CN108701597B - Composite sheet for forming protective film - Google Patents

Composite sheet for forming protective film Download PDF

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Publication number
CN108701597B
CN108701597B CN201680081330.5A CN201680081330A CN108701597B CN 108701597 B CN108701597 B CN 108701597B CN 201680081330 A CN201680081330 A CN 201680081330A CN 108701597 B CN108701597 B CN 108701597B
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Prior art keywords
protective film
forming
film
meth
acrylate
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CN201680081330.5A
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CN108701597A (en
Inventor
佐伯尚哉
佐佐木辽
米山裕之
山本大辅
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Lintec Corp
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Abstract

The composite sheet for forming a protective film of the present invention is provided with a support sheet, a film for forming a protective film on one surface of the support sheet, and a coating layer on a surface of the support sheet opposite to a side having the film for forming a protective film, wherein a surface roughness Ra of a surface of the coating layer opposite to a side in contact with the support sheet is smaller than a surface roughness Ra of a surface of the support sheet opposite to the side having the coating layer.

Description

Composite sheet for forming protective film
Technical Field
The present invention relates to a composite sheet for forming a protective film on the back surface of a semiconductor chip.
The present application claims priority based on Japanese patent application No. 2016-042689 filed in Japan on 4/3/2016, and the contents of which are incorporated herein by reference.
Background
In recent years, a so-called flip-chip (face down) mounting method has been used to manufacture a semiconductor device. In the flip chip method, a semiconductor chip having electrodes such as bumps on a circuit surface, which are bonded to a substrate, is used. Therefore, the back surface of the chip opposite to the circuit surface may be exposed.
On the back surface of the exposed chip, a resin film made of an organic material is sometimes formed as a protective film and mounted in a semiconductor device in the form of a semiconductor chip with a protective film. The protective film is used to prevent cracks from occurring in the chip after the dicing step and the packaging.
In forming such a protective film, a composite sheet for forming a protective film is used, which is formed by providing a film for forming a protective film on a support sheet. As the support sheet, for example, a laminated structure of a resin base material, a pressure-sensitive adhesive layer, and the like is used, and the laminated surface of a protective film-forming film of the base material, the pressure-sensitive adhesive layer, and the like may be subjected to surface treatment. In the composite sheet for forming a protective film, the film for forming a protective film has a protective film forming ability, the support sheet can function as a dicing sheet, and the film for forming a protective film and the dicing sheet can be formed integrally.
The base material before being used for processing the support sheet usually has a concavo-convex shape on one surface or both surfaces thereof. This is because, if the substrate does not have such a concave-convex shape, the contact surface between the substrates sticks to each other and blocking occurs when the substrate is wound up to form a roll, which makes it difficult to use. If at least one of the contact surfaces of the base materials has a concave-convex shape, the area of the contact surface is reduced, and therefore blocking can be suppressed.
Such a conventional composite sheet for forming a protective film using a base material having an uneven surface typically has a structure as shown in fig. 4. Fig. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film. In the drawings used in the following description, for example, in order to facilitate understanding of the features of the composite sheet for forming a protective film, a part of the composite sheet as a main part may be enlarged for convenience, and the dimensional ratio of each component is not limited to the actual one.
The conventional composite sheet 9 for forming a protective film shown here is formed by providing the film 13 for forming a protective film on the support sheet 90, and the support sheet 90 is formed of a laminated structure of the base material 91 and the pressure-sensitive adhesive layer 12, and further, the film 13 for forming a protective film is provided on the pressure-sensitive adhesive layer 12. The protective film forming film 13 becomes a protective film by curing. The composite sheet for forming a protective film 9 further includes a release film 15 on the film for forming a protective film 13, and the release film 15 is removed when the composite sheet for forming a protective film 9 is used. In the composite sheet 9 for forming a protective film, a surface (back surface) 90b of the support sheet 90 opposite to the surface (front surface) 90a provided with the film 13 for forming a protective film, that is, a surface (back surface) 91b of the base material 91 opposite to the surface (front surface) 91a provided with the adhesive layer 12 is formed as an uneven surface. In this way, the composite sheet 9 for forming a protective film has an uneven surface formed by the back surface 91b of the base material 91, and blocking can be suppressed when the sheet is wound into a roll. That is, the adhesion of the laminated composite sheets 9 for forming a protective film, more specifically, the adhesion of the back surface 91b of the base material 91 and the exposed surface (front surface) 15a of the release film 15 can be suppressed.
On the other hand, the protective film-forming composite sheet may be printed by irradiating a surface of the protective film formed of the protective film on the support sheet side with laser light (hereinafter, may be referred to as "laser printing"). In laser printing, irradiation is performed from the side of the support sheet opposite to the side on which the protective film is formed. In this case, for example, in the case of the composite sheet 9 for forming a protective film, the protective film is irradiated with laser light from the back surface 91b side of the base material 91 through the support sheet 90, but since the back surface 91b of the base material 91 is uneven, there is a problem that diffuse reflection occurs in the light, and laser printing is not clear.
As a composite sheet for forming a protective film capable of preventing such diffuse reflection of light, a composite sheet 8 for forming a protective film having a structure as shown in fig. 5 is known (for example, see patent document 1). Fig. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.
The conventional composite sheet 8 for forming a protective film shown here includes the film 13 for forming a protective film on the support sheet 80, in the same manner as the composite sheet 9 for forming a protective film, and the support sheet 80 is composed of a laminated structure of the base 81 and the pressure-sensitive adhesive layer 12, and includes the film 13 for forming a protective film on the pressure-sensitive adhesive layer 12. However, in the support sheet 80, the arrangement of the uneven surface of the base material 81 is opposite to the base material 91 in the support sheet 90. That is, in the composite sheet 8 for forming a protective film, the surface (front surface) 81a of the base 81 provided with the pressure-sensitive adhesive layer 12 is a concave-convex surface, and the surface (back surface) 81b of the base 81 opposite to the front surface 81a is a smooth surface. The base 81, the protective film forming film 13, and the release film 15 in the support sheet 80 are the same as the base 91, the protective film forming film 13, and the release film 15 in the support sheet 90, respectively.
However, in the case of the composite sheet 8 for forming a protective film, the back surface 81b of the base 81, that is, the surface (back surface) 80b of the support sheet 80 opposite to the surface (front surface) 80a provided with the pressure-sensitive adhesive layer 12 becomes a smooth surface, and when the composite sheet 8 for forming a protective film is wound up and rolled up, adhesion between the back surface 81b of the base 81 and the exposed surface (front surface) 15a of the release film 15, that is, blocking cannot be suppressed. When the blocking occurs, the protective film forming composite sheet 8 is wrinkled, or the release film 15 is peeled off from the protective film forming film 13 when the protective film forming composite sheet 8 is continuously taken out from the roll. In addition, the adhesive layer 12 needs to have a sufficient thickness on the surface 81a of the base 81 in order to eliminate the uneven shape. When the thickness of the pressure-sensitive adhesive layer 12 is insufficient, the uneven shape of the base material 81 is reflected so that the surface (back surface) 13b of the protective film-forming film 13 on the support sheet 80 side has the uneven shape, and there is a problem that laser printing performed on the surface of the protective film formed of such a protective film-forming film 13 on the support sheet side becomes unclear.
Therefore, there is no composite sheet for forming a protective film that can suppress blocking and can perform laser printing clearly on the protective film.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5432853
Disclosure of Invention
Problems to be solved by the invention
The invention provides a composite sheet for forming a protective film, which is used for forming a protective film on the back surface of a semiconductor chip, can inhibit adhesion and can clearly carry out laser printing on the protective film.
Means for solving the problems
The present invention provides a composite sheet for forming a protective film, which comprises a support sheet, a film for forming a protective film on one surface of the support sheet, and a coating layer on the surface of the support sheet opposite to the side having the film for forming a protective film, wherein the surface roughness Ra of the surface of the coating layer opposite to the side in contact with the support sheet is smaller than the surface roughness Ra of the surface of the support sheet opposite to the side having the coating layer.
The composite sheet for forming a protective film of the present invention may be one which comprises a protective film-forming film and a release film provided on the protective film-forming film, wherein the release film has a release force of 10mN/50mm or less as measured by the following method,
(method of measuring peeling force of peeling film)
The composite sheet for forming a protective film having a release film on a film for forming a protective film and having a width of 50mm and a length of 100mm was laminated so that the coating layers were all oriented in the same direction and the total thickness of the coating layers was 10 to 60 μm to form a laminate having one outermost layer as a coating layer and the other outermost layer as a release film, the laminate was allowed to stand at 40 ℃ for 3 days with a force of 980.665mN applied in the lamination direction of the composite sheet for forming a protective film, and then the release film closest to the outermost coating layer was peeled from the adjacent coating layer in the lamination direction at a peeling speed of 300 mm/min and a peeling angle of 180 °, and the peeling force at that time was measured.
The protective film-forming composite sheet of the present invention may be one in which the support sheet is formed by laminating a base material and an adhesive layer, and the protective film-forming composite sheet is formed by laminating the coating layer, the base material, the adhesive layer, and the protective film-forming film in this order.
In the composite sheet for forming a protective film of the present invention, the adhesive layer may be an energy ray-curable or non-energy ray-curable adhesive layer.
In the composite sheet for forming a protective film of the present invention, the film for forming a protective film may be a thermosetting or energy ray-curable film.
ADVANTAGEOUS EFFECTS OF INVENTION
The protective film-forming composite sheet of the present invention is used for forming a protective film on the back surface of a semiconductor chip, and the use of the protective film-forming composite sheet can suppress blocking of the protective film-forming composite sheet and can clearly perform laser printing on the protective film.
Drawings
Fig. 1 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 3 is a plan view showing the composite sheet for forming a protective film produced in the example.
Fig. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film.
Fig. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.
Description of the symbols
1.2 8230and composite sheet for forming protective film
10 8230a support sheet
10a 8230and the surface of the supporting sheet
10b 8230and back of supporting sheet
11 \ 8230and base material
11a 8230and the surface of the substrate
11b 8230and back surface of substrate
12' \ 8230and adhesive layer
12a 8230and the surface of the adhesive layer
13. 23 8230A film for forming a protective film
13a, 23a 8230, surface of film for forming protective film
14 method 8230coating layer
14a 8230coated layer surface
14b 8230a rear surface of a coating layer
15 (8230); stripping film
15a 8230and the surface of the release film
16' \ 8230and adhesive layer for jig
16a 8230and adhesive layer surface for jig
Detailed Description
Composite sheet for forming very good protective film
The composite sheet for forming a protective film of the present invention includes a support sheet, a film for forming a protective film on one surface of the support sheet, and a coating layer on a surface of the support sheet opposite to a side having the film for forming a protective film, wherein a surface roughness Ra of a surface of the coating layer opposite to a side in contact with the support sheet is smaller than a surface roughness Ra of a surface of the support sheet on the side having the coating layer.
In the composite sheet for forming a protective film, a surface roughness Ra of a surface of the support sheet opposite to a side of the coating layer in contact with the support sheet is smaller than a surface roughness Ra of a surface of the support sheet provided with the coating layer. That is, the surface of the coating layer opposite to the side in contact with the support sheet is a smooth surface or a surface with suppressed unevenness. Therefore, when the laser beam is irradiated, the diffuse reflection of the laser beam on the surface having a small surface roughness Ra of the coating layer is suppressed. Thus, when the protective film obtained by curing the protective film-forming film is irradiated with laser light from the coating layer side through the support sheet, the protective film can be printed clearly with laser light.
The coating layer in the composite sheet for forming a protective film is easy to appropriately slide against a contact object with the coating layer, and has antistatic properties. Therefore, when the composite sheet for forming a protective film is wound up to be a roll, the adhesion of the laminated composite sheets for forming a protective film to each other can be suppressed, that is, blocking can be suppressed.
In the present specification, the protective film-forming composite sheet is also referred to as a "protective film-forming composite sheet" as long as the laminated structure of the support sheet and the protective film is maintained after the protective film is formed by curing the protective film-forming film by heating or irradiation with energy rays. In the case where the support sheet is a laminated structure of a base material and an adhesive layer in the composite sheet for forming a protective film, the composite sheet for forming a protective film is also referred to as "composite sheet for forming a protective film" as long as the laminated structure of the base material, the cured product of the adhesive layer, and the film for forming a protective film or the protective film is maintained after curing the adhesive layer.
Fig. 1 is a cross-sectional view schematically showing one embodiment of the composite sheet for forming a protective film of the present invention.
The composite sheet 1 for forming a protective film shown here is provided with a support sheet 10, a film 13 for forming a protective film on one surface 10a of the support sheet 10, and an application layer 14 on the other surface (back surface) 10b of the support sheet 10. The support sheet 10 is formed by laminating a base material 11 and an adhesive layer 12, and has the adhesive layer 12 on one surface 11a of the base material 11, a coating layer 14 on the other surface (back surface) 11b of the base material 11, and a protective film forming film 13 on the adhesive layer 12. Further, the composite sheet for forming a protective film 1 is provided with an exfoliation film 15 on the film for forming a protective film 13, and the exfoliation film 15 is removed when the composite sheet for forming a protective film 1 is used. The protective film forming film 13 becomes a protective film by curing.
In the composite sheet 1 for forming a protective film, the adhesive layer 12 is laminated on the surface 11a of the substrate 11, and the film 13 for forming a protective film is laminated on a part of the surface 12a of the adhesive layer 12. Further, the release film 15 is laminated on the exposed surface of the surface 12a of the pressure-sensitive adhesive layer 12 on which the protective film forming film 13 is not laminated and the surface 13a (in other words, the upper surface and the side surfaces) of the protective film forming film 13.
A gap may be present between the release film 15 and the surface 12a of the pressure-sensitive adhesive layer 12 or the surface 13a of the protective film forming film 13. For example, the void tends to be formed in the side surface of the protective film forming film 13 or in the vicinity of the surface 12a of the pressure-sensitive adhesive layer 12 in the region near the protective film forming film 13.
In the composite sheet 1 for forming a protective film, the surface (back surface) 10b of the support sheet 10 opposite to the surface (front surface) 10a provided with the film 13 for forming a protective film, in other words, the surface (back surface) 11b of the base material 11 opposite to the surface (front surface) 11a provided with the adhesive layer 12 is an uneven surface. Further, an application layer 14 is provided to cover the uneven surface. The surface roughness Ra of the surface (back surface) 14b of the coating layer 14 opposite to the surface (front surface) 14a in contact with the support sheet 10 (base material 11) is smaller than the surface roughness Ra of the back surface 10b of the support sheet 10 (in other words, the back surface 11b of the base material 11). When laser printing is performed on a protective film (not shown) formed of the protective film forming film 13, a surface of the protective film on the side of the support sheet 10 is irradiated with laser light from the side of the application layer 14. In this case, as described above, the diffuse reflection of the laser beam on the coated layer 14 can be suppressed by reducing the surface roughness Ra of the back surface 14b of the coated layer 14. Therefore, the protective film can be printed clearly by laser.
In the present specification, unless otherwise specified, "surface roughness Ra" means so-called arithmetic mean roughness defined in JIS B0601: 2001.
Further, by providing the coating layer 14, even when the composite sheet 1 for forming a protective film is wound up and rolled up, the composite sheets 1 for forming a protective film after lamination can be prevented from sticking to each other, that is, blocking can be prevented. More specifically, the adhesion between the back surface 11b of the base material 11 and the exposed surface (front surface) 15a of the release film 15 can be suppressed.
In the composite sheet 1 for forming a protective film, the surface 11a of the substrate 11 is formed as a smooth surface here, but may be a rough surface having low smoothness. However, as will be described later, the surface 11a of the substrate 11 is preferably a smooth surface in order to suppress the occurrence of voids between the substrate 11 and the pressure-sensitive adhesive layer 12 and to make it easier to obtain a composite sheet 1 for forming a protective film having desirable characteristics.
In the composite sheet 1 for forming a protective film shown in fig. 1, the release film 15 is removed at the time of use, and the back surface of the semiconductor wafer (not shown) is bonded to the front surface 13a of the film 13 for forming a protective film. Further, an exposed surface of the surface 12a of the pressure-sensitive adhesive layer 12 on which the protective film forming film 13 is not laminated is attached to a jig such as a ring frame.
Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In fig. 2, the same components as those shown in fig. 1 are denoted by the same reference numerals as those in fig. 1, and detailed description thereof will be omitted. This is also true in the figures subsequent to fig. 2.
In the composite sheet 2 for forming a protective film shown here, the film 23 for forming a protective film is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12, and the adhesive layer 16 for a jig is laminated on a part of the surface 23a of the film 23 for forming a protective film. In the composite sheet 2 for forming a protective film, the release film 15 is laminated on an exposed surface of the surface 23a of the protective film 23 on which the adhesive layer 16 for a jig is not laminated and the surface 16a (in other words, the upper surface and the side surfaces) of the adhesive layer 16 for a jig. Except for the above points, the composite sheet 2 for forming a protective film is the same as the composite sheet 1 for forming a protective film shown in fig. 1.
A gap may be present between the release film 15 and the surface 23a of the protective film forming film 23 or the surface 16a of the jig adhesive layer 16. For example, the above-described void portion is likely to occur in the vicinity of the side surface of the adhesive layer 16 for jig or the front surface 23a of the film 23 for protective film.
In the composite sheet 2 for forming a protective film, the back surface 10b of the support sheet 10 (the back surface 11b of the base material 11) is formed as an uneven surface, and the coating layer 14 is provided so as to cover the uneven surface, as in the case of the composite sheet 1 for forming a protective film. Therefore, the surface roughness Ra of the back surface 14b of the application layer 14 is smaller than that of the back surface 10b of the support sheet 10. Therefore, the protective film formed of the protective film forming film 23 can be clearly printed by laser.
Further, by providing the coating layer 14, even when the composite sheet 2 for forming a protective film is wound up and rolled up, the composite sheets 2 for forming a protective film after lamination can be prevented from sticking to each other, that is, blocking can be prevented.
In the composite sheet 2 for forming a protective film shown in fig. 2, the release film 15 is removed at the time of use, and the back surface of the semiconductor wafer (not shown) is bonded to the front surface 23a of the film 23 for forming a protective film. Further, the upper surface of the surface 16a of the adhesive layer 16 for a jig is bonded to a jig such as a ring frame.
The composite sheet for forming a protective film of the present invention is not limited to the example shown in fig. 1 to 2, and may be a structure in which a part of the composition of the composite sheet shown in fig. 1 to 2 is modified or deleted, or a structure in which another configuration is further added to the above-described example, within a range in which the effect of the present invention is not impaired.
Hereinafter, each configuration of the composite sheet for forming a protective film of the present invention will be described in more detail.
Supporting sheet
The support sheet is not particularly limited as long as the protective film-forming film can be provided. Examples of the support sheet include a release sheet used for preventing dust or the like from adhering to the surface of the protective film-forming film, and a sheet that functions as a dicing sheet or the like for protecting the surface of the protective film-forming film in a dicing step or the like.
Preferred examples of the support sheet include a support sheet composed of only a base material, a support sheet in which a base material and an adhesive layer are laminated, and the like, which are generally used in the field of a sheet for processing a semiconductor wafer.
The support sheet may be composed of 1 layer (single layer) or a plurality of layers of 2 or more. When the support sheet is formed 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 some layers may be the same. When the plurality of layers are different from each other, the combination of the plurality of layers is not particularly limited. Here, the 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.
The thickness of the support sheet may be appropriately selected according to the purpose, but is preferably 10 to 500 μm, more preferably 20 to 350 μm, particularly preferably 30 to 200 μm, and may be any thickness of, for example, 40 to 175 μm and 50 to 150 μm, from the viewpoint of enabling clearer laser printing of the protective film, enabling sufficient flexibility to be imparted to the protective film-forming composite sheet, and improving adhesion to the semiconductor wafer.
Here, the "thickness of the support sheet" refers to the total thickness of the layers constituting the support sheet, and for example, in the case of a support sheet in which a substrate and an adhesive layer are laminated, the total value of the thickness of the substrate and the thickness of the adhesive layer is referred to.
At least one surface of the support sheet may be an uneven surface, and the thickness of the support sheet may be calculated from a point of the support sheet including the convex portion of the uneven surface, with the tip of the convex portion as a starting point.
Base material
The material of the substrate is preferably various resins.
Specific examples of the resin include: polyethylene (low density polyethylene (LDPE), orthotropic low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene, ethylene-propylene copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, urethane acrylate, polyimide, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, polystyrene, polycarbonate, fluororesin, and hydrogenated products, modified products, crosslinked products, or copolymers of any of these resins.
In the present specification, the term "(meth) acrylic acid" includes both "acrylic acid" and "methacrylic acid".
When the support sheet is formed by laminating a base material and another member such as an adhesive layer, the thickness of the base material may be appropriately selected depending on the purpose, but is preferably 15 to 300 μm, more preferably 20 to 200 μm, and may be any of 30 to 175 μm, 40 to 150 μm, and 50 to 125 μm, for example. 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 can be further improved.
The substrate may be composed of 1 layer (single layer) or 2 or more layers. When the substrate is composed of a plurality of layers, the plurality of layers may be the same or different from each other. Here, "the plurality of layers may be the same as or different from each other" means the same as in the case of the support sheet.
When the substrate is composed of a plurality of layers, the total thickness of the layers may be set to the preferred substrate thickness.
The surface roughness Ra of the surface (surface) of the substrate provided with the pressure-sensitive adhesive layer is preferably 0.001 to 0.1. Mu.m, more preferably 0.005 to 0.08. Mu.m, and particularly preferably 0.01 to 0.04. Mu.m. When the surface roughness Ra of the substrate surface is equal to or less than the upper limit value, the laser printing can be performed more clearly on the protective film.
The surface roughness Ra of the substrate surface can be adjusted by, for example, the molding conditions of the substrate, the surface treatment conditions of the substrate, and the like.
As a method for singulating the semiconductor wafer into semiconductor chips by dicing, for example, there are given: a method of dicing a semiconductor wafer with a dicing blade, a method of laser dicing a semiconductor wafer by laser irradiation, or a method of water dicing a semiconductor wafer by spraying water containing an abrasive.
On the other hand, as a method for singulating a semiconductor wafer into semiconductor chips, in addition to the above-described method using dicing, there can be mentioned the following methods: the semiconductor wafer is divided into individual pieces at the formation site of the modified layer by irradiating a laser beam in the infrared region while focusing on a focal point set inside the semiconductor wafer to form the modified layer inside the semiconductor wafer and then applying a force to the semiconductor wafer.
When the surface roughness Ra of the substrate surface is, for example, 0.01 to 0.2 μm, the composite sheet for forming a protective film having such a substrate is preferably used when the semiconductor wafer is singulated by forming the modified layer in the semiconductor wafer.
On the other hand, the surface roughness Ra of the surface (back surface) of the base opposite to the surface (front surface) provided with the pressure-sensitive adhesive layer, in other words, the surface roughness Ra of the surface (back surface) of the support sheet opposite to the surface (front surface) provided with the film for forming the protective film, is preferably 0.001 to 4 μm, more preferably 0.005 to 3.7 μm, further preferably 0.01 to 3.4 μm, and particularly preferably 0.02 to 3.1 μm. By setting the surface roughness Ra of the back surface of the base material to the upper limit value or less, the surface roughness Ra of the surface of the coating layer opposite to the side in contact with the support sheet can be reduced more easily, and the laser printing of the protective film can be performed more easily.
The surface roughness Ra of the back surface of the base material can be adjusted by, for example, the molding conditions of the base material, the surface treatment conditions of the base material, and the like.
As the resin as a material of the base material, a crosslinked resin may be used.
The substrate made of a resin may be a sheet formed by extrusion molding of a thermoplastic resin, may be a sheet obtained by stretching, or may be a sheet formed by thinning and curing a curable resin by a known method.
The base material may be colored or printed.
A polypropylene-containing substrate is preferable because it has excellent heat resistance, has expansion flexibility due to appropriate flexibility, and has good pickup flexibility.
The polypropylene-containing substrate may be, for example, a single-layer or multi-layer substrate composed of polypropylene alone, or a multi-layer (2 or more) substrate composed of a polypropylene layer and a resin layer other than polypropylene.
When the film for forming a protective film is thermosetting, the base material is made to have heat resistance, whereby deterioration due to heat of the base material can be suppressed, and occurrence of defects in the process for producing a semiconductor device can be effectively suppressed.
In order to improve the adhesion between the substrate and the adhesive layer or the film for forming a protective film provided thereon, the surface of the substrate may be subjected to a roughening treatment by sandblasting, solvent treatment, or the like; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and other oxidation treatments. The substrate may be a material having a surface subjected to an undercoating treatment.
Adhesive layer
The adhesive layer may be any known adhesive layer.
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing various components such as a pressure-sensitive adhesive for constituting the pressure-sensitive adhesive layer. The ratio of the content of the components that do not vaporize at normal temperature in the adhesive composition is generally the same as the ratio of the content of the above components in the adhesive layer. In the present specification, "normal temperature" means a temperature that is not particularly cold or hot, that is, a normal temperature, and includes, for example, a temperature of 15 to 25 ℃.
The thickness of the pressure-sensitive adhesive layer may be appropriately selected depending on the purpose, and is preferably 1 to 100 μm, more preferably 2 to 80 μm, particularly preferably 3 to 50 μm, and may be any thickness of, for example, 3 to 35 μm, 3 to 20 μm, and 3 to 10 μm.
The pressure-sensitive adhesive layer may be composed of 1 layer (single layer) or 2 or more layers. When 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 plurality of layers may be the same or different from each other" means the same as in the case of the support sheet.
When the pressure-sensitive adhesive layer is composed of a plurality of layers, the total thickness of each layer may be the preferred thickness of the pressure-sensitive adhesive layer.
Examples of the pressure-sensitive adhesive include pressure-sensitive adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, and vinyl ether resins. In addition, when the binder is classified from the viewpoint of its function, for example, an energy ray curable resin and the like can be given.
In the present specification, the term "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged ion beam, and examples thereof include ultraviolet rays, radiation, electron beams, and the like. 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, an LED lamp, or the like as an ultraviolet ray source. The electron beam may radiate a ray generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not causing curing even when irradiated with an energy ray.
Examples of the energy ray-curable resin include resins having a polymerizable group such as a (meth) acryloyl group or a vinyl group.
The adhesive resin is preferably an acrylic resin, and more preferably a (meth) acrylate copolymer containing a structural unit derived from a (meth) acrylate.
When the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with an energy ray, such as an energy ray-curable resin, the pressure-sensitive adhesive layer becomes energy ray-curable, and the adhesiveness thereof is lowered by irradiation with an energy ray, whereby the semiconductor chip with a protective film described later can be easily picked up. Such a pressure-sensitive adhesive layer can be formed using various pressure-sensitive adhesive compositions containing a component that is polymerized by irradiation with an energy ray, for example.
Adhesive composition
The preferred pressure-sensitive adhesive composition includes a pressure-sensitive adhesive composition containing a component that is polymerized by irradiation with an energy ray. Examples of such a binder composition include: a composition containing an acrylic resin and an energy ray-polymerizable compound (hereinafter, may be simply referred to as "adhesive composition (i)"); and a composition containing the acrylic resin having a hydroxyl group and a polymerizable group in a side chain and an isocyanate-based crosslinking agent (hereinafter, may be simply referred to as "adhesive composition (ii)"). Examples of the acrylic resin having a hydroxyl group and a polymerizable group in a side chain thereof include acrylic resins having a hydroxyl group and a polymerizable group in a side chain thereof via a urethane bond.
< adhesive composition (i) >
The pressure-sensitive adhesive composition (i) contains the acrylic resin and the energy ray-polymerizable compound as essential components.
Hereinafter, each component will be described.
[ acrylic resin ]
Among the above-mentioned acrylic resins in the pressure-sensitive adhesive composition (i), preferable acrylic resins include, for example, (meth) acrylate copolymers obtained by polymerizing (meth) acrylate as a monomer and a monomer other than (meth) acrylate used as needed.
Examples of the (meth) acrylate include: alkyl (meth) acrylates having a chain structure in which the carbon number of an alkyl group constituting an alkyl ester is 1 to 18, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (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 ((stearyl (meth) acrylate), isostearyl (meth) acrylate), and the like;
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;
cycloalkoxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylimide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxyl 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.
Examples of the monomer other than the (meth) acrylate ester include: (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like.
The acrylic resin may be composed of only one kind of monomer such as the above (meth) acrylate and a monomer other than the above (meth) acrylate, or may be composed of two or more kinds.
The acrylic resin contained in the pressure-sensitive adhesive composition (i) may be only one type, or two or more types.
The content of the acrylic resin in the pressure-sensitive adhesive composition (i) is preferably 40 to 99% by mass, and more preferably 50 to 91% by mass, based on the total amount of all the components contained in the pressure-sensitive adhesive composition (i) other than the solvent.
[ energy ray-polymerizable Compound ]
The energy ray-polymerizable compound is a compound that is polymerized and cured by irradiation with an energy ray, and examples thereof include compounds having an energy ray-polymerizable group such as an energy ray-curable double bond in the molecule.
Examples of the energy ray-polymerizable compound include low-molecular-weight compounds (monofunctional or polyfunctional monomers and oligomers) having an energy ray-polymerizable group.
More specific examples of the energy ray-polymerizable compound include: acrylates such as trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, etc.;
cyclic aliphatic skeleton-containing acrylates such as dicyclopentadiene dimethoxy diacrylate;
and acrylic compounds such as polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
The molecular weight of the energy ray-polymerizable compound is preferably 100 to 30000, more preferably 300 to 10000.
The energy ray-polymerizable compound contained in the pressure-sensitive adhesive composition (i) may be only one kind, or two or more kinds.
The content of the energy ray-polymerizable compound in the pressure-sensitive adhesive composition (i) is preferably 1 to 125 parts by mass, more preferably 10 to 125 parts by mass, based on 100 parts by mass of the acrylic resin.
[ photopolymerization initiator ]
The pressure-sensitive adhesive composition (i) may contain a photopolymerization initiator in addition to the acrylic resin and the energy ray-polymerizable compound.
The photopolymerization initiator may be a known photopolymerization initiator.
Specific examples of the photopolymerization initiator include: α -ketol compounds such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α, α' -dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one;
acetophenone compounds such as methoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one;
benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether;
ketal compounds such as benzoin dimethyl ether;
aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride;
optically active oximes such as 1-phenone-1, 1-propanedione-2- (O-ethoxycarbonyl) oxime;
benzophenone compounds such as benzophenone, benzoylbenzoic acid, and 3,3' -dimethyl-4-methoxybenzophenone;
thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone;
camphorone; a halogenated ketone; an acylphosphine oxide; acyl phosphonates and the like.
The photopolymerization initiator contained in the adhesive composition (i) may be only one kind, or two or more kinds.
When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (i) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the content of the energy ray-polymerizable compound. By setting the content of the photopolymerization initiator to the lower limit or more, the effects of using the photopolymerization initiator can be sufficiently obtained. In addition, when the content of the photopolymerization initiator is not more than the upper limit, the by-product component generated by an excessive amount of the photopolymerization initiator can be suppressed, and the adhesive layer can be cured more favorably.
[ crosslinking agent ]
The pressure-sensitive adhesive composition (i) may contain a crosslinking agent in addition to the acrylic resin and the energy ray-polymerizable compound.
Examples of the crosslinking agent include organic polyisocyanate compounds and organic polyimine compounds.
Examples of the organic polyisocyanate compound include: an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and trimers, isocyanurates and adducts of these compounds; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound, or the alicyclic polyisocyanate compound with a polyol compound. The adduct is a reaction product of the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil.
More specifically, the organic polyisocyanate compound includes, for example: 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-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding either or both of toluene diisocyanate and hexamethylene diisocyanate to all or part of the hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyimine compound include: n, N ' -diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinylpropionate, tetramethylolmethane-tris- β -aziridinylpropionate, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine, and the like.
When an isocyanate compound is used as the crosslinking agent, a hydroxyl group-containing polymer is preferably used as the acrylic resin. When the crosslinking agent has an isocyanate group and the acrylic resin has a hydroxyl group, a crosslinked structure can be easily introduced into the pressure-sensitive adhesive layer by the reaction between the isocyanate group and the hydroxyl group.
The crosslinking agent contained in the adhesive composition (i) may be one kind only, or two or more kinds.
When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (i) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 16 parts by mass, based on 100 parts by mass of the content of the acrylic resin.
[ solvent ]
The pressure-sensitive adhesive composition (i) preferably further contains a solvent in addition to the acrylic resin and the energy ray-polymerizable compound.
The solvent is not particularly limited.
Preferred examples of the solvent include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The binder composition (i) may contain only one kind of solvent, or may contain two or more kinds of solvents.
When the binder composition (i) contains a solvent, the solvent content of the binder composition (i) is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.
[ other ingredients ]
The pressure-sensitive adhesive composition (i) may contain, in addition to the acrylic resin and the energy ray-polymerizable compound, other components not included in the photopolymerization initiator, the crosslinking agent, and the solvent, within a range not impairing the effects of the present invention.
The other components may be those known in the art, and may be arbitrarily selected according to the purpose, and are not particularly limited. Preferable examples of the other components include: dyes, pigments, deterioration inhibitors, antistatic agents, flame retardants, organosilicon compounds, chain transfer agents, and the like.
The other component contained in the adhesive composition (i) may be only one kind or two or more kinds.
< adhesive composition (ii) >)
The pressure-sensitive adhesive composition (ii) contains, as essential components, an acrylic resin having a hydroxyl group and a polymerizable group in a side chain, and an isocyanate-based crosslinking agent. Here, as the acrylic resin, for example, an acrylic resin having a hydroxyl group and a polymerizable group having a side chain via a urethane bond can be given.
In the case of using the pressure-sensitive adhesive composition (ii), since the acrylic resin has a polymerizable group in a side chain, as in the case of the pressure-sensitive adhesive composition (i), the releasability from the adherend due to the decrease in the adhesiveness of the pressure-sensitive adhesive layer after the polymerization reaction (curing) is improved and the pick-up property of the semiconductor chip with the protective film is improved, as compared with the case of using an energy ray polymerizable compound and irradiating an energy ray to perform a polymerization reaction.
In the present specification, the expression "acrylic resin" in the pressure-sensitive adhesive composition (ii) means "acrylic resin having a polymerizable group in a side chain" unless otherwise specified.
[ acrylic resin ]
Examples of the acrylic resin having a polymerizable group in a side chain include: a resin obtained by copolymerizing a hydroxyl group-containing compound such as a (meth) acrylate having no hydroxyl group (sometimes referred to as "non-hydroxyl group-containing (meth) acrylate" in the present specification) and a hydroxyl group-containing compound such as a (meth) acrylate having a hydroxyl group (sometimes referred to as "hydroxyl group-containing (meth) acrylate" in the present specification) as monomers, and reacting the hydroxyl group of the obtained hydroxyl group-containing copolymer with the isocyanate group of the compound having an isocyanate group and a polymerizable group to form a urethane bond.
Examples of the (meth) acrylate containing no hydroxyl group include (meth) acrylates other than the (meth) acrylate containing a hydroxyl group in the (meth) acrylate of the adhesive composition (i).
Examples of the hydroxyl group-containing compound include the same compounds as those of the hydroxyl group-containing (meth) acrylate in the adhesive composition (i).
The acrylic resin may be composed of only one kind of the non-hydroxyl group-containing (meth) acrylate and two or more kinds of the hydroxyl group-containing compounds.
Examples of the compound having an isocyanate group and a polymerizable group include isocyanate group-containing (meth) acrylates such as 2-methacryloyloxyethyl isocyanate.
The acrylic resin may be composed of only one kind of the compound having an isocyanate group and a polymerizable group, or two or more kinds of the compounds.
The acrylic resin contained in the pressure-sensitive adhesive composition (ii) may be only one type, or two or more types.
The content of the acrylic resin in the pressure-sensitive adhesive composition (ii) is preferably 80 to 99% by mass, more preferably 90 to 97% by mass, based on the total amount of all the components contained in the pressure-sensitive adhesive composition (ii) other than the solvent.
[ Cross-linking agent of isocyanate group ]
Examples of the isocyanate-based crosslinking agent include those similar to the organic polyisocyanate compounds described above as the crosslinking agent in the adhesive composition (i).
The isocyanate-based crosslinking agent contained in the adhesive composition (ii) may be one kind or two or more kinds.
The number of moles of the isocyanate group contained in the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) is preferably 0.2 to 3 times the number of moles of the hydroxyl group contained in the acrylic resin in the pressure-sensitive adhesive composition (ii). When the number of moles of the isocyanate group is equal to or greater than the lower limit value, the releasability from the adherend due to the decrease in the adhesiveness of the cured adhesive layer is improved, and the pick-up property of the semiconductor chip with the protective film is improved. When the number of moles of the isocyanate group is not more than the upper limit, the by-product generated by the reaction between the isocyanate-based crosslinking agents can be further suppressed.
The content of the isocyanate-based crosslinking agent in the adhesive composition (ii) is preferably adjusted so that the number of moles of the isocyanate group is in the above range.
The content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.3 to 12 parts by mass, based on 100 parts by mass of the acrylic resin, in such a manner that the above-described condition of the number of moles of the isocyanate group is satisfied.
[ photopolymerization initiator ]
The pressure-sensitive adhesive composition (ii) may contain a photopolymerization initiator in addition to the acrylic resin and the isocyanate-based crosslinking agent.
Examples of the photopolymerization initiator include the same photopolymerization initiators as in the case of the adhesive composition (i).
The photopolymerization initiator contained in the adhesive composition (ii) may be only one kind, or two or more kinds.
When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (ii) is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of the content of the acrylic resin. By setting the content of the photopolymerization initiator to the lower limit or more, the effects of using the photopolymerization initiator can be sufficiently obtained. In addition, when the content of the photopolymerization initiator is not more than the upper limit, the by-product component generated by an excessive amount of the photopolymerization initiator can be suppressed, and the adhesive layer can be cured more favorably.
[ solvent ]
The pressure-sensitive adhesive composition (ii) preferably further contains a solvent in addition to the acrylic resin and the isocyanate-based crosslinking agent.
Examples of the solvent include the same solvents as in the case of the adhesive composition (i).
The binder composition (ii) may contain only one kind of solvent, or may contain two or more kinds of solvents.
When the binder composition (ii) contains a solvent, the solvent content of the binder composition (ii) is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.
[ other ingredients ]
The pressure-sensitive adhesive composition (ii) may contain other components than the photopolymerization initiator and the solvent, in addition to the acrylic resin and the isocyanate-based crosslinking agent, within a range not impairing the effects of the present invention.
Examples of the other components include other components similar to those in the case of the adhesive composition (i).
The other components contained in the adhesive composition (ii) may be only one type or two or more types.
The pressure-sensitive adhesive composition containing a component that is polymerized by irradiation with an energy ray has been described above, but a pressure-sensitive adhesive composition containing no component that is polymerized by irradiation with an energy ray may be used in forming the pressure-sensitive adhesive layer. That is, the adhesive layer may be a non-energy ray-curable adhesive layer having no energy ray-curability.
Examples of the preferable non-energy ray-curable adhesive composition include an adhesive composition containing an acrylic resin and a crosslinking agent (hereinafter, may be simply referred to as "adhesive composition (iii)"). The adhesive composition (iii) may contain any component such as a solvent, other component not belonging to the solvent, and the like.
< adhesive composition (iii) >
The acrylic resin, the crosslinking agent, the solvent and other components contained in the pressure-sensitive adhesive composition (iii) are the same as those in the pressure-sensitive adhesive composition (i), respectively.
The content of the acrylic resin in the pressure-sensitive adhesive composition (iii) is preferably 40 to 99% by mass, and more preferably 50 to 93% by mass, based on the total amount of all the components contained in the pressure-sensitive adhesive composition (iii) other than the solvent.
The content of the crosslinking agent in the pressure-sensitive adhesive composition (iii) is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the content of the acrylic resin.
The adhesive composition (iii) is the same as the adhesive composition (i) except for the above points.
Production method of adhesive composition
The pressure-sensitive adhesive compositions (i) to (iii) and the like can be obtained by blending the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive and the like for components constituting each pressure-sensitive adhesive composition.
The order of addition 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 can be appropriately selected from known methods such as a method of mixing by rotating a stirrer, a paddle, or the like, a method of mixing using a mixer, and a method of mixing by applying ultrasonic waves.
The temperature and time for adding and mixing the components are not particularly limited as long as the components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
Protective film Forming film
The protective film-forming film may be either thermosetting or energy ray-curable. The protective film-forming film is cured to finally become a protective film having high impact resistance. The protective film can prevent the generation of cracks in the semiconductor chip after the dicing step, for example.
The protective film-forming film can be formed using a thermosetting protective film-forming composition or an energy ray-curable protective film-forming composition (hereinafter, these are sometimes referred to as "protective film-forming composition" inclusive) described later.
The protective film-forming film may be a single layer (1 layer) or a multilayer having 2 or more layers, and when the protective film is a multilayer, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
The thickness of the film for forming the protective film is not particularly limited, but is preferably 1 to 100. Mu.m, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the protective film forming film is not less than the lower limit value, the adhesion force to the semiconductor wafer and the semiconductor chip as the object to be bonded is further increased. Further, by setting the thickness of the film for forming a protective film to the upper limit value or less, the protective film as a cured product can be cut more easily by a shear force at the time of picking up a semiconductor chip.
Film for Forming thermosetting protective film
Examples of a preferable thermosetting protective film-forming film include a thermosetting protective film-forming film containing a polymer component (a) and a thermosetting component (B). The polymer component (a) is a component which can be considered to be formed by polymerization of a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction by using heat as a trigger of the reaction. In the present invention, the polymerization reaction also includes a polycondensation reaction.
Composition for forming thermosetting protective film
The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film containing the constituent material. For example, a thermosetting protective film-forming composition is applied to a surface to be formed with a thermosetting protective film-forming film, and the composition is dried as necessary, whereby the thermosetting protective film-forming film can be formed at a target site. The content ratio of the components that do not vaporize at room temperature in the thermosetting protective film-forming composition is generally the same as the content ratio of the above components in the thermosetting protective film-forming composition. Here, "ordinary temperature" is as described above.
The coating of the thermosetting protective film-forming composition can be carried out according to a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the thermosetting protective film-forming composition are not particularly limited, and when the thermosetting protective film-forming composition contains a solvent described later, it is preferably dried by heating. The thermosetting protective film-forming composition containing a solvent is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
< composition (III-1) for Forming 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 the present specification, the composition may be simply referred to as "composition (III-1) for forming a protective film").
[ 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) for forming a protective film and the thermosetting film for forming a protective film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include: acrylic resins (resins having a (meth) acryloyl group), polyesters, urethane resins (resins having a urethane bond), acrylic urethane resins, silicone resins (resins having a siloxane bond), rubber resins (resins having a rubber structure), phenoxy resins, thermosetting polyimides, and the like, with acrylic resins being preferred.
As the acrylic resin in the polymer component (a), known acrylic polymers can be cited.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000. When the weight average molecular weight of the acrylic resin is not less than the lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. Further, by setting the weight average molecular weight of the acrylic resin to be not more than the upper limit, the thermosetting protective film-forming film can easily follow the uneven surface of the adherend, and generation of voids and the like between the adherend and the thermosetting protective film-forming film can be further suppressed.
The glass transition temperature (Tg) of the acrylic resin is preferably from-60 to 70 ℃, more preferably from-30 to 50 ℃. When the Tg of the acrylic resin is not less than the lower limit, the adhesion between the protective film and the supporting sheet can be suppressed, and the peelability of the supporting sheet can be improved. When the Tg of the acrylic resin is not more than the upper limit, the adhesion between the thermosetting protective film-forming film and the object to be adhered and the protective film can be improved.
Examples of the acrylic resin include polymers of one or two or more kinds of (meth) acrylic acid esters; and copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
Examples of the (meth) acrylate constituting the acrylic resin include: alkyl (meth) acrylates having a chain structure in which the number of carbon atoms constituting an alkyl group is 1 to 18, such as 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, stearyl (meth) acrylate);
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;
cycloalkoxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylimide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxyl 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 (meth) acrylates containing a substituted amino group such as N-methylaminoethyl (meth) acrylate. The "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may be obtained by copolymerizing one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide, in addition to the (meth) acrylic acid ester.
The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio of the monomers can be arbitrarily selected.
Examples of the acrylic resin include functional groups 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 above functional group of the acrylic resin may be bonded to other compounds by a crosslinking agent (F) described later, or may be directly bonded to other compounds without the aid of the crosslinking agent (F). When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the composite sheet for forming a protective film tends to be improved.
In the present invention, as the polymer component (a), a thermoplastic resin other than the acrylic resin (hereinafter, may be simply referred to as "thermoplastic resin") may be used in combination with the acrylic resin. By using the thermoplastic resin, the peeling property of the protective film from the support sheet is improved, or the thermosetting protective film forming film easily follows the uneven surface of the adherend, and the generation of a void 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, and 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: polyester, polyurethane, phenoxy resin, polybutylene, polybutadiene, polystyrene, and the like.
The thermoplastic resin contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1) for forming a protective film, the proportion of the content of the polymer component (a) relative to the total content of all components other than the solvent (i.e., the content of the polymer component (a) in the thermosetting film for forming a protective film) does not depend on the type of the polymer component (a), and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass.
The polymer component (a) may correspond to the thermosetting component (B). In the present invention, when the protective film-forming composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the protective film-forming 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 film for forming a thermosetting protective film to form a hard protective film.
The thermosetting component (B) contained in the composition for forming a protective film (III-1) and the 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.
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 preferred.
(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 for forming a protective film (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.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include: polyfunctional epoxy resins, biphenyl compounds, bisphenol A glycidyl ethers and hydrides thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenylene skeleton epoxy resins, and the like, and epoxy compounds having 2 or more functional groups.
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 high compatibility with the acrylic resin, as compared with the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof with an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include a vinyl group, a 2-propenyl group, a (meth) acryloyl group, and a (meth) acrylamido group, and an acryloyl group is preferred.
In the present specification, the term "derivative" refers to a compound in which 1 or more hydrogen atoms of the original compound are substituted with a group (substituent) other than a hydrogen atom.
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, and particularly preferably 300 to 3000, from the viewpoints of curability of the thermosetting protective film-forming film, and strength and heat resistance of the protective film after curing.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1100g/eq, more preferably 150 to 1000g/eq.
One epoxy resin (B1) may be used alone, or two or more epoxy resins may be used in combination, and when two or more epoxy resins are used 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: and a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an acid group, and the like, preferably a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (B2) include: multifunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl phenol resins, and the like.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (B2) include: dicyandiamide (hereinafter also simply referred to as "DICY") 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 phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of the phenol resin, or the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.
When a phenol curing agent is used as the heat curing agent (B2), the heat curing agent (B2) is preferably a heat curing 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.
The heat-curing agent (B2) is preferably a heat-curing agent which is solid at room temperature and does not exhibit curing activity to the epoxy resin (B1), but dissolves by heating and exhibits curing activity to the epoxy resin (B1) (hereinafter, may be simply referred to as "heat-active latent epoxy resin curing agent").
The thermally active latent epoxy resin curing agent is stably dispersed in the epoxy resin (B1) in the film for forming a thermosetting protective film at normal temperature, but is compatible with the epoxy resin (B1) by heating and reacts with the epoxy resin (B1). By using the thermally active latent epoxy resin curing agent, the storage stability of the composite sheet for forming a protective film is significantly improved. For example, the movement of the curing agent from the protective film forming film to the adjacent support sheet is suppressed, and the thermosetting degradation of the thermosetting protective film forming film can be effectively suppressed. In addition, since the thermosetting degree of the film for forming a thermosetting protective film by heating is further increased, the pick-up property of the semiconductor chip with a protective film described later is further improved.
Examples of the thermally active latent epoxy resin curing agent include: onium salts, dibasic acid hydrazides, dicyandiamide, amine adducts of curing agents, and the like.
In the thermosetting agent (B2), the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl phenol resin is preferably 300 to 30000, more preferably 400 to 10000, and 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 heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof may be arbitrarily selected.
In the protective film-forming composition (III-1) and the thermosetting protective film-forming film, the content of the thermosetting curing agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, based on 100 parts by mass of the content of the epoxy resin (B1). When the content of the thermosetting agent (B2) is not less than the lower limit, the film for forming a thermosetting protective film can be more easily cured. When the content of the thermosetting agent (B2) is not more than the upper limit, the moisture absorption rate of the thermosetting protective film-forming 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 protective film-forming composition (III-1) and the thermosetting protective film-forming 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 1 to 100 parts by mass, more preferably 1.5 to 85 parts by mass, and particularly preferably 2 to 70 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 releasability of the support sheet can be improved.
[ curing Accelerator (C) ]
The composition (III-1) for forming a protective film 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 speed of the composition (III-1) for forming a protective film.
Preferred examples of the curing accelerator (C) include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which 1 or more hydrogen atoms are replaced with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which 1 or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl radical
Figure BDA0001758059730000271
Tetraphenylborate such as tetraphenylborate and triphenylphosphine tetraphenylborate.
The curing accelerator (C) contained in the composition for forming a protective film (III-1) and the 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 curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the content of the thermosetting component (B) in the protective film-forming composition (III-1) and the thermosetting protective film-forming film. By setting the content of the curing accelerator (C) to the lower limit value or more, the effects of using the curing accelerator (C) can be more remarkably obtained. When the content of the curing accelerator (C) is not more than the above upper limit, for example, the effect of suppressing the occurrence of segregation by the highly polar curing accelerator (C) moving to the side of the adhesive interface with the adherend in the thermosetting protective film forming film under high temperature/high humidity conditions is improved, and the reliability of the package obtained by using the thermosetting protective film forming film is further improved.
[ Filler (D) ]
The composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain a filler (D). By incorporating the filler (D) into 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 thermal expansion coefficient for the object to be protected, the reliability of the package obtained by using the thermosetting protecting-film forming film is further improved. Further, by incorporating the filler (D) into 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.
Preferred inorganic fillers include, for example: powders of silica, alumina, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride, and the like; forming the inorganic filler into spherical beads; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
Of these materials, the inorganic filler material is preferably silica or alumina.
The filler (D) contained in the composition for forming a protective film (III-1) and the thermosetting film for forming a protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the case of using the filler (D), the content ratio of the filler (D) (i.e., the content of the filler (D) in the thermosetting protective film-forming film) in the protective film-forming composition (III-1) is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass, based on the total content of all the components other than the solvent. When the content of the filler (D) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.
[ coupling agent (E) ]
The composition (III-1) for forming a protective film 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 adhesion of the thermosetting protective film-forming film to the adherend can be improved. In addition, by using the coupling agent (E), the heat resistance of the 1 st protective film 1a obtained by curing the film for forming a thermosetting protective 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 the functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.
Preferred examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane, etc.
The coupling agent (E) contained in the composition (III-1) for forming a protective film 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film. When the content of the coupling agent (E) is not less than the lower limit described above, the effects of using the coupling agent (E) such as improvement in dispersibility of the filler (D) in the resin and improvement in adhesiveness between the thermosetting protective film-forming film and the adherend can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of outgassing (outgas) can be further suppressed.
[ crosslinking agent (F) ]
When the polymer component (a) is a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group capable of bonding with another compound, such as the acrylic resin described above, the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain the crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and the initial adhesion and cohesion of the film for forming a thermosetting protective film can be adjusted by crosslinking in this way.
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 also collectively referred to simply as "aromatic polyisocyanate compound or the like"); trimers, isocyanurates and adducts such as the aromatic polyisocyanate compounds; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound and the like with a polyol compound. The "adduct" means a reaction product of the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. Examples of the adduct include xylylene diisocyanate adducts of trimethylolpropane described later. In addition, the "terminal isocyanate urethane prepolymer" is as described previously.
More specifically, the organic polyisocyanate compound includes, for example: 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate 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-tris- β -aziridinylpropionate, tetramethylolmethane-tris- β -aziridinylpropionate, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine, and the like.
When an organic polyisocyanate compound is used as the crosslinking agent (F), a hydroxyl group-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (F) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film for forming a thermosetting protective film by the reaction of the crosslinking agent (F) with the polymer component (a).
The crosslinking agent (F) contained in the composition for forming a protective film (III-1) and the thermosetting film for forming a 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 crosslinking agent (F) is used, the content of the crosslinking agent (F) in the protective film-forming composition (III-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. When the content of the crosslinking agent (F) is not more than the upper limit, the adhesive strength between the film for forming a thermosetting protective film and the supporting sheet and the adhesive strength between the film for forming a thermosetting protective film and the semiconductor wafer or semiconductor chip can be suppressed from being excessively lowered.
In the present invention, the effects of the present invention can be sufficiently obtained even without using the crosslinking agent (F).
[ energy ray-curable resin (G) ]
The composition (III-1) for forming a protective film may contain an energy ray-curable resin (G). The film for forming a thermosetting protective film can change its properties by irradiation with energy rays by containing the energy ray-curable resin (G).
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 acrylate compound having a (meth) acryloyl group.
Examples of the acrylic ester compounds include: (meth) acrylates having a chain-like 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; cyclic aliphatic skeleton-containing (meth) acrylates such as dicyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; a urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylates; polyether (meth) acrylates other than the polyalkylene glycol (meth) acrylates; 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 only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The energy ray-curable resin (G) contained in the protective film-forming composition (III-1) 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.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the protective film forming composition (III-1) is preferably 1 to 95% by mass, more preferably 2 to 90% by mass, and particularly preferably 3 to 85% by mass.
[ photopolymerization initiator (H) ]
When the protective film-forming composition (III-1) contains the energy ray-curable resin (G), a photopolymerization initiator (H) may be contained in order to efficiently progress the polymerization reaction of the energy ray-curable resin (G).
The photopolymerization initiator (H) in the protective film-forming composition (III-1) may be the same photopolymerization initiator as that in the adhesive composition (ii).
The photopolymerization initiator (H) contained in the protective film-forming composition (III-1) 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 photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the protective film-forming 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, relative to 100 parts by mass of the content of the energy ray-curable resin (G).
[ colorant (I) ]
The composition (III-1) for forming a protective film 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 dye, cyanine dye, merocyanine dye, croconic acid dye, and squaric acid
Figure BDA0001758059730000321
Pigment system, azulium (azulium) pigment system, polymethine pigment system, naphthoquinone pigment system, and pyrane/bamboo shoot>
Figure BDA0001758059730000322
A phthalocyanine-based coloring matter, a naphthalocyanine-based coloring matter, a naphthalimide-based coloring matter, an azo-based coloring matter, a condensed azo-based coloring matter, an indigo-based coloring matter, a perinone-based coloring matter, a perylene-based coloring matter, and a bis/bamboo unit>
Figure BDA0001758059730000323
Oxazine-based coloring matter, quinacridone-based coloring matter, isoindolinone-based coloring matter, quinophthalone-based coloring matter, pyrrole-based coloring matter, thioindigo-based coloring matter, metal complex-based coloring matter (metal complex salt dye), dithiol metal complex-based coloring matter, indoxyl-based coloring matterTriallylmethane dye, anthraquinone dye and di->
Figure BDA0001758059730000324
Oxazine-based pigments, naphthol-based pigments, azomethine-based pigments, benzimidazolone-based pigments, pyranthrone-based pigments, and threne-based pigments.
Examples of the inorganic pigment include: carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide) -based pigments, ATO (antimony tin oxide) -based pigments, and the like.
The colorant (I) contained in the composition for forming a protective film (III-1) and the thermosetting film for forming a 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 colorant (I) is used, the content of the colorant (I) in the thermosetting protective film-forming film may be appropriately adjusted according to the purpose. For example, the transparency of the protective film can be adjusted by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, including the case where the protective film is printed by laser irradiation, and the visibility of the printed matter can be adjusted. Further, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, it is possible to improve the design of the protective film and to make grinding marks on the back surface of the semiconductor wafer less visible. In view of this, in the composition (III-1) for forming a protective film, the ratio of the content of the colorant (I) to the total content of all components except the solvent (i.e., the content of the colorant (I) in 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, particularly preferably 0.1 to 5% by mass, and may be any content of, for example, 0.1 to 3% by mass and 0.1 to 1% by mass. By setting the content of the colorant (I) to the lower limit or more, the effect of using the colorant (I) can be more remarkably obtained. In addition, when the content of the colorant (I) is not more than the upper limit, excessive decrease in light transmittance of the film for forming a thermosetting protective film can be suppressed.
[ general additive (J) ]
The composition (III-1) for forming a protective film and the thermosetting film for forming a protective film may contain the general-purpose additive (J) in a range not to impair the effects of the present invention.
The general-purpose additive (J) may be a known additive, may be arbitrarily selected depending on the purpose, and is not particularly limited, and preferable general-purpose additives include, for example: plasticizers, antistatic agents, antioxidants, getters, and the like.
The general-purpose additive (I) contained in the composition (III-1) for forming a protective film 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.
The content of the general-purpose additive (I) in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film is not particularly limited and can be appropriately selected depending on the purpose.
[ solvent ]
The composition (III-1) for forming a protective film preferably further contains a solvent. The composition (III-1) for forming a protective film containing a solvent is excellent in handling properties.
The solvent is not particularly limited.
Preferred examples of the solvent include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition (III-1) for forming a 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.
The solvent contained in the composition (III-1) for forming a protective film is preferably methyl ethyl ketone or the like, because the components contained in the composition (III-1) for forming a protective film can be mixed more uniformly.
Method for producing composition for forming thermosetting protective film
The composition for forming a thermosetting protective film such as the composition (III-1) for forming a protective film can be obtained by blending the respective 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.
When a solvent is used, the solvent may be mixed with any compounding ingredient other than the solvent to dilute the compounding ingredient in advance and then used, or the solvent may be mixed with any compounding ingredient other than the solvent without diluting the compounding ingredient in advance and used.
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, a paddle, or the like, a method of mixing using a mixer, and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
Energy ray-curable film for Forming protective film
The film for forming an energy ray-curable protective film contains an energy ray-curable component (a).
The energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive. Here, "energy ray" and "energy ray curability" are as described above
Composition for forming energy ray-curable protective film
The film for forming an energy ray-curable protective film can be formed using a composition for forming an energy ray-curable protective film containing the constituent material. For example, the energy ray-curable protective film-forming film can be formed on a target site by applying the energy ray-curable protective film-forming composition on a surface to be formed of the energy ray-curable protective film-forming film and drying the composition as necessary. The content ratio of the components that do not vaporize at normal temperature in the energy ray-curable protective film-forming composition is generally the same as the content ratio of the components of the energy ray-curable protective film-forming film. Here, "ordinary temperature" is as described above.
The energy ray-curable composition for forming a protective film can be applied by a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the energy ray-curable composition for forming a protective film are not particularly limited, and when the energy ray-curable composition for forming a protective film contains a solvent described later, it is preferably dried by heating. The composition for forming an energy ray-curable protective film containing a solvent is preferably dried at, for example, 70 to 130 ℃ for 10 seconds to 5 minutes.
< composition for Forming protective film (IV-1) >)
Examples of the energy ray-curable composition for forming a protective film include an energy ray-curable composition for forming a protective film (IV-1) containing the energy ray-curable component (a) (in the present specification, the composition may be simply referred to as "composition for forming a protective film (IV-1)"), and the like.
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component that is cured by irradiation with an energy ray, and is also a component for imparting film formability, flexibility, and the like to the energy ray-curable protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a 1) having an energy ray-curable group and having a weight-average molecular weight of 80000 to 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 that is not crosslinked.
(Polymer (a 1) having energy ray-curable group and weight-average molecular weight of 80000 to 2000000.)
Examples of the polymer (a 1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000 include: an acrylic resin (a 1-1) obtained by polymerizing an acrylic polymer (a 11) having a functional group capable of reacting with a group contained in another compound and an energy ray-curable compound (a 12) having a group reactive with the functional group and an energy ray-curable group such as an energy ray-curable double bond.
Examples of the functional group capable of reacting with a group of another compound include: a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which 1 or 2 hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. Among them, from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor chip, or the like, it is preferable that the functional group is a group other than a carboxyl group.
Among these, the 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 functional group and the acrylic monomer having no functional group may be a copolymer obtained by further copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a 11) may be a random copolymer or a block copolymer.
Examples of the acrylic monomer having the functional group include: hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, epoxy-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 such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth) acryloyl skeleton).
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 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 or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a 11) may be one type alone, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include: examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having a chain structure in which the number of carbon atoms of an alkyl group constituting the alkyl ester is 1 to 18, such as 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, and stearyl (meth) acrylate.
Further, as the acrylic monomer having no functional group, for example: alkoxyalkyl group-containing (meth) acrylates such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and (meth) acrylic esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a 11) may be one type only, or two or more types, and in the case of two or more types, 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 type only, two or more types, or two or more types, and 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. When the ratio is in such a range, the content of the energy ray-curable group in the acrylic resin (a 1-1) obtained by copolymerizing the acrylic polymer (a 11) 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 type only, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV-1) for forming a protective film, the content of the acrylic resin (a 1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.
Energy ray-curable compound (a 12)
The energy ray-curable compound (a 12) preferably has one or more groups selected from an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a 11), and more preferably has an isocyanate group as the group. When the energy ray-curable compound (a 12) has, for example, an isocyanate group as the group, the isocyanate group is likely to react with the hydroxyl group of the acrylic polymer (a 11) having a hydroxyl group as a functional group.
The energy ray-curable compound (a 12) preferably has 1 to 5 energy ray-curable groups in 1 molecule, and more preferably 1 to 2 groups.
Examples of the energy ray-curable compound (a 12) include: 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate;
an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and acryloyl monoisocyanate compounds obtained by reacting a diisocyanate compound or a 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 type only, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a 1-1), the proportion of the content of the energy ray-curable group derived from the energy ray-curable compound (a 12) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol% with respect to the content of the functional group derived from the acrylic polymer (a 11). When the content ratio is within 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 compound (having 1 group in the molecule), the upper limit of the proportion of the content is 100 mol%, but in the case where the energy ray-curable compound (a 12) is a polyfunctional compound (having 2 or more groups in the molecule), the upper limit of the proportion of the content may exceed 100 mol%.
The weight average molecular weight (Mw) of the polymer (a 1) is preferably 100000 to 2000000, more preferably 300000 to 1500000.
Here, the "weight average molecular weight" is as described above.
When 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 which does not belong to any of the monomers described as monomers constituting the acrylic polymer (a 11) and has a group reactive with the crosslinking agent and crosslinking the group reactive with the crosslinking agent, or may be a compound obtained by crosslinking 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) for forming a protective film and the film for forming an energy ray-curable protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000.)
The energy ray-curable group of the compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000 includes a group containing an energy ray-curable double bond, and preferably includes a (meth) acryloyl group, a vinyl group, and the like.
The compound (a 2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include: low molecular weight compounds having an energy ray-curable group, epoxy resins having an energy ray-curable group, phenol resins having an energy ray-curable group, and the like.
Examples of the low molecular weight compound having an energy ray-curable group in the compound (a 2) include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylic ester compounds include: <xnotran> 2- -3- () , () , A () ,2,2- [4- (() ) ] , A () ,2,2- [4- (() ) ] ,9,9- [4- (2- () ) ] ,2,2- [4- (() ) ] , () ,1,10- () ,1,6- () ,1,9- () , () , () , () , () , () , () , () ,2,2- [4- (() ) ] , () , </xnotran> Difunctional (meth) acrylates such as ethoxylated polypropylene glycol di (meth) acrylate and 2-hydroxy-1, 3-di (meth) acryloyloxypropane;
polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like;
and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the compound (a 2), for example, the resins described in paragraph 0043 and the like of "jp 2013-194102 a" 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) for forming a protective film and the film for forming an energy ray-curable protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition for forming a protective film (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), it is preferable that the composition 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-based resins, acrylic urethane resins, and the like.
Of these polymers, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and a monomer other than one or more acrylic monomers (non-acrylic monomer).
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include: alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, (meth) acrylates containing a glycidyl group, (meth) acrylates containing a hydroxyl group, (meth) acrylates containing a substituted amino group, and the like. Here, the "substituted amino group" is as described above.
Examples of the alkyl (meth) acrylate include: examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having a chain structure in which the number of carbon atoms of an alkyl group constituting the alkyl ester is 1 to 18, such as 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, and stearyl (meth) acrylate.
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 and the like.
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 the reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group is not particularly limited, and may be appropriately selected depending on the kind of the crosslinking agent. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among these functional groups, a hydroxyl group having high reactivity with an isocyanate group is preferable. When 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 circuit corrosion of a semiconductor wafer, a semiconductor chip, or the like.
Examples of the polymer (b) having no energy ray-curable group and having the reactive functional group include: 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 either or both of the acrylic monomer and the non-acrylic monomer described above as the monomer constituting the polymer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and in addition to these, polymers obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms in the above-mentioned acrylic monomer or non-acrylic monomer are substituted with the above-mentioned 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 to the total amount of the structural units constituting the polymer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By setting the above ratio to such a range, the degree of crosslinking in the polymer (b) can be brought to a more preferable range.
From the viewpoint of improving the film-forming property of the protective film-forming composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000. Here, the "weight average molecular weight" is as described above.
The number of the polymers (b) having no energy ray-curable group contained in the composition (IV-1) for forming a protective film and the film for forming an energy ray-curable protective film may be only one, two or more, and in the case of two or more, the combination and ratio thereof may be arbitrarily selected.
The protective film-forming composition (IV-1) may contain either one or both of the polymer (a 1) and the compound (a 2). When the protective film-forming composition (IV-1) contains the compound (a 2), it preferably further contains a polymer (b) having no energy ray-curable group, and in this case, it preferably further contains the compound (a 1). The protective film-forming 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).
When the protective film-forming 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) in the protective film-forming composition (IV-1) 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 protective film-forming 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 to the total content of components other than the solvent (i.e., 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) 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 energy ray-curable protective film-forming film becomes better.
The protective film-forming composition (IV-1) may contain, in addition to the energy ray-curable component, one or more selected from a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a colorant, and a general-purpose additive, depending on the purpose. For example, by using the composition (IV-1) for forming a protective film containing the energy ray-curable component and the thermosetting component, the adhesion of the formed film for forming an energy ray-curable protective film to an adherend is improved by heating, and the strength of the protective film formed from the film for forming an energy ray-curable protective film is also improved.
The thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the protective film forming composition (IV-1) may be the same as those in the energy ray-curable resin composition (III-1), respectively, for example, the thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant (I) and general-purpose additive (J).
In the composition (IV-1) for forming a protective film, the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the protective film forming composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.
The composition (IV-1) for forming a protective film preferably further contains a solvent, because the handling properties can be improved by dilution.
Examples of the solvent contained in the composition (IV-1) for forming a protective film include the same solvents as those contained in the composition (III-1) for forming a protective film.
The amount of the solvent contained in the composition (IV-1) for forming a protective film may be one kind or two or more kinds.
Method for producing composition for forming energy ray-curable protective film
The energy ray-curable composition for forming a protective film, such as the composition (IV-1) for forming a protective film, can be obtained by blending the respective 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.
When a solvent is used, the solvent may be mixed with any compounding ingredient other than the solvent to dilute the compounding ingredient in advance and then used, or the solvent may be mixed with any compounding ingredient other than the solvent without diluting the compounding ingredient in advance and used.
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, a paddle, and the like, a method of mixing using a mixer, and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.
O coating layer
The surface roughness Ra of the surface of the support sheet opposite to the side in contact with the coating layer is not particularly limited as long as it is smaller than the surface roughness Ra of the support sheet on the side provided with the coating layer.
The coating layer preferably contains, for example, a cured product obtained by curing by irradiation with an energy ray, and preferably contains a coating layer obtained by curing a coating composition containing an energy ray-polymerizable compound, which is polymerized by irradiation with an energy ray. The energy ray-polymerizable compound is preferably (meth) acrylic acid or a derivative thereof.
The composite sheet for forming a protective film has not only a function of forming a protective film for protecting the back surface of a semiconductor chip obtained by dicing, but also a function of being used as a dicing sheet in dicing a semiconductor wafer, for example. In addition, when dicing a semiconductor wafer, the semiconductor wafer to which the composite sheet for forming a protective film is attached may be subjected to expansion, and in this case, the composite sheet for forming a protective film is required to have appropriate flexibility. In order to impart appropriate flexibility to the composite sheet for forming a protective film, for example, a flexible resin such as polypropylene may be selected as a material constituting the support sheet. On the other hand, such a soft resin or the like may be deformed or wrinkled by heating. Therefore, it can be said that the coating layer can be formed from a composition as a raw material by curing by irradiation with an energy ray, not by thermal curing.
The thickness of the coating layer is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.4 to 15 μm, and particularly preferably 0.8 to 10 μm. By setting the thickness of the coating layer to be equal to or greater than the lower limit value, the surface roughness Ra of the surface of the coating layer opposite to the side in contact with the support sheet can be more easily reduced, and the effect of suppressing blocking of the composite sheet for forming the protective film can be further improved. Further, by setting the thickness of the coating layer to the upper limit value or less, it is possible to obtain a clearer inspection image when inspecting the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached with an infrared camera or the like through the sheet, and it is possible to more easily cut the semiconductor wafer accompanied by expansion.
The coating layer may be formed into an uneven surface by covering the uneven surface of the support sheet as described above, and the thickness of the coating layer may be calculated at a portion of the coating layer including the convex portion of the uneven surface, with the tip of the convex portion as one starting point.
The surface roughness Ra of the surface of the coating layer on the side opposite to the side in contact with the support sheet is preferably 0.5 μm or less, more preferably 0.4 μm or less, still more preferably 0.3 μm or less, and particularly preferably 0.2 μm or less. By setting the surface roughness Ra of the coating layer to the upper limit value or less, the protective film can be printed more clearly by laser.
The lower limit value of the surface roughness Ra of the surface of the coating layer opposite to the side in contact with the support sheet is not particularly limited, and may be, for example, 0.005 μm.
That is, the surface roughness Ra may be set to, for example, preferably 0.005 to 0.5 μm, more preferably 0.005 to 0.4 μm, still more preferably 0.005 to 0.3 μm, and particularly preferably 0.005 to 0.2 μm or less.
The surface roughness Ra of the coating layer can be adjusted by, for example, the surface roughness Ra of the surface of the support sheet on the side provided with the coating layer, the thickness of the coating layer, a coating method of a coating composition described later for forming the coating layer, and the like.
The value of [ thickness (μm) of the coating layer ]/[ surface roughness Ra (μm) of the surface of the support sheet on the side provided with the coating layer ] of the coating layer is preferably 0.1 to 30, more preferably 0.3 to 20, and particularly preferably 0.5 to 10. When the value is equal to or greater than the lower limit value, the surface roughness Ra of the surface of the coating layer on the side opposite to the side in contact with the support sheet is further reduced. Therefore, the protective film can be printed with laser light more clearly, and the effect of suppressing blocking of the protective film forming composite sheet is further improved. In addition, by setting the value to be equal to or less than the upper limit value, the thickness of the coating layer can be prevented from becoming excessive.
The surface of the coating layer opposite to the side in contact with the support sheet (the support sheet side) preferably has a gloss value of 32 to 95, more preferably 40 to 90, particularly preferably 45 to 85, and may be, for example, 50 to 80. When the gloss value of the coating layer is in such a range, the protective film can be printed more clearly by laser. Further, by setting the gloss value of the coating layer to be equal to or higher than the lower limit value, a clearer inspection image can be obtained when the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached is inspected with an infrared camera or the like through the sheet. Further, by setting the gloss value of the coating layer to be equal to or less than the upper limit value, it is possible to suppress the phenomenon of the coating layer emitting light when the state of the semiconductor wafer is inspected in the same manner, and it is possible to more easily visually recognize the inspection image by the infrared camera.
The gloss value is a value obtained by measuring the 20 ° specular gloss of the coating layer surface from the side opposite to the support sheet side of the coating layer based on jis k7105 standard.
The haze value measured from the coating layer side of the composite sheet for forming a protective film is preferably 47% or less, more preferably 1 to 47%, further preferably 2 to 40%, and particularly preferably 3 to 30%. When the haze of the composite sheet for forming a protective film is not more than the upper limit, scattering of light can be suppressed, and laser printing can be performed more clearly on the protective film. Further, when the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached is inspected with an infrared camera or the like through the sheet, a clearer inspection image can be obtained. Here, the measured haze value of the composite sheet for forming a protective film is a haze value measured from a direction of a surface of the composite sheet for forming a protective film on a side opposite to a side of the coating layer in contact with the support sheet.
The haze is a value measured according to JIS K7136.
Various properties such as the gloss value of the coating layer can be adjusted by, for example, the thickness of the coating layer, the content of a coating composition described later for forming the coating layer, and the like.
The haze value measured from the coated layer side of the composite sheet for forming a protective film can be adjusted by, for example, the thickness of each layer constituting the composite sheet for forming a protective film, such as a coating layer and a support sheet, and the content of a composition for forming each layer (for example, a coating composition described later).
Coating composition
The coating composition preferably contains one or both (α) (hereinafter, sometimes simply referred to as "component (α)") selected from a silica sol and silica fine particles to which an organic compound having a radical polymerizable unsaturated group is bonded, and one or two or more (β) (hereinafter, sometimes simply referred to as "component (β)") selected from a polyfunctional acrylate monomer and an acrylate prepolymer.
[ component (. Alpha.) ]
The component (α) is a component for reducing the refractive index of the coating layer and reducing the curing shrinkage and the heat and moisture shrinkage of the composite sheet for forming a protective film, thereby suppressing the occurrence of curling of the composite sheet for forming a protective film due to the shrinkage.
Examples of the silica sol in the component (α) include colloidal silica in which silica fine particles are suspended in a colloidal state in an organic solvent such as alcohol or ether derived from ethylene glycol (cellosolve). The average particle diameter of the silica fine particles suspended in the suspension is preferably 0.001 to 1 μm, more preferably 0.03 to 0.05. Mu.m.
The silica fine particles to which the organic compound having a radical polymerizable unsaturated group is bonded in the component (α) are crosslinked and cured by irradiation with an energy ray.
Examples of the silica fine particles to which the organic compound having a radical polymerizable unsaturated group is bonded include: the silanol group present on the surface of the silica fine particles is preferably a silanol group that is reacted with a functional group in the organic compound having a radical polymerizable unsaturated group, and the average particle diameter of the silica fine particles is preferably 0.005 to 1 μm. The functional group in the radical polymerizable unsaturated group-containing organic compound is not particularly limited as long as it can react with the silanol group in the silica fine particles.
Examples of the radical polymerizable unsaturated group-containing organic compound having the functional group include compounds represented by the following general formula (1).
[ chemical formula 1]
Figure BDA0001758059730000471
(in the formula, R 1 Is a hydrogen atom or a methyl group; r is 2 Is a halogen atom or a group represented by any of the following formulae (2 a) to (2 f). )
[ chemical formula 2]
Figure BDA0001758059730000472
As R 2 Examples of the halogen atom in (2) include chlorine, bromine, and iodine.
Preferred examples of the organic compound having a radical polymerizable unsaturated group include: (meth) acrylic acid, (meth) acryloyl chloride, 2-isocyanatoethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 3-iminopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3- (meth) acryloyloxypropyl) trimethoxysilane, and the like.
In the present invention, the radical polymerizable unsaturated group-containing organic compound may be used alone or in combination of two or more.
In the component (α), the silica sol and the silica fine particles to which the organic compound having a radical polymerizable unsaturated group is bonded may be each of only one kind, or two or more kinds.
As the component (α), only a silica sol may be used, only the silica fine particles to which the organic compound having a radical polymerizable unsaturated group is bonded may be used, or a combination of a silica sol and the silica fine particles to which the organic compound having a radical polymerizable unsaturated group is bonded may be used.
The content of the component (α) in the coating composition is preferably selected according to the refractive index of the support sheet, and is generally preferably an amount such that the content of silica derived from the component (α) in the coating layer is 20 to 60 mass%. When the content of silica is not less than the lower limit, the effect of reducing the refractive index of the coating layer and the effect of suppressing the occurrence of curling in the composite sheet for forming a protective film are further improved. Further, by setting the content of silica to the upper limit value or less, the formation of the coating layer becomes easier, and the effect of suppressing the decrease in hardness of the coating layer is further improved.
The content of silica derived from the component (α) in the coating layer is more preferably 20 to 45% by mass in terms of the refractive index, ease of formation, and hardness of the coating layer, and the suppression of the occurrence of curling in the composite sheet for forming a protective film described above.
[ component (. Beta.) ]
The component (β) is a main photocurable component for forming the coating layer.
The polyfunctional acrylate monomer in the component (β) is not particularly limited as long as it is a (meth) acrylic acid derivative having 2 or more (meth) acryloyl groups in 1 molecule.
Preferred examples of the polyfunctional acrylate monomer include: 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol ditrimethylglycolic acid di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, triisocyanate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) triisocyanate, dipentaerythritol penta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.
The acrylate prepolymer in the component (β) is not particularly limited as long as it is a photocurable (meth) acrylate polymer or oligomer.
Preferable examples of the acrylic prepolymer include: polyester acrylate prepolymers, epoxy acrylate prepolymers, urethane acrylate prepolymers, polyol acrylate prepolymers, and the like.
Examples of the polyester acrylate prepolymer include: a polyester acrylate prepolymer obtained by a condensation reaction of a polybasic acid and a polyhydric alcohol, the polyester oligomer having hydroxyl groups at both molecular terminals being esterified with (meth) acrylic acid at the hydroxyl groups; and polyester acrylate prepolymers obtained by esterifying terminal hydroxyl groups of oligomers obtained by addition reaction of an alkylene oxide with a polybasic acid with (meth) acrylic acid.
Examples of the epoxy acrylate prepolymer include: an epoxy acrylate prepolymer obtained by esterifying (meth) acrylic acid with an epoxy ring of a relatively low molecular weight bisphenol-type epoxy resin or a novolak-type epoxy resin.
Examples of the urethane acrylate prepolymer include: urethane acrylate prepolymer obtained by esterifying urethane oligomer obtained by reaction of polyether polyol or polyester polyol with polyisocyanate with (meth) acrylic acid.
Examples of the polyol acrylate prepolymer include: a polyol acrylate prepolymer obtained by esterifying the hydroxyl groups of a polyether polyol with (meth) acrylic acid.
In the component (. Beta.), the polyfunctional acrylate monomer and the acrylate prepolymer may be used alone or in combination of two or more.
As the component (β), the polyfunctional acrylate monomer may be used alone, the acrylate prepolymer may be used alone, or the polyfunctional acrylate monomer and the acrylate prepolymer may be used in combination.
[ solvent ]
The coating composition preferably further contains a solvent in addition to the component (α) and the component (β). By adding a solvent to the coating composition, the coating composition can be more easily applied and dried to form a coating film for forming a coating layer, as described later.
The above solvents may be used alone or in combination of two or more.
Examples of the solvent include: aliphatic hydrocarbons such as hexane, heptane, cyclohexane and the like; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and vinyl chloride; alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolves such as 2-ethoxyethanol (ethyl cellosolve).
[ optional Components ]
The coating composition may contain, in addition to the component (α) and the component (β), various optional components such as a monofunctional acrylate monomer, a photopolymerization initiator, a photosensitive agent, a polymerization inhibitor, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, and a defoaming agent, within a range not to impair the effects of the present invention.
Any of the above components may be used alone or in combination of two or more.
(monofunctional acrylate monomer)
The monofunctional acrylate monomer as an optional component is a photocurable component, and is not particularly limited as long as it is a (meth) acrylic acid derivative having only 1 (meth) acryloyl group in 1 molecule.
Preferred examples of the monofunctional acrylate monomer include: cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), octadecyl (meth) acrylate (stearyl (meth) acrylate), isobornyl (meth) acrylate, and the like.
(photopolymerization initiator)
Examples of the photopolymerization initiator of any component include known photopolymerization initiators conventionally used for radical polymerization.
Preferred examples of the photopolymerization initiator include: aryl ketone photopolymerization initiators such as acetophenone compounds, benzophenone compounds, alkylaminobenzophenone compounds, benzil compounds, benzoin ether compounds, benzyl dimethyl ketal compounds, benzoyl benzoate compounds, and α -acyloxime ester compounds; sulfur-containing photopolymerization initiators such as thioether compounds and thioxanthone compounds; acylphosphine oxide compounds such as acyldiarylphosphine oxides; anthraquinone compounds, and the like.
When the coating composition is cured by electron beam irradiation, a photopolymerization initiator is not required.
In the coating composition, the content of the photopolymerization initiator is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, relative to 100 parts by mass of the total content of the photocurable components.
(photosensitizers)
Examples of the photosensitizer include tertiary amines, p-dimethylaminobenzoate, and thiol sensitizers.
In the coating composition, the content of the photosensitizer is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, with respect to 100 parts by mass of the total content of the photocurable components.
(antioxidant, ultraviolet absorber, light stabilizer)
The antioxidant, ultraviolet absorber and light stabilizer may be known ones, but are preferably reactive antioxidants, ultraviolet absorbers and light stabilizers having a (meth) acryloyl group or the like in the molecule. Since these antioxidant, ultraviolet absorber and light stabilizer are bonded to the polymer chain formed by irradiation with energy rays, the escape of these components from the cured layer with the passage of time can be suppressed, and the functions of these components can be exhibited for a long period of time.
The coating composition preferably contains a silica sol as the component (. Alpha.), more preferably a silica sol containing silica fine particles suspended in a colloidal state and having an average particle diameter of 0.03 to 0.05. Mu.m.
By containing such a silica sol in the coating layer, the effect of suppressing blocking of the composite sheet for forming a protective film is further improved. In addition, in the coating layer, the surface on the side opposite to the support sheet side and the vicinity thereof are more highly doped with the silica sol than in other regions, and the effect of suppressing blocking of the composite sheet for forming a protective film is further improved due to the presence of such unevenness. In the coating layer, the coating conditions of the coating composition may be adjusted so that the silica sol or other component may be unevenly distributed.
Production method of coating composition
The coating composition can be obtained by, for example, blending an energy ray-polymerizable compound such as the component (α) and the component (β), and if necessary, components other than the above components, for each component constituting the coating composition. The coating composition can be obtained by the same method as in the case of the above-mentioned adhesive composition, except that the compounding ingredients are different, for example.
When a solvent is used, the solvent may be mixed with any compounding ingredient other than the solvent to dilute the compounding ingredient in advance and then used, or the solvent may be mixed with any compounding ingredient other than the solvent without diluting the compounding ingredient in advance and used.
The components other than the solvent in the coating composition may be dissolved in the solvent or may be dispersed in the solvent without being dissolved. The concentration and viscosity of each component of the coating composition are not particularly limited as long as the coating composition can be applied.
Method for producing composite sheet for forming protective film
The composite sheet for forming a protective film of the present invention can be produced as follows: the protective film-forming composition is used to form a protective film-forming film, the coating composition is used to form a coating layer, and the coating layer, the support sheet, and the protective film-forming film are sequentially laminated. When the support sheet is formed of a plurality of layers, the support sheet may be produced by laminating the plurality of layers. For example, when the support sheet is formed by laminating a base material and a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be formed using the pressure-sensitive adhesive composition.
The order of formation of the layers (coating layer, support sheet, film for forming a protective film) constituting the composite sheet for forming a protective film is not particularly limited. The composition of each layer may be formed directly on the surface of the adjacent layer in the state of the composite sheet for forming a protective film, or may be formed separately by using a release film (release sheet) and bonding the formed layer to the surface of the adjacent layer in the state of the composite sheet for forming a protective film. However, in order to suppress the generation of voids between the coating layer and the uneven surface (back surface) of the support sheet, the coating layer is preferably formed by directly applying the coating composition to the uneven surface of the support sheet.
An example of a preferred method for producing the composite sheet for forming a protective film is described below.
The coating layer is preferably formed by applying a coating composition to the uneven surface of the support sheet (in fig. 1 and 2, the back surface 10b of the support sheet 10, that is, the back surface 11b of the base material 11), drying the coating composition, and curing the formed coating film as necessary.
The application of the coating composition to the target surface can be carried out by a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
When the coating composition is applied to the uneven surface of the support sheet, it is preferable to suppress the generation of voids between the coating layer and the uneven surface of the support sheet. By suppressing the generation of the void, diffuse reflection of light at the boundary between the coating layer and the uneven surface of the support sheet can be suppressed, and laser printing can be performed more clearly on the surface of the protective film.
In order to suppress the generation of the void, for example, a coating composition having a low viscosity is preferably used. In addition, a coating composition containing an energy ray-polymerizable compound is generally more suitable for suppressing the generation of the above-mentioned void portion.
The drying conditions of the coating composition are not particularly limited, and the coating composition is preferably dried by heating, and in this case, for example, it is preferably dried under the conditions of 70 to 130 ℃ and 0.5 to 5 minutes.
The curing conditions of the coating film formed from the coating composition are not particularly limited, and may be performed according to a known method.
When curing is performed by energy ray irradiation, for example, when ultraviolet rays are irradiated, a high-pressure mercury lamp as an ultraviolet ray source,Preferably, the irradiation dose is set to 100 to 500mJ/cm in a melting H lamp, xenon lamp, black light or LED lamp 2 To perform the irradiation. On the other hand, in the case of irradiation with an electron beam, it is preferable to generate an electron beam by an electron beam accelerator or the like and to perform irradiation with an irradiation dose of preferably 150 to 350 kV. Among these, the formation of the coating layer is preferably performed by ultraviolet irradiation.
When the support sheet is formed by laminating a base material and an adhesive layer, for example, the adhesive composition may be directly applied to the surface of the base material provided with the coating layer (the surface 11a of the base material 11 in fig. 1 and 2) to form the adhesive layer. However, it is generally preferable to employ a method of applying an adhesive composition to the release-treated surface of a release sheet, drying the applied adhesive composition to form an adhesive layer, bonding the formed adhesive layer to the surface of a substrate, removing the release sheet, and the like, and separately forming an adhesive layer and bonding the adhesive layer to the surface of the substrate.
The adhesive composition can be applied to the surface of the object by the same method as in the case of applying the composition.
The adhesive composition after application can be crosslinked by heating, and the crosslinking by heating can also be performed as drying. The heating conditions may be, for example, 100 to 130 ℃ for 1 to 5 minutes, but the present invention is not limited thereto.
In either case where the support sheet is composed of 1 layer (single layer) such as being composed of only the base material or the like, or is composed of a plurality of layers such as being formed by laminating the base material and the adhesive layer, for example, the protective film-forming composition may be directly applied to the surface of the support sheet provided with the coating layer (the surface 10a of the support sheet 10, that is, the surface 12a of the adhesive layer 12 in fig. 1 and 2) to form the protective film-forming film. However, as in the case of the pressure-sensitive adhesive layer, it is generally preferable to employ a method in which a protective film-forming composition is applied to the release-treated surface of a release sheet and dried to form a protective film-forming film, the formed protective film-forming film is bonded to the surface of a support sheet, the release sheet or the like is removed as necessary, and a protective film-forming film is separately formed and bonded to the surface of the support sheet.
The protective film-forming composition can be applied to the surface of the object by the same method as in the case of the coating composition.
The drying conditions of the protective film-forming composition are not particularly limited, and the composition can be dried by the same method as in the case of the coating composition.
When the support sheet is formed by laminating a base material and an adhesive layer, the composite sheet for forming a protective film of the present invention can be produced by a method other than the above-described method. For example, a composite sheet for forming a protective film can be produced by forming a pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition, forming a film for forming a protective film using the composition for forming a protective film, laminating the pressure-sensitive adhesive layer and the film for forming a protective film to each other to form a laminate, and bonding the surface of the substrate provided with a coating layer (the surface 11a of the substrate 11 in fig. 1 and 2) to the surface of the pressure-sensitive adhesive layer of the laminate (the surface of the pressure-sensitive adhesive layer on which the film for forming a protective film is not provided).
The conditions for forming the pressure-sensitive adhesive layer and the protective film-forming film in this case are the same as those in the case of the above-described method.
For example, in the case of manufacturing a composite sheet for forming a protective film in which the surface area of the film for forming a protective film is smaller than the surface area of the pressure-sensitive adhesive layer when the composite sheet for forming a protective film is viewed from above downward as shown in fig. 1, in the above-described manufacturing method, the film for forming a protective film cut into a predetermined size and shape in advance may be provided on the pressure-sensitive adhesive layer.
Method for using composite sheet for forming very good protective film
The method of using the composite sheet for forming a protective film of the present invention is, for example, as follows.
First, a method of using the composite sheet for forming a protective film in the case where the film for forming a protective film is thermosetting will be described.
In this case, first, the back surface of the semiconductor wafer is bonded to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
Subsequently, the protective film-forming film is cured by heating to obtain a protective film. When a back grinding tape (back grinding tape) is attached to the surface (electrode forming surface) of the semiconductor wafer, the back grinding tape is usually removed from the semiconductor wafer, and then a protective film is formed.
Then, the semiconductor wafer is diced to obtain semiconductor chips. The protective film forming composite sheet may be irradiated with laser light from the coating layer side thereof to the protective film during a period from the formation of the protective film to the cutting, thereby printing on the surface of the protective film. In this case, as described above, the surface roughness Ra of the surface (back surface) of the coating layer opposite to the side in contact with the backing sheet is sufficiently reduced, and the back surface of the coating layer is a smooth surface or a surface with suppressed unevenness. Therefore, when the laser beam is irradiated, the diffuse reflection of the laser beam is suppressed on the back surface of the coating layer, and the laser printing can be performed clearly on the protective film.
Further, the state of a semiconductor wafer before dicing or a semiconductor chip obtained by dicing may be inspected by observing the semiconductor wafer from the back surface side (the surface to which the protective film forming composite sheet is attached) with an infrared camera or the like. For example, in the case of a semiconductor chip, the chip may be inspected for defects, cracks, and the like.
On the other hand, in the semiconductor chip with a protective film of the present invention, as described above, the surface roughness Ra of the surface (back surface) of the coating layer opposite to the side in contact with the support sheet is sufficiently reduced, and the generation of voids between the coating layer and the uneven surface (back surface) of the support sheet is suppressed. Therefore, when the composite sheet for forming a protective film is observed from the coating layer side through the protective film by an infrared camera or the like, a clear inspection image can be obtained, and therefore, the inspection can be performed with high accuracy.
Next, the semiconductor chip is peeled off from the support sheet together with the protective film attached to the back surface thereof, and picked up, thereby obtaining a semiconductor chip with a protective film. For example, when the support sheet is formed by laminating a base material and an adhesive layer and the adhesive layer is energy ray-curable, the adhesive layer is cured by irradiation with energy rays, and the semiconductor chip is picked up together with the protective film attached to the back surface of the semiconductor chip from the cured adhesive layer, whereby the semiconductor chip with the protective film can be more easily obtained.
For example, when the composite sheet 1 for forming a protective film shown in fig. 1 is used, the composite sheet 1 for forming a protective film is fixed to a dicing apparatus by attaching the film 13 for forming a protective film of the composite sheet 1 for forming a protective film to the back surface of the semiconductor wafer and attaching the exposed support sheet 10 (pressure-sensitive adhesive layer 12) to a dicing jig (not shown) such as a ring frame. Next, after the protective film is obtained by curing the protective film-forming film 13, the protective film may be subjected to laser printing, dicing, and if necessary, irradiation with energy rays to cure the region of the pressure-sensitive adhesive layer 12 other than the region to be bonded to the jig, and then the semiconductor chip with the protective film may be picked up. In the case of using the composite sheet 1 for forming a protective film in which the pressure-sensitive adhesive layer 12 is energy ray-curable, it is necessary to adjust the pressure-sensitive adhesive layer 12 so that the composite sheet 1 for forming a protective film is not peeled off from the jig and a specific region of the pressure-sensitive adhesive layer 12 is not cured. On the other hand, when the composite sheet 1 for forming a protective film is used, it is not necessary to separately provide a structure for attaching the composite sheet to the jig.
On the other hand, in the case of using the composite sheet 2 for forming a protective film shown in fig. 2, the composite sheet 2 for forming a protective film is fixed to a dicing apparatus by attaching the film 23 for forming a protective film of the composite sheet 2 for forming a protective film to the back surface of the semiconductor wafer and attaching the adhesive layer 16 for a jig to a dicing jig (not shown) such as a ring frame. Next, after the protective film is obtained by curing the protective film-forming film 23, the protective film may be subjected to laser printing, dicing, and if necessary, irradiation with energy rays to cure the adhesive layer 12, and then the semiconductor chip with the protective film may be picked up. In this way, in the case of using the composite sheet 2 for forming a protective film in which the adhesive layer 12 is energy ray-curable, unlike the case of using the composite sheet 1 for forming a protective film, it is not necessary to adjust the adhesive layer so as not to cure a specific region of the adhesive layer 12. On the other hand, unlike the composite sheet 1 for forming a protective film, the composite sheet 2 for forming a protective film needs to be a composite sheet provided with the adhesive layer 16 for a jig. By providing the jig adhesive layer 16, a layer having a wide composition can be selected as the adhesive layer 12 according to the purpose.
Next, a method of using the composite sheet for forming a protective film in the case where the film for forming a protective film is energy ray-curable will be described.
In this case, first, as in the case where the protective film forming film is thermosetting, the back surface of the semiconductor wafer is bonded to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
Then, the protective film-forming film is cured by irradiation with energy rays to form a protective film. In the case where a back-grinding tape is attached to the surface (electrode-forming surface) of the semiconductor wafer, the protective film is usually formed after the back-grinding tape is removed from the semiconductor wafer.
Then, the semiconductor wafer is diced to obtain semiconductor chips. The protective film forming composite sheet may be irradiated with laser light from the coating layer side thereof to the protective film during a period from the formation of the protective film to the cutting, thereby printing on the surface of the protective film. The printing and cutting can be performed in the same manner as in the case where the film for forming a protective film is thermosetting, and in the same manner as in the case where the protective film is printed clearly by laser, and the film can be inspected with high accuracy by an infrared camera or the like.
Then, the semiconductor chip is peeled off together with the protective film attached to the back surface thereof from the supporting sheet and picked up, thereby obtaining a semiconductor chip with a protective film.
This method is particularly suitable when, for example, a composite sheet for forming a protective film is used in which a support sheet is formed by laminating a base material and an adhesive layer, and the adhesive layer is non-energy-ray-curable. In the case where the protective film-forming film is cured by irradiation with energy rays, the semiconductor wafer is diced, and the semiconductor chip with the protective film is picked up, the protective film-forming film may be cured by irradiation with energy rays at any stage before the semiconductor chip is picked up, in the case where the adhesive layer is non-energy-ray-curable.
For example, when a support sheet is used to laminate a substrate and an adhesive layer, and the adhesive layer is an energy ray-curable protective film-forming composite sheet, the following method is preferable.
That is, first, as in the above case, the back surface of the semiconductor wafer is bonded to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
Next, the protective film is irradiated with laser light from the coating layer side of the protective film forming composite sheet, and the semiconductor wafer is cut into semiconductor chips after printing on the surface of the protective film. The printing and cutting can be performed in the same manner as in the case where the film for forming a protective film is thermosetting, and in the same manner as in the case where the protective film is printed clearly by laser, and the film can be inspected with high accuracy by an infrared camera or the like.
Then, the protective film-forming film is cured by irradiation with energy rays to form a protective film, the adhesive layer is cured, and the semiconductor chip is picked up together with the protective film attached to the back surface of the semiconductor chip from the cured adhesive layer, thereby obtaining a semiconductor chip with a protective film.
On the other hand, when the long composite sheet for forming a protective film is wound up, a composite sheet for forming a protective film is generally used in a state where a release film (release film 15 in fig. 1 and 2) is laminated on an exposed surface of the film for forming a protective film. In addition, when the composite sheet for forming a protective film of the present invention has an arbitrary configuration (for example, any of the composite sheet 1 for forming a protective film shown in fig. 1 and the composite sheet 2 for forming a protective film shown in fig. 2), as the composite sheet for forming a protective film is wound into a roll shape, laminated units in which a coating layer, a support sheet, a film for forming a protective film, and a release film are laminated in this order are laminated in the radial direction of the roll. As a result, between the laminated units that are in contact with each other in the radial direction of the roll, the surface of the release film of one laminated unit (the surface opposite to the side on which the protective film forming film is provided) is in contact with the back surface of the coating layer of the other laminated unit (the surface opposite to the side in contact with the base material), and a pressed state is obtained, and when this state is maintained, the roll of the protective film forming composite sheet is stored. However, since the application layer is provided, the adhesion of the release film and the application layer between the laminated units is suppressed, and therefore, the composite sheet for forming a protective film of the present invention can suppress blocking.
A composite sheet for forming a protective film of the present invention having a release film on a film for forming a protective film and having a width of 50mm and a length of 100mm is laminated such that the coating layers are all oriented in the same direction and the total thickness of the coating layers is 10 to 60 μm, thereby producing a laminate having one outermost layer as a coating layer and the other outermost layer as a release film, and 980.665mN (i.e., 100 gf) force (external force) is applied to the laminate in the lamination direction of the composite sheet for forming a protective film, the laminate is left to stand at 40 ℃ for 3 days while maintaining the state, and the release film closest to the coating layer of the outermost layer is released from the adjacent coating layer (the coating layer closest to the coating layer of the outermost layer in the lamination direction) at a release speed of 300 mm/min and a release angle of 180 ° in the lamination direction, and the release force at this time is preferably 10mN/50mm or less, more preferably 7.5mN/50mm or less, and particularly preferably 5mN/50mm or less. Here, the same configuration is applied to the composite sheet for forming a protective film in which a plurality of sheets are stacked. The number of laminated composite sheets for forming a protective film is preferably 10. The level of the blocking inhibiting effect (anti-blocking property) of the composite sheet for forming a protective film of the present invention can be confirmed based on the peeling force of the peeling film.
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
< production of composite sheet for Forming protective film >
[ example 1]
A composite sheet for forming a protective film having the structure shown in fig. 1 was produced. Fig. 3 is a plan view of the composite sheet for forming a protective film. More specifically, as described below.
[ production of the first laminate ]
(preparation of thermosetting protective film-forming composition)
A protective film-forming composition (III-1) having a solid content of 51 mass% was obtained by blending the following components in the following amounts (solid contents) and further blending methyl ethyl ketone.
(Polymer component (A))
(A) -1: acrylic resin (weight average molecular weight 400000, glass transition temperature-1 ℃) obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate, and 150 parts by mass of acrylic resin
(thermosetting component (B))
Epoxy resin (B1)
(B1) -1: 60 parts by mass of bisphenol A type epoxy resin ("JER 828" manufactured by Mitsubishi chemical corporation, epoxy equivalent weight of 183-194 g/eq, molecular weight of 370)
(B1) -2: 10 parts by mass of bisphenol A type epoxy resin ("JER 1055", manufactured by Mitsubishi chemical corporation), epoxy equivalent of 800 to 900g/eq, and molecular weight of 1600
(B1) -3: 30 parts by mass of dicyclopentadiene type epoxy resin ("EPICLON HP-7200HH" manufactured by DIC Co., ltd., epoxy equivalent of 274 to 286 g/eq)
Heat-curing agent (B2)
(B2) -1: dicyandiamide (solid dispersion type latent curing agent, "Adeka Harden 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 Siguo Kasei K.K.)
(Filler (D))
(D) -1: 320 parts by mass of a silica filler (SC 2050MA, admatechs Co., ltd., a silica filler surface-modified with an epoxy compound, having an average particle diameter of 0.5 μm)
(coupling agent (E))
(E) -1: 0.4 part by mass of gamma-glycidoxypropyltrimethoxysilane (silane coupling agent, "KBM403" manufactured by shin-Etsu chemical Co., ltd., methoxy equivalent of 12.7mmol/g, molecular weight of 236.3)
(colorant (I))
(I) -1: carbon Black (pigment, "MA600B" manufactured by Mitsubishi chemical corporation, average particle diameter 28 nm) 1.2 parts by weight
(formation of protective film-Forming film, production of the 1 st laminate)
The obtained composition (III-1) for forming a protective film was applied to the release-treated surface of the No. 1 release film (SP-P502010, manufactured by Lindcaceae, having a thickness of 50 μm) by means of a blade coater, and dried at 120 ℃ for 2 minutes to form a film (having a thickness of 25 μm) for forming a protective film.
Then, a peel-treated surface of a2 nd peel-off film (SP-PET 381031C manufactured by Lindelco., ltd., thickness 38 μm) was bonded to the surface of the protective film-forming film opposite to the surface on which the 1 st peel-off film was provided, to obtain a long laminate in which the 1 st peel-off film, the protective film-forming film, and the 2 nd peel-off film were sequentially laminated. Next, the long laminate is wound up to be a roll, and then the laminate is wound in the width direction (reference numeral w of the composite sheet 1 for forming a protective film shown in fig. 3) 1 Shown in the width direction) to a size of 300 mm.
Then, the cut laminate was half-cut from the 2 nd release film side at the center in the width direction so that the 2 nd release film and the protective film forming film each drawn a circle having a diameter of 220mm in a plan view. In the present specification, the "plan view" of the laminate means that the laminate is viewed from above and below in the stacking direction. Then, the 2 nd release film and the protective film forming film were removed from the laminate so that only the circular portion formed by half-cutting remained, and a1 st laminate in which the protective film forming film and the 2 nd release film which were circular in a plan view were sequentially laminated on the release-treated surface of the 1 st release film was obtained. The circular protective film forming film in the 1 st stacked body corresponds to the protective film forming film shown in FIG. 3With a median diameter d of the composite sheet 1 1 A protective film forming film 13 having a circular shape of 220 mm.
(preparation of coating composition)
100 parts by mass of a hard coat agent (Beam575 set CB, manufactured by Mitsukawa chemical industries, ltd., solid content concentration of 100% by mass, and photopolymerization initiator contained) composed of a urethane acrylate and a polyfunctional acrylate monomer was added to 150 parts by mass of a dispersion (OSCAL 1632, manufactured by catalytic chemical industries, ltd., silica sol particle diameter of 30 to 50nm, solid content concentration of 30% by mass) obtained by dispersing a silica sol in 2-ethoxyethanol (ethyl cellosolve), to obtain a coating composition (solid content concentration of 30% by mass).
(formation of coating layer)
Next, the coating composition obtained above was applied to the uneven surface of a polypropylene base material (thickness: 100 μm, melting point: 140 to 160 ℃ C.) having a surface roughness Ra of 0.4 μm on the uneven surface and a surface roughness Ra of 0.02 μm on the surface opposite to the uneven surface by using a Meyer bar coater, dried at 80 ℃ for 1 minute, and then dried at about 230mJ/cm 2 The dried coating film was cured by irradiating ultraviolet light at the light quantity of (2) to form a coating layer (thickness: 3 μm).
(preparation of adhesive composition)
An alkyl (meth) acrylate copolymer (100 parts by mass) and an aromatic polyisocyanate compound (a crosslinking agent, "Takenate D110N", manufactured by mitsui chemical) (10 parts by mass) (solid content) were mixed, and methyl ethyl ketone was mixed to obtain a pressure-sensitive adhesive composition (iii) having a solid content concentration of 30% by mass.
The alkyl (meth) acrylate copolymer was an acrylic resin having a weight average molecular weight of 600000 obtained by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of 2-hydroxyethyl acrylate.
(formation of adhesive layer (support sheet), production of 2 nd laminate)
The pressure-sensitive adhesive composition (iii) obtained above was applied to the release-treated surface of a 38 μm thick 3 rd release film (SP-PET 381031C, manufactured by leydetaceae) formed from a polyethylene terephthalate film, which was obtained by release-treating a silicone-based release agent layer on one side thereof by forming the release-treated surface, using a knife coater, and dried to form a pressure-sensitive adhesive layer (5 μm thick).
Next, after the surface of the base material opposite to the uneven surface on which the coating layer was formed was subjected to corona treatment, the pressure-sensitive adhesive layer was bonded to the corona-treated surface, thereby obtaining a2 nd long laminate including a support sheet and a coating layer, a base material, a pressure-sensitive adhesive layer, and a 3 rd release film laminated in this order.
Next, the long 2 nd laminate is wound up to be a roll, and then the 2 nd laminate is wound up in the width direction thereof (reference numeral w of the composite sheet 1 for forming a protective film shown in fig. 3) 1 Shown in the width direction) to a size of 300 mm.
(production of composite sheet for Forming protective film)
The 2 nd release film was removed from the 1 st stacked body obtained above, and the circular protective film-forming film was exposed. Further, the 3 rd release film was removed from the 2 nd laminate obtained above, and the pressure-sensitive adhesive layer was exposed. Then, the exposed surface of the protective film-forming film was bonded to the exposed surface of the pressure-sensitive adhesive layer to obtain a 3 rd laminate corresponding to the protective film-forming composite sheet in which the coating layer, the base material, the pressure-sensitive adhesive layer, the protective film-forming film, and the 1 st release film were laminated in this order.
The 3 rd laminate obtained above was half-cut with a cut-in notch from the coating layer side so that the coating layer, the base material, and the pressure-sensitive adhesive layer each drawn a circle having a diameter of 270mm in plan view. In the half-cut, cuts were made into the coating layer, the base material, and the adhesive layer, and the circle having a diameter of 270mm in plan view and the circle having a diameter of 220mm formed by the protective film-forming film were made concentric.
Then, half-cuts having cuts made in all of the coating layer, the base material, and the pressure-sensitive adhesive layer were made from the coating layer side at a position 20mm away from the radially outer side of the above-mentioned circle having a diameter of 270mm in plan view so as to be in the width direction of the 3 rd laminated body (symbol w of the composite sheet for forming a protective film 1 shown in fig. 3) 1 Width shownDirection) describes an opposing pair of arcs. The cuts corresponding to the pair of arcs form the curved peripheral portions of the pressure-sensitive adhesive layer indicated by reference numeral 121 in the composite sheet for forming a protective film 1 shown in fig. 3. The distance (20 mm) between the circle having a diameter of 270mm and the arc corresponds to the symbol w in the composite sheet 1 for forming a protective film shown in FIG. 3 2 。
The half-cut portion describing the 2 concentric circles and the pair of arcs is cut in the longitudinal direction of the 3 rd laminated body (denoted by reference numeral w of the composite sheet 1 for forming a protective film shown in fig. 3) 1 The illustrated directions orthogonal to the width direction) are performed, half cuts with cuts are made from the coating layer side to the coating layer, the base material, and the adhesive layer, and 2 straight lines connecting arcs in the longitudinal direction between adjacent portions in a plan view are drawn. The cuts corresponding to the 2 straight lines form the planar peripheral edge of the pressure-sensitive adhesive layer indicated by reference numeral 122 in the composite sheet 1 for forming a protective film shown in fig. 3.
Next, the coating layer, the base material, and the adhesive layer were removed from the portion between the circle having a diameter of 270mm and the pair of arcs and the portion sandwiched by the 2 straight lines connecting the arcs in a plan view, thereby obtaining a composite sheet for forming a protective film shown in fig. 1 and 3. The circular adhesive layer (support sheet) in the composite sheet for forming a protective film corresponds to the diameter d in fig. 3 2 A 270mm circular adhesive layer 12 (support sheet 10). The first release film 1 in the composite sheet for forming a protective film corresponds to the release film 15 in fig. 3.
[ example 2]
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a base material having a surface roughness Ra of uneven surface of 1 μm instead of 0.4 μm was used as shown in table 1.
[ example 3]
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a base material having a surface roughness Ra of the uneven surface of 1 μm instead of 0.4 μm was used and the thickness of the coating layer was 1 μm instead of 3 μm, as shown in table 1.
[ example 4]
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that the thickness of the coating layer was 1 μm instead of 3 μm as shown in table 1.
[ example 5]
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a base material having a surface roughness Ra of the uneven surface of 1 μm instead of 0.4 μm was used and the thickness of the coating layer was set to 6 μm instead of 3 μm as shown in table 1.
[ example 6]
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a base material having a surface roughness Ra of the uneven surface of 3 μm instead of 0.4 μm was used and the thickness of the coating layer was set to 6 μm instead of 3 μm as shown in table 1.
Comparative example 1
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a base material having a surface roughness Ra of uneven surface of 1 μm instead of 0.4 μm was used and no coating layer was formed, as shown in table 1.
Comparative example 2
As shown in table 1, a composite sheet for forming a protective film was obtained in the same manner as in example 1, except that the base material was disposed so that the uneven surface faced the opposite side, that is, the pressure-sensitive adhesive layer side (inner side) 12395.
Comparative example 3
As shown in table 1, a composite sheet for forming a protective film was obtained in the same manner as in example 1, except that a substrate having a surface roughness Ra of the uneven surface of 1 μm instead of 0.4 μm was used, the substrate was disposed so that the uneven surface faced the opposite side, that is, the pressure-sensitive adhesive layer side (inner side) 12395.
Comparative example 4
A coating composition was prepared in the same manner as in example 1, except that the same amount of spherical silica surface-modified with epoxy groups (SC 2050MA, manufactured by Admatechs corporation, average particle diameter 0.5 μm) was used as the solid content in place of the dispersion liquid obtained by dispersing the silica sol in 2-ethoxyethanol.
A composite sheet for forming a protective film was obtained in the same manner as in example 1, except that the coating composition was used.
In the obtained composite sheet for forming a protective film, the surface roughness Ra of the outermost surface of the base material side was 0.8 μm as shown in table 1.
< evaluation of composite sheet for Forming protective film >
[ laser printability ]
In the composite sheets for forming a protective film obtained in the above examples and comparative examples, the 1 st release film was removed, and the adhesive layer was attached to a stainless steel ring frame using an attaching apparatus ("RAD-2700F/12" manufactured by ledebacaceae) while the film for forming a protective film was attached to the back surface of a silicon wafer (outer diameter 8 inches, thickness 100 μm) heated to 70 ℃.
Subsequently, the protective film-forming film was subjected to a heat treatment at 130 ℃ for 2 hours to thermally cure the protective film-forming film, thereby forming a protective film.
Then, the protective film was irradiated with laser light having a wavelength of 532nm from the base material side under conditions of an output of 0.6W, a frequency of 40kHz, and a scanning speed of 100 mm/sec using a printing apparatus ("VK 9700" manufactured by KEYENCE corporation), and laser printing was performed on the protective film in the following 2 patterns (pattern 1, pattern 2).
(Pattern)
Pattern 1: the size of the characters is 0.4mm multiplied by 0.5mm, the space between the characters is 0.3mm, and the number of the characters is 20
Pattern 2: the size of the characters is 0.2mm multiplied by 0.5mm, the space between the characters is 0.3mm, and the number of the characters is 20
Next, the characters formed on the protective film by the laser printing were evaluated for visibility (laser printability) from the base material side according to the following criteria, and the results are shown in table 1.
(evaluation criteria)
A: all the characters of the patterns 1 and 2 are clear, and the characters of the patterns 1 and 2 can be read without problems.
B: although at least a part of the characters in the pattern 2 are unclear, all the characters in the pattern 1 are clear, and the characters of the pattern 1 can be read without problems.
C: either of the patterns 1 and 2 is at least partially text-unclear.
[ blocking resistance (1) ]
The composite sheets for forming a protective film of each of the examples and comparative examples, which had a length of 10m and was obtained as described above, were wound around a core material made of an ABS resin and left to stand at room temperature for 3 days.
Next, with respect to the composite sheets for forming a protective film of examples 1 to 6 and comparative example 4, it was tried to draw out 10 lamination units in which the coating layer, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the 1 st release film were laminated in this order, and with respect to the composite sheets for forming a protective film of comparative examples 1 to 3, since the coating layer was not present, it was tried to draw out 10 lamination units in which the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the 1 st release film were laminated in this order, and at this time, the degree of sticking was evaluated in accordance with the following criteria with respect to the case where there was no sticking or sticking between the contact portions of the composite sheets for forming a protective film which were in contact with each other at the time of winding up, and the results are shown in table 1.
(evaluation criteria)
A: the adhesion of the contact portions was not confirmed at all.
B: although slight adhesion between the contact portions was confirmed, the composite sheet for forming a protective film could be pulled out without any problem.
C: the contact portions are partially and completely bonded to each other, and when the composite sheet for forming a protective film is taken out, the 1 st release film is peeled from the pressure-sensitive adhesive layer.
[ blocking resistance (2) ]
The composite sheets for forming a protective film obtained in the above examples and comparative examples were cut into a strip shape having a width of 50mm and a length of 100 mm. In the cutting, the longitudinal direction of the tape is aligned with the application direction of the adhesive composition.
10 sheets of the thus-obtained strips were prepared, and the strips were laminated to prepare test pieces. In examples 1 to 6 and comparative example 4, the above-described ribbons were laminated with the coating layer facing upward. However, in each of comparative examples 1 to 3, since the coating layer was not present, the above-described ribbons were laminated with the base material facing upward. Then, the test piece was sandwiched by 2 glass plates (75 mm wide, 15mm long, 5mm thick), and the entire laminate of these glass plates and the test piece was placed at a predetermined position with one glass plate as the lowermost layer, and a weight was placed on the other uppermost glass plate, and the test piece was pressed. At this time, the force applied to the test piece in the stacking direction of the strips was 980.665mN (i.e., 100 gf). In this state, the entire laminate of the glass plate and the test piece was stored at 40 ℃ for 3 days in a moist heat promoter (manufactured by ESPEC corporation), and the test piece was subjected to a heat and pressure promotion test.
Next, the test piece was taken out from the moist heat facilitator, the lowermost 1 st release film (the 1 st release film in contact with the lowermost glass plate) and the protective film-forming film adjacent thereto were removed, and the exposed adhesive layer was bonded to the support plate with a double-sided adhesive tape, whereby the test piece from which only the lowermost 1 st release film and the protective film-forming film adjacent thereto were removed from the test piece after the accelerated heat and pressure test was fixed to the support plate.
Next, in the case of examples 1 to 6 and comparative example 4, the laminate composed of the coating layer, the base material, the pressure-sensitive adhesive layer, and the protective film forming film, which was the uppermost layer farthest from the support plate, was removed from the fixed sample, and the exposed 1 st release film was peeled from the adjacent coating layer using a tensile tester under conditions of a peeling speed of 300 mm/min and a peeling angle of 180 °, and the peeling force at that time was measured. In comparative examples 1 to 3, the laminate composed of the base material, the pressure-sensitive adhesive layer and the protective film forming film, which was the farthest from the uppermost layer of the support plate in the fixed sample, was removed, and the exposed 1 st release film was peeled from the adjacent base material at a peeling speed of 300 mm/min and a peeling angle of 180 ° using a tensile tester, and the peeling force at this time was measured. The measured value of the peeling force of the 1 st release film thus obtained was used as an index of the blocking resistance of the composite sheet for forming a protective film.
When the peel force of the 1 st release film to be measured is sufficiently small, if the protective film forming film adjacent to the 1 st release film in the lowermost layer (the 1 st release film in contact with the glass plate in the lowermost layer) is removed from the test piece taken out from the moist heat facilitator as described above, the 1 st release film to be measured for the peel force may be peeled from the adjacent layer (the coating layer in the case of examples 1 to 6, comparative example 4, and the base material in the case of comparative examples 1 to 3) first. In this case, after the lowermost 1 st release film was removed from the test piece taken out from the moist heat facilitator, the protective film forming film adjacent thereto was attached to the support plate by a double-sided adhesive tape without removing the protective film forming film, whereby only the lowermost 1 st release film was removed from the test piece, and the sample after the fixing was fixed to the support plate, and the peeling force of the 1 st release film was measured for the sample after the fixing in the same manner as described above.
The results are shown in Table 1.
[ surface roughness Ra of the outermost surface on the substrate side ]
The composite sheets for forming a protective film obtained in examples 1 to 6 and comparative example 4 were measured for surface roughness Ra of the outermost surface of the base material side, that is, the surface of the coating layer opposite to the base material side, using a contact surface roughness meter ("SURFTEST SV-3000" manufactured by Mitutoyo corporation) with a cutoff value λ c of 0.8mm and an evaluation length Ln of 4mm in accordance with JIS B0601:2001 standard, and the results are shown in table 1. Table 1 shows the surface roughness Ra of the surface of the substrate opposite to the pressure-sensitive adhesive layer side as the surface roughness Ra of the outermost surface of the substrate side of the composite sheet for forming a protective film of comparative examples 1 to 3.
[ gloss value of surface of coating layer ]
The composite sheets for forming a protective film obtained in examples 1 to 6 and comparative example 4 were measured for 20 ° specular gloss of the surface of the coating layer from the side opposite to the base material side using a gloss meter (gloss meter "VG2000" manufactured by japan electrochrome corporation) in accordance with JIS K7105, and the measured values were used as gloss values of the surface of the coating layer, and the results are shown in table 1.
[ haze measurement value measured from the coating layer side ]
The composite sheets for forming a protective film obtained in examples 1 to 6 and comparative example 4 were measured for haze from the coating layer side using a haze meter (NDH-2000, manufactured by nippon electro-color co., ltd.) according to JIS K7136, and the results are shown in table 1.
[ Table 1]
Figure BDA0001758059730000661
The composite sheets for forming a protective film of examples 1 to 6 were excellent in both laser printability and blocking resistance by providing a coating layer as the outermost layer on the substrate side.
In particular, the composite sheets for forming a protective film of examples 1, 2,4 and 5 were excellent in laser printability as compared with the composite sheets for forming a protective film of examples 3 and 6, and it is presumed that the values of "[ thickness (μm) of the coating layer ]/[ surface roughness Ra (μm) of the uneven surface of the substrate") of the composite sheets for forming a protective film of examples 1, 2,4 and 5 were larger, and the relative thickness of the coating layer was thicker than the surface roughness Ra of the uneven surface of the substrate, whereby the surface roughness Ra (μm) of the outermost surface on the substrate side (the surface of the coating layer opposite to the substrate side) was smaller.
The reason why the composite sheets for forming a protective film of examples 1 to 4 were superior in blocking resistance to the composite sheets for forming a protective film of examples 5 and 6 was presumably because the composite sheets for forming a protective film of examples 1 to 4 had a thinner coating layer.
In addition, no void portion was observed between the substrate and the pressure-sensitive adhesive layer in any of the protective film-forming composite sheets of examples 1 to 6.
In contrast, the composite sheet for forming a protective film of comparative example 1 had an uneven surface on the surface (back surface) opposite to the surface (front surface) on the side provided with the pressure-sensitive adhesive layer of the base material and no coating layer, as in the composite sheet shown in fig. 4, and therefore had poor laser printability although excellent blocking resistance.
The composite sheet for forming a protective film of comparative example 2 had a smooth surface (back surface) opposite to the surface (front surface) having the pressure-sensitive adhesive layer of the base material and no coating layer, as with the composite sheet shown in fig. 5, and thus had good laser printability but poor blocking resistance. The composite sheet for forming a protective film of comparative example 3 has the same configuration as the composite sheet for forming a protective film of comparative example 2, and not only is it inferior in blocking resistance but also in laser printability. This is presumed to be because the surface (surface) of the substrate on the side provided with the pressure-sensitive adhesive layer was uneven, and the surface roughness Ra was larger than that of the composite sheet for forming a protective film of comparative example 2. In comparative example 3, since the surface roughness Ra of the uneven surface is large, the shape of the uneven surface is also reflected on the surface of the protective film, and the degree of unevenness in the surface of the protective film is larger than in comparative example 2, whereby the diffuse reflection of light is larger, and the laser printability is further deteriorated. It is also presumed that the composite sheets for forming a protective film of comparative examples 2 and 3 each had a void portion between the uneven surface of the base material and the pressure-sensitive adhesive layer, but the surface roughness Ra of the uneven surface of comparative example 3 was larger and the void portion was larger than that of comparative example 2, and therefore, the diffuse reflection of light was larger in comparative example 3 than in comparative example 2, and the laser printability was further deteriorated.
The composite sheet for forming a protective film of comparative example 4 had an uneven surface on the surface (back surface) opposite to the surface (front surface) on the side provided with the pressure-sensitive adhesive layer of the base material and also had a coating layer, and was excellent in blocking resistance but poor in laser printability, as in the composite sheet for forming a protective film of example 1. This is presumably because, in the composite sheet for forming a protective film of comparative example 4, the surface roughness Ra (μm) of the outermost surface on the substrate side (the surface on the opposite side of the coating layer from the substrate side) was larger than the surface (the back surface) on the opposite side of the surface (the surface) on the side provided with the pressure-sensitive adhesive layer of the substrate.
Industrial applicability
The present invention can be used for manufacturing a semiconductor chip or the like whose back surface is protected by a protective film.

Claims (5)

1. A composite sheet for forming a protective film, which comprises a support sheet, a film for forming a protective film on one surface of the support sheet, and a coating layer on the surface of the support sheet opposite to the side having the film for forming a protective film,
the coating layer contains a cured product of a coating composition containing a photopolymerization initiator,
the surface roughness Ra of the surface of the coating layer on the side opposite to the side in contact with the support sheet is smaller than the surface roughness Ra of the surface of the support sheet on the side provided with the coating layer.
2. The composite sheet for forming a protective film according to claim 1, wherein a peeling force of a peeling film is 10mN/50mm or less as measured by the following method using the composite sheet for forming a protective film further comprising the peeling film on the film for forming a protective film,
method for measuring peeling force of release film:
a composite sheet for forming a protective film, which has a release film on a film for forming a protective film and has a width of 50mm and a length of 100mm, is laminated so that the coating layers are all oriented in the same direction and the total thickness of the coating layers is 10 to 60 [ mu ] m, thereby forming a laminate having one outermost layer as a coating layer and the other outermost layer as a release film, the laminate is allowed to stand at 40 ℃ for 3 days while applying 980.665mN of force in the laminating direction of the composite sheet for forming a protective film, and then the release film of the coating layer closest to the outermost layer is released from the adjacent coating layer in the laminating direction at a release speed of 300 mm/min and a release angle of 180 DEG, and the release force at that time is measured.
3. The composite sheet for forming a protective film according to claim 1 or 2, wherein the support sheet is formed by laminating a base material and an adhesive layer,
the composite sheet for forming a protective film is formed by sequentially laminating the coating layer, the base material, the adhesive layer and the film for forming a protective film.
4. The composite sheet for forming a protective film according to claim 3, wherein the adhesive layer is an energy ray-curable or non-energy ray-curable adhesive layer.
5. The composite sheet for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film is a thermosetting or energy ray-curable film.
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