by setting the thickness of the energy ray-curable protective film-forming film to the above upper limit value or less, the formation of excessive thickness can be suppressed.
Here, the "thickness of the energy ray-curable protective film-forming film" refers to the thickness of the entire energy ray-curable protective film-forming film, and for example, the thickness of the energy ray-curable protective film-forming film composed of a plurality of layers refers to the total thickness of all layers constituting the energy ray-curable protective film-forming film.
The curing condition for forming the protective film by bonding the film for forming an energy ray-curable protective film to the back surface of the semiconductor wafer and curing the film is not particularly limited as long as the curing condition is such that the protective film can sufficiently function.
For example, in curing the film for forming an energy ray-curable protective film, the illuminance of the energy ray is preferably 120 to 280mW/cm 2 . In the curing, the amount of light of the energy ray is preferably 200 to 1000mJ/cm 2 。
Composition for forming energy ray-curable protective film
The energy ray-curable protective film-forming film can be formed using an energy ray-curable protective film-forming composition containing the constituent materials thereof. For example, the energy ray-curable protective film-forming composition may be applied to the surface of the energy ray-curable protective film-forming film to be formed, and dried as necessary, thereby forming the energy ray-curable protective film-forming film at the target site. The content ratio of the components that do not vaporize at normal temperature in the composition for forming an energy ray-curable protective film is generally the same as the content ratio of the components of the film for forming an energy ray-curable protective film. Here, "normal temperature" is as described above.
The energy ray-curable protective film-forming composition may be applied, for example, in the same manner as in the case of the adhesive composition.
The drying condition of the composition for forming an energy ray-curable protective film is not particularly limited, and when the composition for forming an energy ray-curable protective film contains a solvent described later, it is preferable to heat-dry it. The composition for forming an energy ray-curable protective film containing a solvent is preferably dried at a temperature of, for example, 70 to 130 ℃ for 10 seconds to 5 minutes.
Composition (IV-1) for forming energy ray-curable protective film
Examples of the composition for forming an energy ray-curable protective film include a composition (IV-1) for forming an energy ray-curable protective film (hereinafter, sometimes simply referred to as "composition (IV-1)") containing the above-mentioned energy ray-curable component (a).
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 formability, flexibility, and the like to the energy ray-curable protective film-forming film, and forming a hard protective film after curing.
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 polymer at least a part of which is crosslinked by a crosslinking agent, or may be a polymer which is not crosslinked.
(Polymer (a 1) having an energy ray-curable group with a weight-average molecular weight of 80000 ～ 2000000)
Examples of the polymer (a 1) having an energy ray-curable group and having a weight average molecular weight of 80000 ～ 2000000 include: an acrylic resin (a 1-1) which is obtained by reacting an acrylic polymer (a 11) having a functional group capable of reacting with a group of another compound and an energy ray curable compound (a 12) having an energy ray curable group such as an energy ray curable double bond, which is a group reactive with the functional group.
Examples of the functional group capable of reacting with a group of another compound include: hydroxyl, carboxyl, amino, substituted amino (a group in which 1 or 2 hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms), epoxy, and the like. Among them, the functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of circuits of a semiconductor wafer, a semiconductor chip, and the like.
Among these, the above functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a 11)
Examples of the acrylic polymer (a 11) having the functional group include: the polymer obtained by copolymerizing the acrylic monomer having the above functional group and the acrylic monomer having no functional group may be a copolymer obtained by copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) other than the above monomers.
The acrylic polymer (a 11) may be a random copolymer or a block copolymer, and the polymerization method may be a known method.
Examples of the acrylic monomer having the functional group include: hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, substituted amino group-containing monomers, epoxy group-containing monomers, and the like.
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 above-mentioned ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the above functional group is 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 in the case where 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 the like are each a chain of 1 to 18 alkyl groups constituting alkyl esters.
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 in the case where 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 in the case where 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 the polymer. By setting the ratio to such a range, the energy ray-curable group content in the acrylic resin (a 1-1) obtained by copolymerizing the acrylic polymer (a 11) and the energy ray-curable compound (a 12) can be easily adjusted 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 in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the resin layer-forming composition (IV-1), the ratio of the content of the acrylic resin (a 1-1) (i.e., the content of the acrylic resin (a 1-1) of the film for forming an energy ray-curable protective film) to the total content of the components other than the solvent is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass, and may be, for example, any of 15 to 50% by mass, 25 to 50% by mass, and 35 to 50% by mass.
Energy ray-curable Compound (a 12)
The energy ray curable compound (a 12) preferably has one or more groups selected from isocyanate groups, epoxy groups and carboxyl groups as groups capable of reacting with the functional groups of the acrylic polymer (a 11), and more preferably has isocyanate groups as the groups. In the case where the energy ray curable compound (a 12) has an isocyanate group as the group, for example, the isocyanate group is likely to react 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 per 1 molecule, more preferably 1 to 3 energy ray curable groups.
Examples of the energy ray-curable compound (a 12) include: 2-methacryloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 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 these compounds, 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 in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The content of the energy ray curable group derived from the energy ray curable compound (a 12) in the acrylic resin (a 1-1) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol% based on the content of the functional group derived from the acrylic polymer (a 11). When the content ratio is in such a range, the adhesion of the cured protective film is further increased. In the case where the energy ray-curable compound (a 12) is a monofunctional (1-molecule having 1 group), the upper limit of the content ratio is 100 mol%, but in the case where the energy ray-curable compound (a 12) is a polyfunctional (1-molecule having 2 or more groups), the upper limit of the content ratio may exceed 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 as described above.
In the case where the polymer (a 1) is a polymer at least a part of which is crosslinked by a crosslinking agent, the polymer (a 1) may be a compound obtained by polymerizing a monomer having a group reactive with the crosslinking agent and crosslinking the monomer having a group reactive with the crosslinking agent, which is not any of the monomers described as monomers constituting the acrylic polymer (a 11), or may be a compound obtained by crosslinking the monomer having a group reactive with the functional group derived from the energy ray-curable compound (a 12).
The polymer (a 1) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one kind only, or two or more kinds, and in the case of two or more kinds, 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)
Examples of the energy ray-curable group included in the compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and (meth) acryl, vinyl, and the like are preferable.
The compound (a 2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include: a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, a phenolic resin 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) may be, for example, a polyfunctional monomer or oligomer, and the like, and an acrylic compound having a (meth) acryloyl group is preferable.
Examples of the acrylic acid ester compound 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) 2, 2-acryloxypropane, 2- ((di (meth) acrylate), difunctional (meth) acrylates such as 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;
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 phenolic resin having an energy ray curable group in the above-mentioned 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 in the present invention, it is treated as the above-mentioned compound (a 2).
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 composition (IV-1) and the energy ray-curable protective film-forming film may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition (IV-1) and the film for forming an energy ray-curable protective film contain the compound (a 2) as the energy ray-curable component (a), the composition preferably further contains a polymer (b) having no energy ray-curable group.
The polymer (b) may be a polymer at least a part of which is crosslinked by a crosslinking agent, or may be a polymer which is not crosslinked.
Examples of the polymer (b) having no energy ray-curable group include: acrylic polymers, phenoxy resins, polyurethane resins, polyesters, rubber resins, acrylic urethane resins, and the like.
Among these polymers, the polymer (b) is preferably an acrylic polymer (hereinafter, may be simply referred to as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known one, 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 the 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, substituted amino group-containing (meth) acrylates, and the like. Here, the "substituted amino group" is as described above.
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 the like are each a chain of 1 to 18 alkyl groups constituting alkyl esters.
Examples of the (meth) acrylate having a cyclic skeleton include: cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (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, 4-hydroxybutyl (meth) acrylate, and the like.
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, at least a part of which is crosslinked by a crosslinking agent, include: a polymer 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, in the case where 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 these functional groups, a hydroxyl group having high reactivity with an isocyanate group is preferable. In the case where the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among these functional groups, a carboxyl group having high reactivity with an epoxy group is preferable. Among them, the reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of circuits of semiconductor wafers, semiconductor chips, and the like.
Examples of the polymer (b) having the reactive functional group and not having an energy ray curable group include: and a polymer obtained by polymerizing at least a monomer having the above reactive functional group. In the case of the acrylic polymer (b-1), a monomer having the reactive functional group may be used as one or both of the acrylic monomer and the non-acrylic monomer, which are listed as monomers constituting the polymer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing (meth) acrylic esters containing a hydroxyl group, and polymers obtained by polymerizing monomers obtained by substituting 1 or 2 or more hydrogen atoms in the acrylic monomer or the non-acrylic monomer mentioned above with the reactive functional group.
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 the polymer. When the ratio is in such a range, the degree of crosslinking in the polymer (b) is more preferably in the range.
From the viewpoint of better film forming property of the composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) having no energy ray curable group is preferably 10000 ～ 2000000, more preferably 100000 ～ 1500000. Here, the "weight average molecular weight" is as described above.
The polymer (b) having no energy ray-curable group contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one kind or two or more kinds, and in the case where two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) may be a composition containing any one or both of the polymer (a 1) and the compound (a 2). In the case where the composition (IV-1) contains the compound (a 2), it is preferable that the composition further contains the polymer (b) having no energy ray curable group, and in this case, the composition further preferably contains the compound (a 1). The composition (IV-1) may contain the polymer (a 1) and the polymer (b) having no energy ray curable group, in addition to the compound (a 2).
In the case where the composition (IV-1) 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, based on 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 composition (IV-1).
In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group (that is, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) in the energy ray-curable protective film-forming film) to the total content of the components other than the solvent is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the content of the energy ray-curable component is in such a range, the energy ray-curability of the film for forming an energy ray-curable protective film becomes more excellent.
The composition (IV-1) may contain, in addition to the above-mentioned energy ray curable component, one or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose. For example, by using the composition (IV-1) containing the above-mentioned energy ray curable component and thermosetting component, the adhesion of the formed energy ray curable protective film to the adherend is improved by heating, and the strength of the protective film formed from the energy ray curable protective film is also improved.
The thermosetting component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H), the colorant (I) and the general-purpose additive (J) in the energy ray-curable resin composition (III-1) are the same as those in the composition (IV-1), respectively.
In the composition (IV-1), one of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive may be used alone, or two or more of them may be used in combination, and in the case where two or more of them are used in combination, the combination and the ratio thereof may be arbitrarily selected.
The content of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant and general-purpose additive in the composition (IV-1) is not particularly limited as long as it is appropriately adjusted according to the purpose.
The composition (IV-1) preferably further contains a solvent in order to improve the handleability thereof by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1) for forming a protective film.
The solvent contained in the composition (IV-1) may be one or two or more.
Method for producing composition for forming energy ray-curable protective film
The composition for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by blending the components for constituting the composition.
The order of addition of the components is not particularly limited, and two or more components may be added simultaneously.
In the case of using a solvent, the solvent may be mixed with any component other than the solvent to dilute the component in advance, or the solvent may be mixed with the component without diluting the component other than the solvent in advance.
The method of mixing the components at the time of mixing is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a paddle, a method of mixing by using a mixer, 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 are not degraded, and the temperature is preferably 15 to 30 ℃.
Method for producing support sheet, and method for producing composite sheet for forming protective film
The support sheet and the protective film-forming composite sheet may be manufactured by sequentially laminating the support sheet and the protective film-forming composite sheet in a manner corresponding to the positional relationship of the layers. The method of forming each layer is as described above.
For example, in the case of laminating an adhesive layer on a substrate in the production of a support sheet, the adhesive composition may be applied to the substrate and dried as necessary.
On the other hand, for example, in the case of further laminating a protective film forming film on an adhesive layer already laminated on a substrate in the production of a composite sheet for forming a protective film, the protective film forming film may be directly formed by applying a thermosetting protective film forming composition or an energy ray curable protective film forming composition on the adhesive layer. Thus, when a continuous 2-layer laminate structure is formed using any of the compositions, the composition can be further applied to a layer formed from the composition to form a new layer. Among these, the composition is preferably used to form a layer of the 2 layers stacked after the above, on another release film in advance, and then the exposed surface of the formed layer on the opposite side to the side in contact with the release film is bonded to the exposed surface of the already formed remaining layer, thereby forming a continuous 2-layer stacked structure. In this case, the composition is preferably applied to the release treated surface of the release film. The release film may be removed as needed to form the laminate structure.
That is, in the case of producing a composite sheet for forming a protective film, an adhesive composition is applied to a substrate, and if necessary, the adhesive composition is dried, whereby an adhesive layer is laminated on the substrate, and a thermosetting protective film forming composition or an energy ray curable protective film forming composition is applied to a release film, and if necessary, the composition is dried, whereby a protective film forming film is formed on the release film, and then an exposed surface of the protective film forming film is bonded to an exposed surface of the adhesive layer laminated on the substrate, and a protective film forming film is laminated on the adhesive layer, whereby a composite sheet for forming a protective film is obtained.
On the other hand, in the case of laminating an adhesive layer on a substrate, instead of the method of applying an adhesive composition on a substrate as described above, the following method may be employed: the pressure-sensitive adhesive composition is applied to a release film, and if necessary, the release film is dried to form a pressure-sensitive adhesive layer thereon, and then the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of a substrate to laminate the pressure-sensitive adhesive layer on the substrate.
In either method, the release film may be removed at any time after the formation of the target laminated structure.
In this way, since the layers (the adhesive layer and the protective film forming film) other than the base material constituting the protective film forming composite sheet are formed on the release film in advance and laminated by a method of adhering to the surface of the target layer, the protective film forming composite sheet can be manufactured by appropriately selecting the layers in such a process as necessary.
However, in the present invention, when the surface roughness of the laminated surface of the adhesive layer in the substrate, i.e., the 1 st surface, is a value of 0.1 to 0.4 μm or the vicinity thereof, and the degree of the roughness of the surface cannot be neglected, it is preferable to form the adhesive layer (form the supporting sheet) by a method of applying the adhesive composition on the substrate. This is because, when a pre-formed adhesive layer is bonded to such an uneven surface, for example, the adhesive layer is not filled in the vicinity of the root of the convex portion of the surface, and a void is generated, which results in insufficient embedding of the adhesive layer into the surface (surface 1). Thus, when the embedding of the 1 st surface becomes insufficient, the above-described problem occurs.
In contrast, when the adhesive composition is applied to the 1 st surface of the substrate to form the adhesive layer, the adhesive composition having fluidity fills the portions in the vicinity of the bottoms of the convex portions of the 1 st surface sufficiently, and as a result, these portions are sufficiently embedded in the adhesive layer, and therefore, the occurrence of such a problem can be highly suppressed. However, for example, when the pressure-sensitive adhesive layer is bonded to the 1 st surface of the substrate, the pressure-sensitive adhesive layer may be softened by heating to suppress the generation of the void portion. Therefore, a method of bonding the preformed adhesive layer to the 1 st surface of the substrate may be used.
The composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (e.g., protective film forming film) on the opposite side of the support sheet. Therefore, the composite sheet for forming a protective film can be obtained by applying a composition for forming a thermosetting protective film, a composition for forming an energy ray-curable protective film, or the like to the release film (preferably, the release treated surface thereof) to form a layer constituting the outermost layer, drying the composition as needed, forming a layer constituting the outermost layer on the release film, and then laminating the remaining layers on the exposed surface of the layer on the opposite side of the layer to the side in contact with the release film by any of the above-mentioned methods, thereby obtaining the composite sheet for forming a protective film without removing the release film and maintaining the bonded state.
Examples
Hereinafter, the present invention will be described in more detail by way of specific examples, but the present invention is not limited to the examples shown below.
The composition of each layer of the protective film-forming composite sheet in the following examples and the like is as follows.
< substrate >
The base material constituting the support sheet is shown below.
Substrate Bm1: a substrate which comprises polypropylene as a main constituent material, has a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.05 μm, and a surface roughness (Ra) of a concave-convex surface of 0.1 μm.
Substrate Bm2: a substrate which comprises polypropylene as a main constituent material, has a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.05 μm, and a surface roughness (Ra) of a concave-convex surface of 0.2 μm.
Substrate Bm3: a substrate which comprises polypropylene as a main constituent material, has a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.05 μm, and a surface roughness (Ra) of a concave-convex surface of 0.3 μm.
Substrate Bm4: a substrate comprising polybutylene terephthalate as a main constituent material, having a thickness of 80 [ mu ] m, a tensile elastic modulus of 500MPa, a surface roughness (Ra) of a smooth surface of 0.05 [ mu ] m, and a surface roughness (Ra) of a rugged surface of 0.3 [ mu ] m.
Substrate Bm5: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, and had smooth surfaces with a surface roughness (Ra) of 0.05. Mu.m.
Substrate Bm6: a substrate which comprises polypropylene as a main constituent material, has a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.05 μm, and a surface roughness (Ra) of a concave-convex surface of 0.5 μm.
Substrate Bm7: a substrate which comprises polypropylene as a main constituent material, has a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.05 μm, and a surface roughness (Ra) of a concave-convex surface of 0.055 μm.
Substrate Bm8: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.03 μm, and a surface roughness (Ra) of a concave-convex surface of 0.4 μm.
Substrate Bm9: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.03 μm, and a surface roughness (Ra) of a concave-convex surface of 0.47 μm.
Substrate Bm10: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.35 μm, and a surface roughness (Ra) of a concave-convex surface of 0.4 μm.
Substrate Bm11: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.37 μm, and a surface roughness (Ra) of a concave-convex surface of 0.47 μm.
Substrate Bm12: a substrate which was mainly composed of polypropylene, had a thickness of 80 μm, a tensile elastic modulus of 360MPa, a surface roughness (Ra) of a smooth surface of 0.43 μm, and a surface roughness (Ra) of a concave-convex surface of 0.47 μm.
The tensile elastic modulus and the surface roughness of the base material were measured by the following methods.
(measurement of tensile elastic modulus of substrate)
A test piece was produced by cutting the base material, and the tensile elastic modulus (Young's modulus) of the test piece at 23℃was measured based on JIS K7161:1994. At this time, the width of the test piece at the time of measurement was set to 15mm, and the distance between the jigs was set to 100mm.
(measurement of surface roughness of substrate)
The surface roughness (Ra) of the substrate surface was measured by using a contact surface shape measuring device (SURFTEST SV-3000, mitsutoyo Co., ltd.) based on JIS B0601:2001, with a cut-off value λc of 0.8mm and an evaluation length Ln of 10 mm.
< adhesive resin >)
The adhesive resin used for forming the adhesive layer is as follows.
Adhesive resin (i) -1: an acrylic polymer having a weight average molecular weight of 600000, which was obtained by copolymerizing n-butyl acrylate (hereinafter, abbreviated as "BA") (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter, abbreviated as "HEA") (15 parts by mass).
Adhesive resin (i) -2: an acrylic polymer having a weight average molecular weight of 800000, which was obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter, abbreviated as "2 EHA") (30 parts by mass), isobornyl acrylate (hereinafter, abbreviated as "iBA") (50 parts by mass), and HEA (20 parts by mass).
< raw Material for producing composition for Forming protective film >
The raw materials used for producing the composition for forming a protective film are as follows.
[ Polymer component (A) ]
(A) -1: acrylic resin (weight-average molecular weight 800000, glass transition temperature-1 ℃ C.) (obtained by copolymerizing BA (10 parts by mass), methyl acrylate (70 parts by mass), glycidyl methacrylate (5 parts by mass), HEA (15 parts by mass))
[ thermosetting component (B) ]
Epoxy resin (B1)
(B1) -1: bisphenol A type epoxy resin (Mitsubishi chemical Co., ltd. "JER 828", epoxy equivalent 183-194 g/eq, number average molecular weight 370)
(B1) -2: bisphenol A type epoxy resin (Mitsubishi chemical Co., ltd. "JER1055", epoxy equivalent 800-900 g/eq, number average molecular weight 1600)
(B1) -3: dicyclopentadiene type epoxy resin (EPICLON HP-7200HH, manufactured by DIC Co., ltd.,' epoxy equivalent 255-260 g/eq)
Thermosetting agent (B2)
(B2) -1: dicyandiamide (thermally active latent epoxy curing agent, "Adeka Hardener EH-3636AS", manufactured by ADEKA Co., ltd. ", active hydrogen amount 21 g/eq)
[ curing accelerator (C) ]
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole (CUREZOL 2PHZ, manufactured by Kabushiki Kaisha of chemical industries, ltd.)
[ Filler (D) ]
(D) -1: silica filler (Admatechs company "SC2050MA", silica filler surface-modified with epoxy compound, average particle size 0.5 μm)
[ coupling agent (E) ]
(E) -1: 3-glycidoxypropyl trimethoxysilane (3-glycidoxypropyl trimethoxysilane) (silane coupling agent, "KBM403", methoxy equivalent 12.7mmol/g, molecular weight 236.3, manufactured by Xinyue chemical industries, ltd.)
[ Cross-linker (F) ]
(F) -1: toluene diisocyanate-based crosslinking agent (BHS 8515 manufactured by TOYOCHEM Co., ltd.)
[ photopolymerization initiator (H) ]
Photopolymerization initiator (H) -1: 1-hydroxycyclohexyl phenyl ketone (Irgacure (registered trademark) 184, manufactured by BASF corporation)
[ colorant (I) ]
(I) -1: carbon black (MA 600B, average particle size 28nm, mitsubishi chemical Co., ltd.)
Energy ray-curable component (a)
Energy ray curable component (a) -1: an ultraviolet curable acrylic copolymer having a methacryloxy group in a side chain, which is obtained by reacting 2-methacryloxyethyl isocyanate (hereinafter, abbreviated as "MOI") (an amount obtained by making the total number of moles of isocyanate groups in 2-methacryloxyethyl isocyanate to the total number of moles of hydroxyl groups derived from HEA in the acrylic polymer 0.8 times), with an acrylic polymer obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
Production of composite sheet for Forming protective film
Example 1
(production of composition (III-1) for Forming thermosetting protective film)
The polymer component (A) -1 (40 parts by mass), the epoxy resin (B1) -1 (5 parts by mass), the epoxy resin (B1) -2 (4 parts by mass), the epoxy resin (B1) -3 (10 parts by mass), the thermosetting agent (B2) -1 (1 part by mass), the curing accelerator (C) -1 (1 part by mass), the filler (D) -1 (36 parts by mass), the coupling agent (E) -1 (1 part by mass), and the colorant (I) -1 (2 parts by mass) were mixed, and then diluted with methyl ethyl ketone to a solid content concentration of 45% by mass, thereby obtaining the thermosetting protective film-forming composition (III-1). The blending amounts of the components other than methyl ethyl ketone shown here are all solid component amounts.
(formation of protective film Forming film)
The composition (III-1) obtained above was applied to the release treated surface of a release film (SP-PET 381031, manufactured by Lindeke Co., ltd., thickness: 38 μm) obtained by release treatment of one surface of a polyethylene terephthalate film by silicone treatment, and dried at 100℃for 3 minutes, whereby a protective film-forming film Pf1 having a thickness of 25 μm was formed.
(production of adhesive composition)
The adhesive resin (I) -1 (100 parts by mass) and a toluene diisocyanate-based crosslinking agent (TOYOCHEM Co., ltd. "BHS 8515") (1 parts by mass) were mixed and diluted with methyl ethyl ketone to a solid content concentration of 35% by mass, to obtain a non-energy ray-curable adhesive composition (I-4) -1. The blending amounts of the components other than methyl ethyl ketone shown here are all solid component amounts.
(formation of adhesive layer and production of supporting sheet)
The adhesive composition (I-4) -1 obtained above was applied to a smooth surface of the substrate Bm1 having a surface roughness of 0.05. Mu.m, and dried at 100℃for 1 minute, thereby forming an adhesive layer Ad1 having a thickness of 5. Mu.m, which was not energy ray-curable, to obtain a support sheet Ss1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 on the side not having the release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss1 are laminated, whereby a composite sheet for protective film formation having the structure shown in fig. 2 is obtained.
The protective film-forming composite sheet is formed by stacking a base material Bm1, an adhesive layer Ad1, a protective film-forming film Pf1, and a release film in the order of their thickness, wherein the surface of the base material Bm1 on the side provided with the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm1 on the opposite side to the side provided with the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 2
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the coating amount of the adhesive composition (I-4) -1 was changed to form a non-energy ray-curable adhesive layer Ad2 having a thickness of 20 μm instead of 5 μm at the time of forming the adhesive layer, to obtain a support sheet Ss2, and the obtained support sheet Ss2 was used.
That is, the composite sheet for forming a protective film is formed by stacking a base material Bm1, an adhesive layer Ad2, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, the surface of the base material Bm1 on the side having the adhesive layer Ad2 is a smooth surface, and the surface (exposed surface) of the base material Bm1 on the opposite side to the side having the adhesive layer Ad2 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 3
(production of adhesive composition)
The adhesive resin (I) -2 (100 parts by mass) and a toluene diisocyanate-based crosslinking agent (TOYOCHEM corporation "BHS 8515") (10 parts by mass) were mixed and then diluted with methyl ethyl ketone to a solid content concentration of 35% by mass, thereby obtaining a non-energy ray-curable adhesive composition (I-4) -2. The blending amounts of the components other than methyl ethyl ketone shown here are all solid component amounts.
(formation of adhesive layer and production of supporting sheet)
The adhesive composition (I-4) -2 obtained above was applied to a smooth surface of the substrate Bm1 having a surface roughness of 0.05. Mu.m, and dried at 100℃for 1 minute to form a non-energy ray-curable adhesive layer Ad3 having a thickness of 5. Mu.m, to obtain a support sheet Ss3.
(production of composite sheet for Forming protective film)
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the support sheet Ss3 obtained above was used instead of the support sheet Ss 1.
That is, the composite sheet for forming a protective film is formed by stacking a base material Bm1, an adhesive layer Ad3, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, the surface of the base material Bm1 on the side having the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) of the base material Bm1 on the side opposite to the side having the adhesive layer Ad3 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 4
(production of adhesive composition)
Adhesive composition (I-4) -2 was obtained in the same manner as in example 3.
(formation of adhesive layer and production of supporting sheet)
The adhesive composition (I-4) -2 obtained above was applied to a smooth surface of the substrate Bm2 having a surface roughness of 0.05. Mu.m, and dried at 100℃for 1 minute to form a non-energy ray-curable adhesive layer Ad3 having a thickness of 5. Mu.m, to obtain a support sheet Ss4.
(production of composite sheet for Forming protective film)
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the support sheet Ss4 obtained above was used instead of the support sheet Ss 1.
That is, the composite sheet for forming a protective film is formed by stacking a base material Bm2, an adhesive layer Ad3, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, the surface of the base material Bm2 on the side having the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) of the base material Bm2 on the opposite side to the side having the adhesive layer Ad3 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 5
(production of adhesive composition)
Adhesive composition (I-4) -2 was obtained in the same manner as in example 3.
(formation of adhesive layer and production of supporting sheet)
The adhesive composition (I-4) -2 obtained above was applied to a smooth surface of the substrate Bm3 having a surface roughness of 0.05. Mu.m, and dried at 100℃for 1 minute to form a non-energy ray-curable adhesive layer Ad3 having a thickness of 5. Mu.m, to obtain a support sheet Ss5.
(production of composite sheet for Forming protective film)
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the support sheet Ss5 obtained above was used instead of the support sheet Ss 1.
That is, the composite sheet for forming a protective film is formed by stacking a base material Bm3, an adhesive layer Ad3, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, the surface of the base material Bm3 on the side having the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) of the base material Bm3 on the opposite side to the side having the adhesive layer Ad3 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 6
(production of adhesive composition)
Adhesive composition (I-4) -2 was obtained in the same manner as in example 3.
(formation of adhesive layer and production of supporting sheet)
The adhesive composition (I-4) -2 obtained above was applied to a smooth surface of the substrate Bm4 having a surface roughness of 0.05. Mu.m, and dried at 100℃for 1 minute to form a non-energy ray-curable adhesive layer Ad3 having a thickness of 5. Mu.m, to obtain a support sheet Ss6.
(production of composite sheet for Forming protective film)
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the support sheet Ss6 obtained above was used instead of the support sheet Ss 1.
That is, the composite sheet for forming a protective film is formed by stacking a base material Bm4, an adhesive layer Ad3, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, the surface of the base material Bm4 on the side provided with the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) of the base material Bm4 on the side opposite to the side provided with the adhesive layer Ad3 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 7
(production of composition (IV-1) for Forming an energy ray-curable protective film)
The energy ray-curable composition (IV-1) was obtained by mixing the energy ray-curable component (a) -1 (42 parts by mass), the filler (D) -1 (55 parts by mass), the coupling agent (E) -1 (0.3 part by mass), the crosslinking agent (F) -1 (1 part by mass), the photopolymerization initiator (H) -1 (0.3 part by mass), and the colorant (I) -1 (1 part by mass), and diluting the mixture with methyl ethyl ketone to a solid content concentration of 45% by mass. The blending amounts of the components other than methyl ethyl ketone shown here are all solid component amounts.
(formation of protective film Forming film)
The composition (IV-1) obtained above was applied to the release treated surface of a release film (SP-PET 381031, manufactured by Lindeke Co., ltd., thickness: 38 μm) obtained by release treatment of one surface of a polyethylene terephthalate film by silicone treatment, and dried at 100℃for 3 minutes, thereby forming a protective film-forming film Pf2 having a thickness of 25 μm.
(production of adhesive composition)
Adhesive composition (I-4) -2 was obtained in the same manner as in example 3.
(formation of adhesive layer and production of supporting sheet)
The adhesive layer Ad3 was formed in the same manner as in example 5, to obtain a support sheet Ss5.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film having the above-described side without the release film and the exposed surface of the adhesive layer Ad3 of the support sheet Ss5 were laminated to obtain a protective film-forming composite sheet having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm3, an adhesive layer Ad3, a film Pf2 for forming a protective film, and a release film in this order in the thickness direction, wherein the surface of the base material Bm3 on the side having the adhesive layer Ad3 is a smooth surface, and the surface (exposed surface) of the base material Bm3 on the opposite side to the side having the adhesive layer Ad3 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 1.
Example 8
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss11 was obtained in the same manner as in example 1, except that the above-described base material Bm7 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.05 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss11 were laminated to obtain a composite sheet for protective film formation having the structure shown in fig. 2.
The protective film-forming composite sheet is formed by stacking a base material Bm7, an adhesive layer Ad1, a protective film-forming film Pf1, and a release film in this order in the thickness direction, wherein the surface of the base material Bm7 on the side having the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm7 on the side opposite to the side having the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 2.
Example 9
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss12 was obtained in the same manner as in example 1, except that the above-described base material Bm8 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.03 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss12 were laminated to obtain a composite sheet for protective film formation having the structure shown in fig. 2.
The protective film-forming composite sheet is formed by stacking a base material Bm8, an adhesive layer Ad1, a protective film-forming film Pf1, and a release film in this order in the thickness direction, wherein the surface of the base material Bm8 on the side having the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm8 on the opposite side to the side having the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 2.
Example 10
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss13 was obtained in the same manner as in example 1, except that the above-described base material Bm9 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.03 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss13 were laminated to obtain a composite sheet for forming a protective film having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm9, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in this order in the thickness direction, wherein the surface of the base material Bm9 on the side having the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm9 on the opposite side to the side having the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 2.
Example 11
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss14 was obtained in the same manner as in example 1, except that the above-described base material Bm10 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.35 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss14 were laminated to obtain a composite sheet for protective film formation having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm10, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, wherein the surface of the base material Bm10 on the side provided with the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm10 on the side opposite to the side provided with the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 2.
Example 12
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss15 was obtained in the same manner as in example 1, except that the above-described base material Bm11 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.37 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss15 were laminated to obtain a composite sheet for forming a protective film having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm11, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, wherein the surface of the base material Bm11 on the side provided with the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm11 on the opposite side to the side provided with the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 2.
Reference example 1
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
In the same manner as in example 4 except that the application amount of the adhesive composition (I-4) -2 was changed to form an adhesive layer Ad4 having a thickness of 20 μm instead of 5 μm at the time of the formation of the adhesive layer, a support sheet Ss7 was obtained.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad4 of the support sheet Ss7 were laminated to obtain a composite sheet for protective film formation having the structure shown in fig. 2.
The protective film-forming composite sheet is formed by stacking a base material Bm2, an adhesive layer Ad4, a protective film-forming film Pf1, and a release film in this order in the thickness direction, wherein the surface of the base material Bm2 on the side having the adhesive layer Ad4 is a smooth surface, and the surface (exposed surface) of the base material Bm2 on the opposite side to the side having the adhesive layer Ad4 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 3.
Comparative example 1
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss8 was obtained in the same manner as in example 1, except that the above-described base material Bm5 was used instead of the base material Bm1, and an adhesive layer Ad1 having a thickness of 5 μm was formed on one surface (smooth surface) thereof.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss8 were laminated to obtain a composite sheet for forming a protective film having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm5, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, and both the surface of the base material Bm5 on the side provided with the adhesive layer Ad1 and the surface (exposed surface) of the base material Bm5 on the side opposite to the side provided with the adhesive layer Ad1 are smooth surfaces. The composition of the protective film-forming composite sheet is shown in table 3.
Comparative example 2
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss9 was obtained in the same manner as in example 2, except that the above-mentioned base material Bm6 was used instead of the base material Bm1, and the adhesive composition (I-4) -1 obtained above was applied to the uneven surface having a surface roughness of 0.5 μm to form an adhesive layer Ad 2.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad2 of the support sheet Ss9 were laminated to obtain a composite sheet for forming a protective film having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm6, an adhesive layer Ad2, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, wherein the surface of the base material Bm6 on the side provided with the adhesive layer Ad2 is a concave-convex surface, and the surface (exposed surface) of the base material Bm6 on the side opposite to the side provided with the adhesive layer Ad2 is a smooth surface. The composition of the protective film-forming composite sheet is shown in table 3.
Comparative example 3
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss10 was obtained in the same manner as in example 1, except that the above-mentioned base material Bm6 was used instead of the base material Bm1, and the adhesive composition (I-4) -1 obtained above was applied to a smooth surface having a surface roughness of 0.05 μm to form an adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss10 were laminated to obtain a composite sheet for forming a protective film having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm6, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, wherein the surface of the base material Bm6 on the side provided with the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm6 on the opposite side to the side provided with the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 3.
Comparative example 4
(formation of protective film Forming film)
The protective film forming film Pf1 was formed in the same manner as in example 1.
(formation of adhesive layer and production of supporting sheet)
A support sheet Ss16 was obtained in the same manner as in example 1, except that the above-described base material Bm12 was used instead of the base material Bm1, and a smooth surface having a surface roughness of 0.43 μm was used as the formation surface of the adhesive layer Ad 1.
(production of composite sheet for Forming protective film)
The exposed surface of the protective film-forming film Pf1 having no release film and the exposed surface of the adhesive layer Ad1 of the support sheet Ss16 were laminated to obtain a composite sheet for protective film formation having the structure shown in fig. 2.
The composite sheet for forming a protective film is formed by laminating a base material Bm12, an adhesive layer Ad1, a film Pf1 for forming a protective film, and a release film in the thickness direction thereof in this order, wherein the surface of the base material Bm12 on the side provided with the adhesive layer Ad1 is a smooth surface, and the surface (exposed surface) of the base material Bm11 on the opposite side to the side provided with the adhesive layer Ad1 is a concave-convex surface. The composition of the protective film-forming composite sheet is shown in table 3.
Evaluation of composite sheet for Forming protective film
The composite sheet for forming a protective film obtained as described above was evaluated for laser printability, infrared ray examination property, blocking resistance, embedding property of the adhesive layer into the surface of the substrate, and chipping resistance according to the following method, and the results are shown in tables 1 to 3 (the table is shown as "embedding property").
[ laser printability ]
The release film was removed from the composite sheet for forming a protective film, and the composite sheet for forming a protective film was adhered to a stainless steel annular frame using an adhesion device (RAD-2700F/12 "manufactured by linden corporation), and the film for forming a protective film in the composite sheet for forming a protective film was adhered to the back surface of a silicon wafer (outer diameter 8 inches, thickness 100 μm) heated to 70 ℃.
Next, in the case where the film for forming a protective film is thermosetting, the film is cured by heat treatment at 130℃for 2 hours, and in the case where the film for forming a protective film is energy ray-curable, the film is cured at an illuminance of 145mW/cm 2 Light quantity 230mJ/cm 2 The film was cured by irradiation with ultraviolet light 2 times under the conditions of (2) to form a protective film.
Subsequently, the protective film was irradiated with laser light having a wavelength of 532nm from the substrate side using a printing device (MD-S9910A, manufactured by KEYENCE Co., ltd.) under the conditions of an output of 4.8W, a frequency of 80kHz, and a scanning speed of 500 mm/sec, and laser printing was performed on the protective film in the following 2 patterns (pattern 1, pattern 2).
(Pattern)
Pattern 1: the characters are 0.30mm multiplied by 0.5mm, the character interval is 0.05mm, and the number of characters is 20
Pattern 2: the characters are 0.15mm multiplied by 0.3mm, the character interval is 0.05mm, and the number of characters is 20
Next, the characters formed on the protective film by the laser printing described above were observed through the support sheet, and the laser printability was evaluated according to the following criteria. If the gas generated by the protective film due to laser printing is accumulated between the adhesive layer and the protective film, it becomes a cause of chipping at the time of dicing, and therefore, a sample in which the gas is not accumulated is taken as an evaluation target.
(evaluation criterion)
A: all the characters of the patterns 1 and 2 can be clearly printed.
B: although some characters in the pattern 2 are blurred and not clearly printed, all characters in the pattern 1 can be clearly printed.
C: patterns 1 and 2 were printed with some characters unclear.
[ Infrared inspectability ]
The release film was removed from the composite sheet for forming a protective film, and the composite sheet for forming a protective film was adhered to a stainless steel annular frame using an adhesion device (RAD-2700F/12 "manufactured by linde corporation), and the film for forming a protective film in the composite sheet for forming a protective film was adhered to the back surface of a silicon wafer (diameter 8 inches, thickness 100 μm) heated to 70 ℃, that is, #2000 polished surface.
Next, in the case where the film for forming a protective film is thermosetting, the film is cured by heat treatment at 130℃for 2 hours, and in the case where the film for forming a protective film is energy ray-curable, the film is cured at an illuminance of 145mW/cm 2 Light quantity 230mJ/cm 2 The film was cured by irradiation with ultraviolet light 2 times under the conditions of (2) to form a protective film.
Then, a silicon wafer was divided by cutting with a cutter (DFD 6361 manufactured by DISCO corporation) at a cutting speed of 30000rpm at a cutting speed of 30 mm/sec, whereby silicon chips having a size of 2mm×2mm were obtained.
The obtained silicon chip was observed on the grinding surface (back surface of the silicon chip) and the dividing surface (side surface of the silicon chip) through the supporting sheet by using an infrared microscope (BX-IR manufactured by olympic corporation), and the infrared inspectability was evaluated according to the following criteria.
(evaluation criterion)
A: the grinding marks on the grinding surface can be clearly confirmed, and chipping of a size of 2 μm or more and less than 5 μm formed from the dividing surface of the silicon chip toward the inner side of the silicon chip can be clearly confirmed.
B: the grinding marks on the ground surface were clearly confirmed, but the chips having a size of 2 μm or more and less than 5 μm formed from the dividing surface of the silicon chip toward the inner side of the silicon chip were not clearly confirmed.
C: the grinding marks of the grinding surface cannot be confirmed at all or clearly, and the chips of any size cannot be confirmed at all or clearly.
[ blocking resistance ]
The composite sheet for forming a protective film having a length of 10m was wound around an ABS resin core material having a diameter of 3 inches, and left standing at room temperature for 3 days in this state.
Next, the composite sheet for forming a protective film in a roll shape after storage was pulled out, the release film was removed, the pulled out composite sheet for forming a protective film was stuck to a stainless steel ring frame by using a sticking device (RAD-2700F/12 "manufactured by linden corporation), and the film for forming a protective film in the composite sheet for forming a protective film was stuck to the back surface of a silicon wafer (diameter 8 inches, thickness 100 μm) heated to 70 ℃ to try to continuously perform 10 silicon wafers. Based on the handling property at this time, blocking resistance was evaluated according to the following criteria.
(evaluation criterion)
A: the blocking does not occur at all, and the above operation can be performed without problems.
B: although the protective film forming film can be adhered to the silicon wafer, in the roll obtained by winding the protective film forming composite sheet, partial adhesion occurs at the contact surface between the base material and the release film, and partial release is found between the base material and the adhesive layer or between the adhesive layer and the protective film forming film when the protective film forming composite sheet is pulled out.
C: in a roll obtained by winding up the composite sheet for forming a protective film, the contact surface between the base material and the release film is partially stuck, and the adhesion is remarkably generated, and when the composite sheet for forming a protective film is pulled out, partial peeling occurs between the adhesive layer and the film for forming a protective film, and the supporting sheet (laminate of the base material and the adhesive layer) is transferred onto the release film, or the composite sheet for forming a protective film cannot be pulled out.
[ embedding Property of adhesive layer into substrate surface ]
The support sheet obtained above was observed with a digital microscope (VHS-1000, manufactured by Keyence Co., ltd.) and the embeddability of the adhesive layer into the surface of the substrate was evaluated according to the following criteria.
O: no bubbles were found between the substrate and the adhesive layer.
X: bubbles were found between the substrate and the adhesive layer.
[ chipping resistance ]
For 10 silicon chips having a size of 2mm×2mm used for the evaluation of the infrared ray examination, 4 divided surfaces (side surfaces of the silicon chips) were observed with an optical microscope, and the chipping resistance was evaluated according to the following criteria.
O: the number of chipping sites of 30 μm or more formed from the division of the silicon chip toward the inner side of the silicon chip is less than 1 site per 1 silicon chip on average.
X: the number of chipping sites of 30 μm or more formed from the division of the silicon chip toward the inner side of the silicon chip is 1 site or more per 1 silicon chip on average.
Table 1
TABLE 2
TABLE 3
As is clear from the above results, in the composite sheet for forming a protective film of examples 1 to 12, the surface roughness of the 1 st surface of the base material was 0.37 μm or less, and the surface roughness of the 2 nd surface of the base material was 0.055 to 0.47 μm, which was larger than the surface roughness of the 1 st surface, and the composite sheet was excellent in blocking resistance, laser printability, and infrared ray examination property. In addition, in any of the examples, chipping resistance and embeddability were also excellent. Among these, the surface roughness of the 2 nd surface of the base material of the composite sheet for forming a protective film of examples 1 to 3 and example 8 was small, and the laser printability and the infrared ray inspection were particularly excellent. In contrast, the 2 nd surface of the base material in the composite sheet for forming a protective film of examples 5 to 7 and examples 9 to 12 has a large surface roughness and is particularly excellent in blocking resistance. The surface roughness of the 2 nd surface of the base material of the composite sheet for forming a protective film of example 4 was intermediate, and the anti-blocking property, the laser printability and the infrared ray examination property were particularly excellent.
In contrast, the surface roughness of the 2 nd surface of the base material in the composite sheet for forming a protective film of comparative example 1 was too small, and the blocking resistance was poor.
In the composite sheet for forming a protective film of comparative example 2, the surface roughness of the 1 st surface of the base material was too large, the surface roughness of the 2 nd surface of the base material was too small, and the blocking resistance, the laser printability, and the infrared ray examination were poor. In the composite sheet for forming a protective film of comparative example 2, the surface roughness of the 1 st surface of the base material was too high, and the embeddability was also poor.
In the composite sheet for forming a protective film of comparative example 3, the surface roughness of the 2 nd surface of the base material was too large, and the laser printability and the infrared ray examination were poor.
In the composite sheet for forming a protective film of comparative example 4, the surface roughness of the 1 st surface of the base material was too high, and the laser printability, infrared ray examination property and embedding property were poor.
The composite sheet for forming a protective film of reference example 1 was excellent in blocking resistance, laser printability and infrared ray examination properties, since the conditions of 0.4 μm or less in surface roughness of the 1 st surface of the substrate and 0.053 to 0.48 μm in surface roughness of the 2 nd surface of the substrate were satisfied. However, since the adhesive layer is too thick, chipping resistance is poor.
Industrial applicability
The present invention can be used for manufacturing a semiconductor device.

Claims (6)

1. A composite sheet for forming a protective film, comprising a support sheet, wherein the support sheet is provided with a protective film forming film on the adhesive layer,
the support sheet comprises a base material and an adhesive layer laminated on the base material,
the surface roughness (Ra) of the surface of the substrate on the side provided with the adhesive layer is less than or equal to 0.4 mu m,
the surface roughness (Ra) of the surface of the substrate opposite to the side provided with the adhesive layer is greater than the surface roughness of the surface provided with the adhesive layer and is 0.053-0.48 mu m,
the adhesive layer has a storage modulus of 30kPa or more.
2. The protective film-forming composite sheet according to claim 1, wherein the adhesive layer has a thickness of 15 μm or less.
3. The protective film-forming composite sheet according to claim 1 or 2, wherein the adhesive layer is non-energy ray curable.
4. The protective film-forming composite sheet according to claim 1 or 2, wherein the base material and the adhesive layer are transmissive to light having a wavelength of 532nm and light having a wavelength of 1600 nm.
5. The composite sheet for forming a protective film according to claim 1 or 2, wherein a surface roughness (Ra) of a surface of the base material opposite to the side provided with the adhesive layer is 0.15 to 0.48 μm.
6. The protective film-forming composite sheet according to claim 1 or 2, wherein the protective film-forming film is used for protecting a semiconductor wafer or a semiconductor chip.
CN201780016815.0A 2016-03-24 2017-03-13 Support sheet and composite sheet for forming protective film Active CN108966671B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016-060577 2016-03-24
JP2016060577 2016-03-24
PCT/JP2017/009921 WO2017163971A1 (en) 2016-03-24 2017-03-13 Supporting sheet and composite sheet for protective film formation

Publications (2)

Publication Number Publication Date
CN108966671A CN108966671A (en) 2018-12-07
CN108966671B true CN108966671B (en) 2023-09-26

Family

ID=59899422

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780016815.0A Active CN108966671B (en) 2016-03-24 2017-03-13 Support sheet and composite sheet for forming protective film

Country Status (6)

Country Link
JP (1) JP6893500B2 (en)
KR (1) KR102313074B1 (en)
CN (1) CN108966671B (en)
SG (1) SG11201807645SA (en)
TW (1) TWI761335B (en)
WO (1) WO2017163971A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7059553B2 (en) * 2017-10-04 2022-04-26 昭和電工マテリアルズ株式会社 Adhesive tape for stealth dicing, dicing die bonding integrated tape, and method for manufacturing semiconductor devices
TWI791650B (en) * 2017-10-27 2023-02-11 日商琳得科股份有限公司 Film for forming protective coating, composite sheet for forming protective coating, and method of manufacturing semiconductor chip
US11358374B2 (en) * 2017-10-31 2022-06-14 Toray Advanced Film Co., Ltd. Laminated film
JP7138448B2 (en) * 2018-02-22 2022-09-16 リンテック株式会社 Adhesive sheet roll
WO2019172438A1 (en) * 2018-03-09 2019-09-12 リンテック株式会社 Composite sheet for forming protective film and method for producing semiconductor chip with protective film
JP7119070B2 (en) * 2018-03-30 2022-08-16 リンテック株式会社 Method for manufacturing composite sheet for forming protective film, method for manufacturing semiconductor chip with protective film, and method for manufacturing semiconductor device
CN111542912B (en) * 2018-03-30 2023-10-13 琳得科株式会社 Composite sheet for forming protective film and method for producing same
KR102534931B1 (en) * 2018-03-30 2023-05-19 린텍 가부시키가이샤 Composite sheet for forming support sheet and protective film
WO2019187014A1 (en) * 2018-03-30 2019-10-03 リンテック株式会社 Support sheet and composite sheet for protective film formation
KR102519799B1 (en) * 2018-03-30 2023-04-10 린텍 가부시키가이샤 Composite sheet for forming support sheet and protective film
JP7203087B2 (en) * 2018-03-30 2023-01-12 リンテック株式会社 COMPOSITE SHEET FOR PROTECTIVE FILM FORMATION AND METHOD FOR MANUFACTURING SAME
WO2020218519A1 (en) * 2019-04-26 2020-10-29 リンテック株式会社 Method for producing three-layer body, method for producing four-layer body, method for producing semiconductor device equipped with rear surface protective film, and three-layer body
JP7478524B2 (en) * 2019-09-05 2024-05-07 リンテック株式会社 Film for forming protective film, composite sheet for forming protective film, and method for manufacturing workpiece with protective film
JP7387510B2 (en) * 2020-03-26 2023-11-28 リンテック株式会社 Protective film-forming film, protective film-forming composite sheet, and method for transporting workpieces with protective film-forming film
TWI811636B (en) * 2020-03-31 2023-08-11 日商東洋紡股份有限公司 Inorganic substrate/engineering plastic film laminate with protective film, stacking of laminates, storage method of laminates, and transportation method of laminates
CN111777961B (en) * 2020-07-15 2022-05-17 宁波东旭成新材料科技有限公司 Preparation method of UV (ultraviolet) anti-adhesion protective film
JP2022143454A (en) 2021-03-17 2022-10-03 リンテック株式会社 Support sheet, composite sheet for protective film formation, and method for manufacturing apparatus

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010042665A (en) * 2008-07-15 2010-02-25 San Totsukusu Kk Base film
WO2015178346A1 (en) * 2014-05-23 2015-11-26 リンテック株式会社 Composite sheet for forming protective film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5124778B2 (en) * 2008-09-18 2013-01-23 リンテック株式会社 Laser dicing sheet and semiconductor chip manufacturing method
JP5452353B2 (en) 2010-05-14 2014-03-26 三井化学東セロ株式会社 Adhesive film for protecting semiconductor wafer and adhesive film roll for protecting semiconductor wafer
JP5391158B2 (en) * 2010-06-30 2014-01-15 古河電気工業株式会社 Wafer sticking adhesive sheet and wafer processing method using the same
JP5432853B2 (en) 2010-07-30 2014-03-05 日東電工株式会社 Dicing tape-integrated film for semiconductor back surface, manufacturing method thereof, and manufacturing method of semiconductor device
JP6010945B2 (en) * 2012-03-16 2016-10-19 住友ベークライト株式会社 Dicing film
JP5607847B1 (en) * 2013-11-29 2014-10-15 古河電気工業株式会社 Adhesive tape for semiconductor processing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010042665A (en) * 2008-07-15 2010-02-25 San Totsukusu Kk Base film
WO2015178346A1 (en) * 2014-05-23 2015-11-26 リンテック株式会社 Composite sheet for forming protective film

Also Published As

Publication number Publication date
JPWO2017163971A1 (en) 2019-01-31
TW201739078A (en) 2017-11-01
KR102313074B1 (en) 2021-10-14
TWI761335B (en) 2022-04-21
CN108966671A (en) 2018-12-07
SG11201807645SA (en) 2018-10-30
WO2017163971A1 (en) 2017-09-28
JP6893500B2 (en) 2021-06-23
KR20180124868A (en) 2018-11-21

Similar Documents

Publication Publication Date Title
CN108966671B (en) Support sheet and composite sheet for forming protective film
CN109789666B (en) Composite sheet for forming protective film
CN108701641B (en) Sheet for forming protective film, method for manufacturing sheet for forming protective film, and method for manufacturing semiconductor device
CN109287125B (en) Method for manufacturing semiconductor chip with protective film and method for manufacturing semiconductor device
CN111849377B (en) Composite sheet for forming protective film
CN111279468B (en) Film for forming protective film, composite sheet for forming protective film, and method for manufacturing semiconductor chip
CN111602229B (en) Support sheet and composite sheet for forming protective film
CN108778721B (en) Composite sheet for forming protective film
JP6818009B2 (en) Composite sheet for forming a protective film
CN112154536B (en) Film for forming protective film, composite sheet for forming protective film, inspection method, and recognition method
CN111542912B (en) Composite sheet for forming protective film and method for producing same
CN111373509B (en) Support sheet and composite sheet for forming protective film
CN111630631B (en) Support sheet and composite sheet for forming protective film
TWI850434B (en) Film for forming protective film, composite sheet for forming protective film, and method for producing workpiece having protective film
CN113444271B (en) Protective film forming film, composite sheet for forming protective film, and method for conveying work with protective film forming film
CN111466014B (en) Composite sheet for forming protective film and method for producing same
CN111587472B (en) Support sheet and composite sheet for forming protective film
TWI845644B (en) Thermosetting resin film, sheet for forming first protective film, kit, and method for producing workpiece with first protective film
CN108701597B (en) Composite sheet for forming protective film
CN118027840A (en) Composite sheet for forming protective film
CN115132634A (en) Film for forming protective film
TW202105484A (en) Method for manufacturing workpiece article with first protective film
CN115132671A (en) Film for forming protective film
TW202104508A (en) Thermosetting resin film and first protective film formation sheet

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant