CN108271381B - Semiconductor processing sheet - Google Patents

Semiconductor processing sheet Download PDF

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Publication number
CN108271381B
CN108271381B CN201780003864.0A CN201780003864A CN108271381B CN 108271381 B CN108271381 B CN 108271381B CN 201780003864 A CN201780003864 A CN 201780003864A CN 108271381 B CN108271381 B CN 108271381B
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adhesive layer
semiconductor processing
semiconductor
release film
film
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CN108271381A (en
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佐藤明德
中村优智
山下茂之
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Lintec Corp
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

The present invention provides a semiconductor processing sheet 1, which at least comprises a base material 10, a semiconductor adhesive layer 80, and a peeling film 30, wherein the arithmetic mean roughness Ra of a first surface 101 of the base material 10 is 0.01-0.8 μm, the ratio (alpha/beta) of alpha to beta is 0 or more and less than 1.0, and the peeling force beta is 10-1000 mN/50mm, when the peeling force at the interface between the first surface 101 of the base material 10 and a second surface 302 of the peeling film 30 is alpha, and the peeling force at the interface between a second surface 802 of the semiconductor adhesive layer 80 and a first surface 301 of the peeling film 30 is beta. The sheet 1 for semiconductor processing has excellent light transmittance and is less likely to cause blocking.

Description

Semiconductor processing sheet
Technical Field
The present invention relates to a sheet for semiconductor processing.
Background
In the production of semiconductor chips from semiconductor wafers, semiconductor processing sheets such as dicing sheets and back grinding sheets are generally used. In recent years, such a semiconductor processing sheet is required to have transparency to light of a desired wavelength (hereinafter, sometimes referred to as "light transparency").
For example, in recent years, silicon wafers or glass wafers having a smaller thickness than ever before are increasingly used. When these wafers are cut with a blade, wafer defects such as chipping and wafer breakage are likely to occur. Therefore, when using these wafers, the shape of the wafer is inspected by crossing the semiconductor processing sheet from the surface of the wafer in contact with the semiconductor processing sheet in a state where the wafer is attached to the semiconductor processing sheet after dicing. In order to perform this inspection satisfactorily, the semiconductor processing sheet must transmit light for inspection.
Further, when slicing a thin wafer, since there is a concern of edge chipping or the like when performing full dicing using a blade, a first dicing method of performing back grinding after half dicing a wafer first may be used; or a stealth dicing (stealth dicing) method in which a modified layer is formed inside a wafer by laser, and then the wafer is diced by back grinding.
When stealth dicing is performed, when a modified layer is formed inside a wafer by laser irradiation and then the wafer is attached to a semiconductor processing sheet, there is a risk that the wafer is broken due to the pressure of attachment. In order to avoid this risk, after the wafer is attached to the semiconductor processing sheet in advance, the wafer is irradiated with laser light over the semiconductor processing sheet, thereby forming a modified layer. In this case, the semiconductor processing sheet must transmit the laser beam in order to be irradiated with the laser beam satisfactorily.
Further, when the wafer is flip-chip packaged, a product surface, a lot number, and the like are generally laser-printed on the back surface of the wafer. In order to perform such laser printing, a step of conveying the wafer whose back surface has been ground to a laser printing apparatus is provided. Thinned wafers used in recent years have a high risk of wafer breakage during transportation. In order to avoid this risk, it has been studied to convey a thinned wafer in a state of being stuck on a semiconductor processing sheet, and to irradiate laser light over the semiconductor processing sheet to perform printing. In order to perform laser printing satisfactorily, the semiconductor processing sheet must transmit laser light.
When a protective film is provided on the back surface of the wafer, the protective film is also subjected to laser printing. At this time, the protective film-forming layer of the semiconductor processing sheet including the protective film-forming layer is irradiated with laser light over the base material and the adhesive layer of the semiconductor processing sheet, and printing is performed. In this case, in order to perform laser printing satisfactorily, the substrate, adhesive layer, and the like of the semiconductor processing sheet must also transmit laser light.
A semiconductor processing sheet generally includes a base material and an adhesive layer laminated on one surface of the base material. Further, in order to protect the adhesive layer until the semiconductor processing sheet is used, a release film is provided on the adhesive layer. For example, patent documents 1 and 2 describe a semiconductor processing sheet in which a base material, an adhesive layer, and a release film are sequentially laminated. In addition, in general, depending on the use of the sheet for semiconductor processing, another layer such as an adhesive layer, a protective film-forming layer, or the like may be provided between the adhesive layer and the release film.
Documents of the prior art
Patent document
Patent document 1: japanese Kaiki Hei No. 8-1220
Patent document 2: japanese Kaiki Hei No. 2-146144
Disclosure of Invention
Technical problem to be solved by the invention
The semiconductor processing sheet can achieve excellent light transmittance to light having a desired wavelength by increasing the light transmittance of the base material and the adhesive layer, respectively. For example, the smoothness can be improved on the surface of the semiconductor processing sheet on the substrate side, that is, the surface of the substrate opposite to the adhesive layer.
However, if the smoothness of the surface of the semiconductor processing sheet on the substrate side is improved in order to obtain a semiconductor processing sheet having high light transmittance, blocking is likely to occur. That is, when a long semiconductor processing sheet is wound in a roll shape, the semiconductor processing sheets easily adhere to each other. When such adhesion occurs, it becomes difficult to unwind the semiconductor processing sheet from the roll or to cause peeling at an undesired interface (for example, an interface between the adhesive layer and the release film). In addition, in the semiconductor processing sheet in which the base material and the adhesive layer are precut in accordance with the shape of the wafer, if such blocking occurs, when the semiconductor processing sheet is unwound from a roll, there are problems that the laminate of the base material and the adhesive layer is peeled off from the release film, or the base material side of the peeled laminate is stuck to the back surface of the release film.
Here, patent documents 1 and 2 disclose: the surface of the release film opposite to the adhesive layer is subjected to embossing, and the purpose is to prevent air from being trapped between the semiconductor processing sheets when the semiconductor processing sheets are wound in a roll.
On the other hand, the semiconductor processing sheet disclosed in patent document 1 or 2 does not have high smoothness on the surface on the substrate side, and cannot be used for inspection, laser dicing, stealth dicing, laser printing, and the like of the above-described sheet for transmission through a semiconductor processing.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a sheet for semiconductor processing which has excellent light transmittance and is less likely to cause blocking.
Means for solving the problems
In order to achieve the above object, a first aspect of the present invention provides a semiconductor processing sheet, comprising at least: a base material having a first surface and a second surface located on the opposite side of the first surface; a semiconductor adhesive layer laminated on the second surface side of the base material, and having a first surface on a side close to the base material and a second surface on a side far from the base material; and a release film laminated on the second surface side of the semiconductor attachment layer, and having a first surface on a side close to the semiconductor attachment layer and a second surface on a side far from the semiconductor attachment layer; the method is characterized in that: the arithmetic mean roughness Ra of the first surface of the base material is 0.01 to 0.8 [ mu ] m, and when the peeling force at the interface between the first surface of the base material and the second surface of the peeling film after the first surface of the base material and the second surface of the peeling film are laminated and stored at 40 ℃ for 3 days is set to [ alpha ], and the peeling force at the interface between the second surface of the semiconductor adhesive layer and the first surface of the peeling film after the second surface of the semiconductor adhesive layer and the first surface of the peeling film are adhered and stored at 40 ℃ for 3 days is set to [ beta ], the ratio of [ alpha ]/[ beta ] is 0 or more and less than 1.0, and the peeling force [ beta ] is 10 to 1000mN/50mm (invention 1).
According to the above invention (invention 1), the smoothness of the surface on the substrate side is improved and the substrate has high light transmittance to light of a desired wavelength by setting the arithmetic average roughness Ra of the first surface of the substrate to 0.01 to 0.8 μm. Further, when the ratio (α/β) of the peeling force α to the peeling force β is 0 or more and less than 1.0, the adhesiveness between the semiconductor processing sheet in a state of being wound in a roll shape is not higher than the adhesiveness between the layers constituting the semiconductor processing sheet, and excellent blocking resistance is exhibited. This enables satisfactory unwinding, and prevents undesirable interface peeling during unwinding. Further, since the peeling force beta is 10 to 1000mN/50mm, the laminate including the base material and the semiconductor adhesive layer can be peeled from the peeling film with an appropriate peeling force when the semiconductor processing sheet is used.
In the above invention (invention 1), the arithmetic average roughness Ra of the second surface of the release film is preferably 0.02 to 0.8 μm (invention 2).
In the above inventions (inventions 1 and 2), the release film preferably includes release agent layers on the first surface side and the second surface side, respectively (invention 3).
In the above inventions (inventions 1 to 3), the semiconductor adhesive layer may be an adhesive layer (invention 4).
In the above inventions (inventions 1 to 3), the semiconductor attaching layer may be an adhesive layer (invention 5).
In the above inventions (inventions 1 to 3), the semiconductor adhesive layer may be a protective film forming layer (invention 6).
In the above inventions (inventions 1 to 3), the semiconductor adhesive layer may be composed of an adhesive layer and an adhesive layer located between the adhesive layer and the release film (invention 7).
In the above inventions (inventions 1 to 3), the semiconductor adhesive layer may be composed of an adhesive layer and a protective film forming layer located between the adhesive layer and the release film (invention 8).
In the above inventions (inventions 1 to 8), the semiconductor processing sheet may be a laminate comprising the base material and the semiconductor adhesive layer, the laminate having a shape different from that of the release film in a plan view, and being laminated on the long release film (invention 9).
A second aspect of the present invention provides a semiconductor processing sheet, including at least: a base material having a first surface and a second surface located on the opposite side of the first surface; a semiconductor adhesive layer laminated on the second surface side of the base material, and having a first surface on a side close to the base material and a second surface on a side far from the base material; a jig adhesive layer which is laminated on the second surface side of the semiconductor adhesive layer, and which has a first surface on the side close to the semiconductor adhesive layer and a second surface on the side away from the semiconductor adhesive layer; and a release film that is laminated on at least a second surface side of the adhesive agent layer for a clip, and that has a first surface on a side close to the adhesive agent layer for a clip and a second surface on a side away from the adhesive agent layer for a clip, characterized in that: the arithmetic mean roughness Ra of the first surface of the substrate is 0.01 to 0.8 [ mu ] m, the peeling force at the interface between the first surface of the substrate and the second surface of the release film after the first surface of the substrate and the second surface of the release film are laminated and stored at 40 ℃ for 3 days is defined as alpha, and the ratio (alpha/beta) of the alpha to the beta is 0 or more and less than 1.0, and the peeling force beta is 10 to 1000mN/50mm (invention 10), when the peeling force at the interface between the second surface of the adhesive layer for a jig and the first surface of the release film after the second surface of the adhesive layer for a jig and the first surface of the release film are attached and stored at 40 ℃ for 3 days is defined as beta.
Effects of the invention
According to the present invention, a semiconductor processing sheet having excellent light transmittance and less blocking can be provided.
Drawings
Fig. 1 is a sectional view of a semiconductor processing sheet according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view showing a semiconductor processing sheet according to a first embodiment of the present invention in a stacked state.
Fig. 3 is a cross-sectional view of a semiconductor processing sheet according to a first embodiment of the present invention.
Fig. 4 is a sectional view of a semiconductor processing sheet according to a second embodiment of the present invention.
Fig. 5 is a sectional view of a semiconductor processing sheet according to a third embodiment of the present invention.
Fig. 6 is a cross-sectional view of a semiconductor processing sheet according to a fourth embodiment of the present invention.
Fig. 7 is a plan view of a semiconductor processing sheet according to a fifth embodiment of the present invention.
Fig. 8 is a sectional view of a semiconductor processing sheet according to a second embodiment of the present invention.
Fig. 9 is a sectional view of a semiconductor processing sheet according to a third embodiment of the present invention.
Fig. 10 is a sectional view taken along line a-a of fig. 9.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
Fig. 1 shows a semiconductor processing sheet 1 according to a first embodiment. The semiconductor processing sheet 1 is formed by sequentially laminating a base 10, a semiconductor adhesive layer 80, and a release film 30. The substrate 10 has a first surface 101 on a side away from the semiconductor adhesion layer 80 and a second surface 102 on a side close to the semiconductor adhesion layer 80. The semiconductor adhesive layer 80 has a first surface 801 on the side close to the substrate 10, and a second surface 802 on the side close to the release film 30. The release film 30 has a first surface 301 on the side close to the semiconductor adhesive layer 80 and a second surface 302 on the side away from the semiconductor adhesive layer 80.
In the semiconductor processing sheet 1 of the present embodiment, the arithmetic mean roughness Ra of the first surface 101 of the base material 10 is 0.01 to 0.8. mu.m. By smoothing the first surface 101 of the substrate 10 in this manner, scattering of light irradiated on the first surface 101 on the surface can be reduced, and the substrate 10 can exhibit high light transmittance.
In the semiconductor processing sheet 1 of the present embodiment, the ratio (α/β) of the peeling force α to the peeling force β is 0 or more and less than 1.0. Here, the peeling force α is a peeling force at an interface between the first surface 101 of the substrate 10 and the second surface 302 of the release film 30, as described later; the peeling force β is a peeling force at an interface between the second surface 802 of the semiconductor adhesive layer 80 and the first surface 301 of the release film 30, as described later. Thus, the adhesion between the semiconductor processing sheets 1 in the state where the semiconductor processing sheets 1 are wound in a roll shape is not higher than the adhesion between the layers constituting the semiconductor processing sheets 1, and excellent blocking resistance is exhibited. Therefore, unwinding can be performed satisfactorily, and undesired peeling at the interface does not occur at the time of unwinding.
Further, in the semiconductor processing sheet 1 of the present embodiment, the peeling force β is 10 to 1000mN/50 mm. Thus, when the semiconductor processing sheet is used, the laminate including the base material and the semiconductor adhesive layer can be peeled from the release film with an appropriate peeling force.
1. Physical properties of semiconductor processing sheet
In the semiconductor processing sheet 1 of the present embodiment, when the peeling force at the interface between the first surface 101 of the base 10 and the second surface 302 of the release film 30 is α and the peeling force at the interface between the second surface 802 of the semiconductor adhesive layer 80 and the first surface 301 of the release film 30 is β, the ratio (α/β) of the α to the β is 0 or more, preferably 0.05 or more, and particularly preferably 0.1 or more. The ratio (α/β) is less than 1.0, preferably 0.5 or less, and particularly preferably 0.2 or less. Here, the peeling force α is the peeling force of the release film 30 with respect to the substrate 10 after the first surface 101 of the substrate 10 and the second surface 302 of the release film 30 are laminated and stored at 40 ℃ for 3 days in a dry state. The peeling force β is a peeling force of the peeling film 30 to the semiconductor adhesive layer 80 after storing at 40 ℃ for 3 days in a dry state in a state where the second surface 802 of the semiconductor adhesive layer 80 and the first surface 301 of the peeling film 30 are adhered. When the ratio (α/β) is 0, the value of the peeling force α is 0, which means that the peeling force α is too small to be measured or the peeling film 30 is peeled from the substrate 10 before the measurement. When the ratio (α/β) of the peeling force α to the peeling force β is 0 or more and less than 1.0, as shown in fig. 2, when the semiconductor processing sheets 1 are stacked on each other, the adhesiveness between the semiconductor processing sheets 1 is not higher than the adhesiveness between the layers constituting the semiconductor processing sheets. Specifically, the adhesiveness between the first surface 101 of the substrate 10 and the second surface 302 of the release film 30 facing the first surface is not higher than the adhesiveness between the substrate 10 and the semiconductor adhesive layer 80 and the adhesiveness between the semiconductor adhesive layer 80 and the release film 30. Thus, when the semiconductor processing sheet 1 wound up and laminated in a roll shape is unwound, the first surface 101 of the substrate 10 of the semiconductor processing sheet 1 does not adhere to the second surface 302 of the release film 30 of the semiconductor processing sheet 1 superposed thereon, exhibiting excellent blocking resistance. Further, the occurrence of peeling at an undesired interface of the semiconductor processing sheet 1 at the time of unwinding is suppressed. This enables the semiconductor processing sheet 1 to be favorably unwound.
In the present specification, the peeling force β is defined as a peeling force at an interface between the peeling film 30 and a main layer in contact therewith. For example, in the semiconductor processing sheet 1, the peeling force β at the interface between the semiconductor adhesive layer 80 and the peeling film 30 is defined because the peeling film 30 is in contact with the semiconductor adhesive layer 80. On the other hand, in the semiconductor processing sheet 2 (see fig. 8) of the second embodiment including the adhesive agent layer 60 for a jig, which will be described later, the semiconductor adhesive layer 80 and the adhesive agent layer 60 for a jig simultaneously contact the release film 30. Here, the contact between the release film 30 and the jig adhesive layer 60 has a greater influence on the peeling force when peeling the release film 30 from the semiconductor processing sheet 2 than the contact between the release film 30 and the semiconductor adhesive layer 80. Therefore, in the semiconductor processing sheet 2 including the adhesive layer 60 for a jig, as described later, the peeling force β at the interface between the surface (second surface 602) of the adhesive layer 60 for a jig on the side of the release film 30 and the surface (first surface 301) of the adhesive layer 60 for a jig of the release film 30 is defined.
In the semiconductor processing sheet 1 of the present embodiment, the peeling force β is 10 to 1000mN/50mm, preferably 10 to 500mN/50mm, and particularly preferably 30 to 200mN/50 mm. When the peeling force β is less than 10mN/50mm, the laminate of the base material 10 and the semiconductor adhesive layer 80 is easily peeled from the peeling film 30 when the semiconductor processing sheet 1 is unwound from a roll or at an unintended stage other than the unwinding. When the peeling force β is greater than 1000mN/50mm, the laminated body of the base material 10 and the semiconductor adhesive layer 80 is difficult to peel from the peeling film 30 when the semiconductor processing sheet 1 is used, and workability is deteriorated. In particular, when the laminate is sequentially bonded to a semiconductor wafer using a wafer laminator, a problem occurs in that the laminate cannot be satisfactorily peeled from the release film 30 and thus cannot be bonded.
The thickness of the semiconductor processing sheet 1 of the present embodiment is not limited as long as the semiconductor processing sheet 1 can function properly in the process used. The thickness is preferably 50 to 300 μm, particularly preferably 50 to 250 μm, and further preferably 50 to 230 μm. The thickness of the semiconductor processing sheet 1 in the present specification means a thickness after removing the release film 30 peeled before the use of the semiconductor processing sheet 1.
2. Base material
In the semiconductor processing sheet 1 of the present embodiment, the arithmetic mean roughness Ra of the first surface 101 of the base material 10 is 0.01 to 0.8. mu.m, particularly preferably 0.02 to 0.5. mu.m, and more preferably 0.03 to 0.3. mu.m. If the arithmetic average roughness Ra is less than 0.01 μm, the first surface 101 becomes excessively smooth, the value of the peeling force α becomes excessively large, blocking is likely to occur when the semiconductor processing sheet 1 is wound in a roll shape, and the peeling force α and the peeling force β hardly satisfy the above-described relationship. When the arithmetic average roughness Ra is larger than 0.8 μm, the light irradiated on the first surface 101 is easily scattered on the surface, and the light transmittance is deteriorated. The arithmetic average roughness Ra in the present specification is a value measured according to JIS B0601:2013, and the details of the measurement method are shown in examples described later.
In order to achieve the arithmetic average roughness Ra, it is preferable to manufacture the base material 10 so as to have the arithmetic average roughness Ra. For example, the substrate 10 having the arithmetic average roughness Ra is preferably manufactured by adjusting the surface roughness of a roll used for extrusion molding of the substrate 10. Or, when the substrate 10 is produced by the blow molding method, the roughness of the surface to be the first surface 101 is preferably adjusted to the arithmetic average roughness Ra.
The arithmetic average roughness Ra of the second surface 102 of the substrate 10 may be set as appropriate as long as the light transmittance of the substrate 10 can be ensured, and is preferably 0.01 to 2.0 μm, more preferably 0.03 to 1.5 μm, and still more preferably 0.05 to 1.0 μm, for example.
In the semiconductor processing sheet 1 of the present embodiment, the material constituting the base material 10 is not particularly limited as long as it exhibits excellent light transmittance to light of a desired wavelength and the semiconductor processing sheet 1 can exhibit a desired function in the step of use. The substrate 10 may include a film (resin film) mainly made of a resin-based material. The substrate 10 is preferably composed of only a resin film. Specific examples of the resin film include an ethylene-vinyl acetate copolymer film; ethylene-based copolymer films such as ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid methyl ester copolymer films, and other ethylene- (meth) acrylic acid ester copolymer films; polyolefin films such as polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, ethylene-norbornene copolymer films, and norbornene resin films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; polyester-based films such as polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film; a (meth) acrylate copolymer film; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; fluororesin films, and the like. Examples of the polyethylene film include a Low Density Polyethylene (LDPE) film, a Linear Low Density Polyethylene (LLDPE) film, and a High Density Polyethylene (HDPE) film. Further, modified membranes such as crosslinked membranes and ionic polymer membranes can also be used. The substrate 10 may be a film composed of the above-described 1 kind of material, or may be a film composed of a combination of the above-described 2 kinds or more of materials. Further, the multilayer structure may be a multilayer film in which a plurality of layers made of 1 or more of the above materials are laminated. In the laminated film, the materials constituting the respective layers may be the same kind or different kinds. Among the above films, an ethylene-vinyl acetate copolymer film, an ethylene-methyl methacrylate copolymer film, a polyvinyl chloride film, or a polypropylene film is preferably used as the substrate 10. In the present specification, "(meth) acrylic" refers to both acrylic and methacrylic. Other similar terms are also the same.
The substrate 10 may further contain various additives such as a flame retardant, a plasticizer, an antistatic agent, a lubricant, an antioxidant, a colorant, an infrared absorber, an ultraviolet absorber, and an ion scavenger in the film as long as the excellent light transmittance to light of a desired wavelength is not impaired. The content of these additives is not particularly limited, but is preferably within a range in which the substrate 10 exhibits excellent light transmittance and a desired function.
As described later, the adhesive layer 20 may be used as the semiconductor adhesive layer 80, and when the adhesive layer 20 is cured using an energy ray, the substrate 10 is preferably light-transmissive to the energy ray. Examples of the energy ray include ultraviolet rays and electron beams.
The second surface 102 of the substrate 10 may be subjected to surface treatment such as primer treatment, corona treatment, or plasma treatment in order to improve adhesion to the semiconductor adhesive layer 80, as long as the light transmittance of the semiconductor processing sheet 1 is not impaired.
The thickness of the substrate 10 is not limited as long as the semiconductor processing sheet 1 can function properly in the process used. The thickness is preferably 20 to 450 μm, particularly preferably 25 to 300 μm, and further preferably 50 to 200 μm.
3. Release film
The arithmetic average roughness Ra of the second surface 302 of the release film 30 is preferably 0.02 to 0.8. mu.m, particularly preferably 0.03 to 0.5. mu.m, and further preferably 0.05 to 0.3. mu.m. By making the arithmetic average roughness Ra of the second surface 302 be 0.02 to 0.8 μm, the second surface 302 has an appropriate roughness without the value of the peeling force α becoming too large. This makes it easy for the peeling force α and the peeling force β to satisfy the above relationship. Further, by setting the arithmetic mean roughness Ra of the second surface 302 to 0.02 μm or more, the second surface 302 of the release film 30 does not easily adhere to the first surface 101 of the smooth substrate 10 even when the semiconductor processing sheet 1 is wound into a roll, and as a result, blocking can be effectively prevented from occurring. Further, by setting the arithmetic mean roughness Ra of the second surface 302 to 0.8 μm or less, when the semiconductor processing sheet 1 is wound up in a roll shape, even if the surface shape of the second surface 302 of the release film 30 is transferred to the first surface 101 of the substrate 10, it is possible to prevent the smoothness of the first surface 101 from being lowered.
In order to achieve the arithmetic average roughness Ra, the release film 30 may be manufactured to have the arithmetic average roughness Ra. Or after the constituent material of the release film 30 is made into a sheet shape, the sheet is subjected to a surface treatment so as to have the above arithmetic average roughness Ra. In the former case, the release film 30 having the arithmetic average roughness Ra can be produced by adjusting the roughness of a roll used for extrusion molding of the release film 30, for example. In the latter case, the release film 30 having the arithmetic average roughness Ra can be produced by, for example, subjecting the sheet to sandblasting, embossing, or the like.
The arithmetic average roughness Ra of the first surface 301 of the release film 30 can be appropriately set as long as the above-described relationship between the release force α and the release force β and the above-described value of the release force β can be achieved, and is preferably 0.02 to 0.10 μm, particularly preferably 0.02 to 0.07 μm, and further preferably 0.03 to 0.05 μm, for example.
In order to exhibit releasability from the semiconductor adhesive layer 80, the release film 30 is usually provided with a release agent layer on the first surface 301 side. In addition, the release film 30 of the sheet 1 for semiconductor processing according to the present embodiment may be provided with a release agent layer on each of the first surface 301 side and the second surface 302 side. In this case, the release film 30 has a structure in which release agent layers are provided on both surfaces of a base material such as a resin film. By providing the release agent layer on the first surface 301 side, the release force β can easily achieve the above value. Further, by providing a release agent layer on the second surface 302 side, the above relationship between the release force α and the release force β can be easily achieved. As the release agent, silicone release agents, alkyd release agents, fluorine release agents, long-chain alkyl release agents, rubber release agents, and the like can be used. Among them, from the viewpoint of easy adjustment of the peeling force β to the above value, a silicone-based peeling agent is preferably used on the first surface 301 side, and from the viewpoint of easy adjustment of the ratio (α/β) of the peeling force α to the peeling force β to the above value, a silicone-based peeling agent or an alkyd-based peeling agent is preferably used on the second surface 302 side.
As a material constituting the release film 30, for example, a resin film can be used. Specific examples of the resin film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin films such as polypropylene and polyethylene.
The thickness of the release film 30 is not particularly limited, but is usually about 12 to 250 μm.
4. Semiconductor attaching layer
The semiconductor adhesive layer 80 is a layer to which a semiconductor wafer or the like is adhered or a layer to which a semiconductor wafer or the like is adhered when the semiconductor processing sheet 1 of the present embodiment is used. The bonding at this time may be performed temporarily when the semiconductor processing sheet 1 is used, or may be performed continuously even after the semiconductor processing sheet 1 is used. Preferred examples of the semiconductor adhesive layer 80 include an adhesive layer 20, an adhesive layer 40, a protective film-forming layer 50, a laminate composed of the adhesive layer 20 and the adhesive layer 40, and a laminate composed of the adhesive layer 20 and the protective film-forming layer 50.
Fig. 3 shows a first embodiment of the semiconductor processing sheet 1 according to the first embodiment. In the semiconductor processing sheet 1a of this embodiment, the semiconductor adhesive layer 80 is the adhesive layer 20. In the semiconductor processing sheet 1a, the adhesive layer 20 has a first surface 201 on the side close to the substrate 10, and a second surface 202 on the side close to the release film 30. The semiconductor processing sheet 1a can be used as a dicing sheet, for example.
Fig. 4 shows a second embodiment of the semiconductor processing sheet 1 according to the first embodiment. In the semiconductor processing sheet 1b of this embodiment, the semiconductor adhesion layer 80 is the adhesive layer 40. In the semiconductor processing sheet 1b, the adhesive layer 40 has a first surface 401 on the side close to the substrate 10, and a second surface 402 on the side close to the release film 30. The semiconductor processing sheet 1b can be used as a die bonding sheet, for example.
Fig. 5 shows a third embodiment of the semiconductor processing sheet 1 according to the first embodiment. In the semiconductor processing sheet 1c of this embodiment, the semiconductor adhesive layer 80 is the protective film formation layer 50. In the semiconductor processing sheet 1c, the protective film formation layer 50 has a first surface 501 on the side close to the substrate 10, and a second surface 502 on the side close to the release film 30. The semiconductor processing sheet 1c can be used as a protective film forming sheet, for example.
Fig. 6 shows a fourth mode of the semiconductor processing sheet 1 according to the first embodiment. In the semiconductor processing sheet 1d of this embodiment, the semiconductor adhesive layer 80 is a laminate composed of the adhesive layer 20 and the adhesive layer 40. In the semiconductor processing sheet 1d, the adhesive layer 20 is located on the side close to the substrate 10, and the adhesive layer 40 is located on the side close to the release film 30. Further, the adhesive layer 20 has a first face 201 on the side close to the substrate 10, and a second face 202 on the side close to the release film 30. Further, the adhesive layer 40 has a first face 401 on the side close to the substrate 10, and a second face 402 on the side close to the release film 30. The semiconductor processing sheet 1d is used as a dicing die bonding sheet, for example.
Fig. 7 shows a fifth embodiment of the semiconductor processing sheet 1 according to the first embodiment. In the semiconductor processing sheet 1e of this embodiment, the semiconductor adhesive layer 80 is a laminate composed of the adhesive layer 20 and the protective film forming layer 50. In the semiconductor processing sheet 1e, the adhesive layer 20 is located on the side close to the substrate 10, and the protective film forming layer 50 is located on the side close to the release film 30. Further, the adhesive layer 20 has a first face 201 on the side close to the substrate 10, and a second face 202 on the side close to the release film 30. Further, the protective film forming layer 50 has a first face 501 on the side close to the substrate 10, and a second face 502 on the side close to the release film 30. The semiconductor processing sheet 1e can be used for dicing a semiconductor wafer, and after dicing, a protective film can be formed on a semiconductor chip by heating the protective film forming layer 50 or the like. The semiconductor processing sheet 1e can also be used as a protective film forming sheet.
(1) Adhesive layer
In the semiconductor processing sheet 1 of the present embodiment, the adhesive layer 20 may be composed of a non-energy ray-curable adhesive (a polymer that is not energy ray-curable) or an energy ray-curable adhesive. The non-energy ray-curable adhesive preferably has a desired adhesive force and removability, and for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, or the like can be used. Among these, acrylic adhesives are preferred which can effectively prevent the semiconductor wafer, the semiconductor chip, and the like from coming off in the dicing step and the like.
On the other hand, since the energy ray-curable adhesive is reduced in adhesive force by irradiation with an energy ray, when it is intended to separate a semiconductor wafer, a semiconductor chip, or the like from the semiconductor processing sheet 1, it can be easily separated by irradiation with an energy ray.
The energy ray-curable adhesive constituting the adhesive layer 20 may contain, as a main component, a polymer having energy ray-curing properties, or a mixture of a non-energy ray-curable polymer (a polymer having no energy ray-curing properties) and a monomer and/or oligomer having at least 1 or more energy ray-curable groups. Further, the curable resin composition may be a mixture of a polymer curable with energy rays and a non-energy ray-curable polymer, a mixture of a polymer curable with energy rays and a monomer and/or oligomer having at least 1 or more energy ray-curable groups, or a mixture of the above 3 kinds.
First, a case where the energy ray-curable adhesive contains a polymer having energy ray-curing properties as a main component will be described below.
The polymer having energy ray curability is preferably a (meth) acrylate (co) polymer (a) having an energy ray-curable functional group (energy ray-curable group) introduced into a side chain thereof (hereinafter, sometimes referred to as "energy ray-curable polymer (a)"). The energy ray-curable polymer (a) is preferably obtained by reacting an acrylic copolymer (a1) having a functional group-containing monomer unit with an unsaturated group-containing compound (a2) having a functional group bonded to the functional group.
The acrylic copolymer (a1) is composed of a structural unit introduced from a functional group-containing monomer and a structural unit introduced from a (meth) acrylate monomer or a derivative thereof.
The functional group-containing monomer as a structural unit of the acrylic copolymer (a1) is preferably a monomer having a polymerizable double bond and a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, or an epoxy group in the molecule.
Examples of the hydroxyl group-containing monomer include 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. These can be used alone, also can be combined with more than 2.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These can be used alone, also can be combined with more than 2.
Examples of the amino group-containing monomer or substituted amino group-containing monomer include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. These can be used alone, also can be combined with more than 2.
As the (meth) acrylate monomer constituting the acrylic copolymer (a1), an alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms, a cycloalkyl (meth) acrylate, and benzyl (meth) acrylate can be used. Among them, alkyl (meth) acrylates having an alkyl group of 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, are particularly preferably used.
The acrylic copolymer (a1) is generally formed by containing the structural unit introduced by the functional group-containing monomer at a ratio of 3 to 100% by mass, preferably 5 to 40% by mass, and generally containing the structural unit introduced by the (meth) acrylate monomer or its derivative at a ratio of 0 to 97% by mass, preferably 60 to 95% by mass.
The acrylic copolymer (a1) can be obtained by copolymerizing the functional group-containing monomer described above with a (meth) acrylate monomer or a derivative thereof by a conventional method, and besides these monomers, dimethylacrylamide, vinyl formate, vinyl acetate, styrene, and the like can be copolymerized.
The energy ray-curable polymer (a) can be obtained by reacting the acrylic copolymer (a1) having the functional group-containing monomer unit with the unsaturated group-containing compound (a2) having a functional group bonded to the functional group.
The functional group of the unsaturated group-containing compound (a2) can be appropriately selected depending on the type of functional group of the functional group-containing monomer unit of the acrylic copolymer (a 1). For example, when the functional group of the acrylic copolymer (a1) is a hydroxyl group, an amino group or a substituted amino group, the functional group of the unsaturated group-containing compound (a2) is preferably an isocyanate group or an epoxy group; when the functional group of the acrylic copolymer (a1) is an epoxy group, the functional group of the unsaturated group-containing compound (a2) is preferably an amino group, a carboxyl group, or an aziridine group.
The unsaturated group-containing compound (a2) contains at least 1, preferably 1 to 6, and more preferably 1 to 4 energy ray-polymerizable carbon-carbon double bonds in 1 molecule. Specific examples of such unsaturated group-containing compound (a2) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate; an acryloyl group-monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate; a acryloyl group-monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with a polyol compound, hydroxyethyl (meth) acrylate; glycidyl (meth) acrylate; (meth) acrylic acid, 2- (1-aziridinyl) ethyl (meth) acrylate, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and the like.
The unsaturated group-containing compound (a2) is used in an amount of usually 5 to 95 mol%, preferably 10 to 95 mol%, based on the functional group-containing monomer of the acrylic copolymer (a 1).
In the reaction of the acrylic copolymer (a1) and the unsaturated group-containing compound (a2), the reaction temperature, pressure, solvent, time, the presence or absence of a catalyst, and the type of a catalyst may be appropriately selected depending on the combination of the functional group of the acrylic copolymer (a1) and the functional group of the unsaturated group-containing compound (a 2). Thus, the functional group present in the acrylic copolymer (a1) reacts with the functional group in the unsaturated group-containing compound (a2), and an unsaturated group is introduced into the side chain of the acrylic copolymer (a1), whereby the energy ray-curable polymer (a) is obtained.
The weight average molecular weight of the energy ray-curable polymer (A) thus obtained is preferably 10,000 or more, particularly preferably 150,000 to 1,500,000, and more preferably 200,000 to 1,000,000. The weight average molecular weight (Mw) in the present specification is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
When the energy ray-curable adhesive contains, as a main component, a polymer having energy ray curability, such as the energy ray-curable polymer (a), the energy ray-curable adhesive may further contain an energy ray-curable monomer and/or oligomer (B).
Examples of the energy ray-curable monomer and/or oligomer (B) include esters of polyhydric alcohols and (meth) acrylic acid.
Examples of the energy ray-curable monomer and/or oligomer (B) include monofunctional acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyfunctional acrylates such as dimethylol tricyclodecane di (meth) acrylate, polyester oligo (meth) acrylate, and polyurethane oligo (meth) acrylate.
When the energy ray-curable monomer and/or oligomer (B) is blended with the energy ray-curable polymer (a), the content of the energy ray-curable monomer and/or oligomer (B) in the energy ray-curable adhesive is preferably 10 to 40 parts by mass, and particularly preferably 30 to 350 parts by mass, based on 100 parts by mass of the energy ray-curable polymer (a).
When ultraviolet rays are used as the energy rays for obtaining the energy ray-curable adhesive, it is preferable to add a photopolymerization initiator (C) and use the photopolymerization initiator (C) can reduce the polymerization curing time and the irradiation amount of light.
Specific examples of the photopolymerization initiator (C) include benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, 2, 4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, bibenzyl (dibenzyl), diacetyl, β -chloroanthraquinone, (2,4, 6-trimethylbenzyldiphenyl) phosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamic acid, oligo { 2-hydroxy-2-methyl-1- [4- (1-propenyl) phenyl ] acetone }, 2-dimethoxy-1, 2-diphenylethan-1-one, and the like. They may be used alone or in combination of 2 or more.
When the energy ray-curable monomer and/or oligomer (B) is blended with the energy ray-curable copolymer (a), the photopolymerization initiator (C) is used in an amount of 0.1 to 10 parts by mass, particularly preferably in an amount of 0.5 to 6 parts by mass, based on 100 parts by mass of the total amount of the energy ray-curable copolymer (a) and the energy ray-curable monomer and/or oligomer (B).
In addition to the above components, other components may be appropriately blended in the energy ray-curable adhesive. Examples of the other components include a non-energy ray-curable polymer component or oligomer component (D), a crosslinking agent (E), and the like.
Examples of the non-energy ray-curable polymer component or oligomer component (D) include polyacrylates, polyesters, polyurethanes, polycarbonates, polyolefins, and the like, and polymers or oligomers having a weight average molecular weight (Mw) of 3,000 to 2,500,000 are preferable. By blending the component (D) into the energy ray-curable adhesive, the adhesiveness and releasability before curing, the strength after curing, the adhesion to other layers, the storage stability, and the like can be improved. The blending amount of the component (D) is not particularly limited.
As the crosslinking agent (E), a polyfunctional compound reactive with a functional group of the energy ray-curable copolymer (a) or the like can be used. Examples of such polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, melamine compounds, aziridine compounds, hydrazine compounds, aldehyde compounds, oxazoline compounds, metal alkoxide compounds, metal chelate compounds, metal salts, ammonium salts, reactive phenol resins, and the like. By blending the component (E) into the energy ray-curable adhesive, the adhesion and releasability before curing, the cohesive property of the adhesive, and the like can be improved. The amount of the component (E) is not particularly limited, and is suitably determined within a range of 0 to 15 parts by mass per 100 parts by mass of the energy ray-curable copolymer (A).
Next, a case will be described below in which the energy ray-curable adhesive contains, as main components, a mixture of a non-energy ray-curable polymer component and a monomer and/or oligomer having at least 1 or more energy ray-curable groups.
As the non-energy ray-curable polymer component, for example, the same components as those of the acrylic copolymer (a1) described above can be used.
As the monomer and/or oligomer having at least 1 or more energy ray-curable groups, the same monomer and/or oligomer as the component (B) described above can be selected. Regarding the blending ratio of the non-energy ray-curable polymer component to the monomer and/or oligomer having at least 1 or more energy ray-curable groups, the monomer and/or oligomer having 1 or more less energy ray-curable groups is preferably 10 to 250 parts by mass, and particularly preferably 25 to 100 parts by mass, based on 100 parts by mass of the non-energy ray-curable polymer component.
In this case, as well, the photopolymerization initiator (C), the crosslinking agent (E), and the like may be appropriately blended as described above.
The thickness of the adhesive layer 20 is not particularly limited as long as the semiconductor processing sheet 1 can function properly in the process used. Specifically, the particle size is preferably 1 to 50 μm, particularly preferably 2 to 40 μm, and more preferably 3 to 30 μm.
(2) Adhesive layer
The material constituting the adhesive layer 40 can be used without any particular limitation as long as the wafer can be fixed at the time of dicing and the adhesive layer can be formed on the diced chip. As the material constituting such an adhesive layer 40, a material composed of a thermosetting adhesive component of a low molecular weight and a thermoplastic resin, a material composed of a thermosetting adhesive component of a B-stage (semi-cured state), or the like is used. Among them, as a material constituting the adhesive layer 40, a material containing a thermoplastic resin and a thermosetting adhesive component is preferable. Examples of the thermoplastic resin include (meth) acrylic copolymers, polyester resins, urethane resins, phenoxy resins, polybutene, polybutadiene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, ethylene (meth) acrylic copolymers, ethylene (meth) acrylate copolymers, polystyrene, polycarbonate, polyimide, and the like, and particularly (meth) acrylic copolymers are preferable in terms of adhesiveness and film-forming properties (sheet processability). Examples of the thermosetting adhesive component include epoxy resins, polyimide resins, phenol resins, silicone resins, cyanate ester resins, bismaleimide triazine resins, allylated polyphenylene ether resins (thermosetting PPE), formaldehyde resins, unsaturated polyesters or copolymers thereof, and epoxy resins are particularly preferable from the viewpoint of adhesion. The material constituting the adhesive layer 40 is particularly preferably a material containing a (meth) acrylic copolymer and an epoxy resin, because of excellent adhesion to a semiconductor wafer, particularly excellent releasability from the adhesive layer 20 in the semiconductor processing sheet 1d shown in fig. 6.
The (meth) acrylic copolymer is not particularly limited, and conventionally known (meth) acrylic copolymers can be used. The weight average molecular weight (Mw) of the (meth) acrylic copolymer is preferably 10,000 to 2,000,000, and particularly preferably 100,000 to 1,500,000. By setting the Mw of the (meth) acrylic copolymer to 10,000 or more, the peeling property between the adhesive layer 40 and the adhesive layer 20 becomes better in the semiconductor processing sheet 1d shown in fig. 6 in particular, and the wafer pickup can be performed efficiently. Further, when the Mw of the (meth) acrylic copolymer is 2,000,000 or less, the adhesive layer 40 can follow the unevenness of the adherend more favorably, and generation of voids and the like can be effectively prevented.
The glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably-60 to 70 ℃ and more preferably-30 to 50 ℃. By setting the Tg of the (meth) acrylic copolymer to-60 ℃ or higher, the peeling property between the adhesive layer 40 and the adhesive layer 20 becomes better in the semiconductor processing sheet 1d shown in fig. 6 in particular, and the wafer pickup can be performed efficiently. Further, by setting the Tg of the (meth) acrylic copolymer to 70 ℃ or lower, the adhesive force for fixing the wafer can be sufficiently obtained.
Examples of the monomer constituting the (meth) acrylic copolymer include (meth) acrylic acid ester monomers or derivatives thereof, and more specifically include alkyl (meth) acrylates having an alkyl group of 1 to 18 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; (meth) acrylates having a cyclic skeleton such as cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate; hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; glycidyl acrylate, glycidyl methacrylate, and the like. In addition, unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, and itaconic acid can also be used. These can be used alone in 1 kind, also can use more than 2 kinds at the same time.
Among the above monomers constituting the (meth) acrylic copolymer, at least a hydroxyl group-containing (meth) acrylate is preferably used in terms of compatibility with the epoxy resin. In this case, the structural unit derived from the hydroxyl group-containing (meth) acrylate is contained in the (meth) acrylic copolymer preferably in a range of 1 to 20% by mass, more preferably in a range of 3 to 15% by mass. As the (meth) acrylic copolymer, specifically, a copolymer of an alkyl (meth) acrylate and a hydroxyl group-containing (meth) acrylate is preferable.
In addition, the (meth) acrylic copolymer may be obtained by copolymerizing monomers such as vinyl acetate, acrylonitrile, and styrene, as long as the object of the present invention is not impaired.
As the epoxy resin, various conventionally known epoxy resins can be used. Examples of the epoxy resin include bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene (DCPD) type epoxy resins, biphenyl type epoxy resins, triphenol methane type epoxy resins, heterocyclic type epoxy resins, stilbene type epoxy resins, condensed aromatic hydrocarbon modified epoxy resins, and epoxy resins containing 2 or more functional groups in a structural unit such as a halide thereof. These epoxy resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent is preferably 150 to 1000 g/eq. The epoxy equivalent in the present specification is a value measured according to JIS K7236: 2009.
The content of the epoxy resin is preferably 1 to 1500 parts by mass, and more preferably 3 to 1000 parts by mass, based on 100 parts by mass of the (meth) acrylic copolymer. When the content of the epoxy resin is 1 part by mass or more per 100 parts by mass of the (meth) acrylic copolymer, a sufficient adhesive force can be obtained. Further, when the content of the epoxy resin is 1500 parts by mass or less based on 100 parts by mass of the (meth) acrylic copolymer, sufficient film forming properties can be obtained, and the adhesive layer 40 can be efficiently formed.
The material constituting the adhesive layer 40 preferably further contains a curing agent for curing the epoxy resin. Examples of the curing agent include compounds having 2 or more functional groups reactive with an epoxy group in the molecule, and examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, and the like. Among them, a phenolic hydroxyl group, an amino group and an acid anhydride group are preferable, and a phenolic hydroxyl group and an amino group are more preferable.
Specific examples of the curing agent include phenolic thermal curing agents such as novolak-type phenol resins, dicyclopentadiene-type phenol resins, triphenol methane-type phenol resins, and aralkyl-type phenol resins; and an amine-based heat curing agent such as DICY (cyanoguanidine). The curing agent can be used alone in 1 kind, also can be used simultaneously in more than 2 kinds.
The content of the curing agent is preferably 0.1 to 500 parts by mass, and more preferably 1 to 200 parts by mass, based on 100 parts by mass of the epoxy resin. When the content of the curing agent is 0.1 parts by mass or more per 100 parts by mass of the epoxy resin, sufficient adhesion can be obtained. Further, by setting the content of the curing agent to 500 parts by mass or less with respect to 100 parts by mass of the epoxy resin, it is possible to effectively prevent an increase in the moisture absorption rate of the adhesive layer 40, and to further improve the reliability of the semiconductor package.
The material (adhesive composition) constituting the adhesive layer 40 may contain, in addition to the above, various additives such as a curing accelerator, a coupling agent, a crosslinking agent, an energy ray-curable compound, a photopolymerization initiator, a plasticizer, an antistatic agent, an antioxidant, a pigment, a dye, and an inorganic filler, if necessary. These additives may be contained alone in 1 kind, or may be contained in combination of 2 or more kinds.
The curing accelerator is used to adjust the curing speed of the adhesive composition. As the curing accelerator, a compound capable of accelerating the reaction of an epoxy group with a phenolic hydroxyl group, an amine, or the like is preferable. Specific examples of the compound include tertiary amines, imidazoles such as 2-phenyl-4, 5-bis (hydroxymethyl) imidazole, organophosphines, and tetraphenylboron salts.
The coupling agent has a function of improving the adhesiveness and adherence of the adhesive composition to an adherend. Further, by using the coupling agent, the water resistance of the cured product obtained by curing the adhesive composition can be improved without impairing the heat resistance of the cured product. The coupling agent is preferably a compound having a group that reacts with the functional group of the (meth) acrylic polymer and the epoxy resin. As such a coupling agent, a silane coupling agent is preferable.
The silane coupling agent is not particularly limited, and a known silane coupling agent can be used. Examples thereof include gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (methacryloxypropyl) trimethoxysilane, gamma-aminopropyltrimethoxysilane, N-6- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylsilane, and the like, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like. These can be used alone in 1 kind, or in combination of 2 or more kinds.
The crosslinking agent is used to adjust the cohesive force of the adhesive layer 40. The crosslinking agent of the (meth) acrylic polymer is not particularly limited, and a known crosslinking agent can be used, and for example, the crosslinking agent described above as a material constituting the adhesive agent layer 20 can be used.
The energy ray-curable compound is a compound which undergoes polymerization curing upon irradiation with an energy ray such as ultraviolet rays. By curing the energy ray-curable compound by irradiation with an energy ray, in particular, in the semiconductor processing sheet 1d shown in fig. 6, since the releasability between the adhesive layer 40 and the adhesive layer 20 can be improved, the pickup of the semiconductor wafer becomes easy.
The energy ray-curable compound is preferably an acrylic compound, and particularly preferably has at least 1 polymerizable double bond in the molecule. Specific examples of such acrylic compounds include dicyclopentadiene dimethoxy diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
The weight average molecular weight of the acrylic compound is usually 100 to 30000, preferably about 300 to 10000.
When the adhesive composition contains an energy ray-curable compound, the content of the energy ray-curable compound is usually 1 to 400 parts by mass, preferably 3 to 300 parts by mass, and more preferably 10 to 200 parts by mass, based on 100 parts by mass of the (meth) acrylic polymer.
When the adhesive layer 40 contains the energy ray-curable compound, the photopolymerization initiator can reduce the polymerization curing time and the irradiation amount of the energy ray when the polymerization curing is performed by the irradiation of the energy ray. The photoinitiator is not particularly limited, and a known photopolymerization initiator can be used, and for example, the photopolymerization initiator described above as a material constituting the adhesive layer 20 can be used.
The thickness of the adhesive layer 40 is usually 3 to 100 μm, preferably 5 to 80 μm.
(3) Protective film forming layer
The protective film forming layer 50 is preferably made of an uncured curable adhesive. In this case, after the semiconductor wafer, the semiconductor chip, or the like is stacked on the protective film formation layer 50, the protective film can be firmly bonded to the semiconductor wafer, the semiconductor chip, or the like by curing the protective film formation layer 50. And a protective film having durability can be formed on a wafer or the like. The protective film forming layer 50 can be printed satisfactorily by irradiating laser light at a stage where the curable adhesive is not cured or at a stage after curing.
The protective film forming layer 50 preferably has adhesiveness at normal temperature or exhibits adhesiveness by heating. Thus, when the semiconductor wafer, the semiconductor chip, or the like is superposed on the protective film formation layer 50 as described above, the semiconductor wafer, the semiconductor chip, or the like can be bonded to each other. Therefore, positioning can be reliably performed before the protective film forming layer 50 is cured, and the semiconductor processing sheets 1c and 1e can be easily handled.
The curable adhesive constituting the protective film forming layer 50 having the above characteristics preferably contains a curable component and a binder polymer component. As the curable component, a thermosetting component, an energy ray curable component, or a mixture thereof can be used. From the viewpoint of the curing method of the protective film forming layer 50 and the heat resistance after curing, it is particularly preferable to use a thermosetting component, and from the viewpoint of the curing time, it is preferable to use an energy ray-curable component.
Examples of the thermosetting component include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, benzoxazine resins, and mixtures thereof. Among them, epoxy resins, phenol resins, and mixtures thereof are preferably used. The thermosetting component is generally a thermosetting component having a molecular weight of about 300 to 10,000.
The epoxy resin has a property of forming a three-dimensional network upon heating to form a strong coating film. As such an epoxy resin, various known epoxy resins can be used, but an epoxy resin having a weight average molecular weight of about 300 to 2500 is generally preferable. Further, it is preferable to use a mixture of an epoxy resin which is liquid in a normal state and has a weight average molecular weight of 300 to 500 and an epoxy resin which is solid at room temperature and has a weight average molecular weight of 400 to 2500, particularly 500 to 2000. The epoxy equivalent of the epoxy resin is preferably 50 to 5000 g/eq.
Specific examples of such epoxy resins include glycidyl ethers of phenols such as bisphenol a, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; an epoxy resin of a glycidyl type or an alkyl glycidyl type obtained by substituting active hydrogen bonded to a nitrogen atom of aniline isocyanurate or the like with a glycidyl group; examples of the epoxy compound include so-called alicyclic epoxy compounds in which an epoxy group is introduced into a carbon-carbon double bond in a molecule by, for example, oxidation, such as vinylcyclohexane diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-bicyclohexane carboxylate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane. Further, epoxy resins having a biphenyl skeleton, a dicyclohexyldiene skeleton, a naphthalene skeleton, or the like can also be used.
Among them, bisphenol type epoxy resins such as glycidyl type epoxy resins, o-cresol novolak type epoxy resins, and phenol novolak type epoxy resins are preferably used. These epoxy resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When an epoxy resin is used, it is preferable to use a thermally active latent epoxy resin curing agent together as an auxiliary agent. The heat-activated latent epoxy resin curing agent is a curing agent which is not reacted with an epoxy resin at room temperature but is activated by heating at a temperature higher than a certain temperature to react with the epoxy resin. As a method for activating a heat-activated latent epoxy resin curing agent, there are a method of generating an active species (anion, cation) by a chemical reaction by heating; a method in which the epoxy resin is stably dispersed in the epoxy resin at around room temperature and the curing reaction is initiated by being compatible and dissolved with the epoxy resin at high temperature; a method of starting a curing reaction by dissolving out a molecular sieve-encapsulated curing agent at a high temperature; microcapsule-based methods, and the like.
As specific examples of the heat-activated latent epoxy resin curing agent, mention may be made ofGive out various kinds of
Figure BDA0001647796080000251
Salts, dibasic acid dihydrazide compounds, cyanoguanidine, amine adduct curing agents, high melting point active hydrogen compounds such as imidazole compounds, and the like. These thermally active latent epoxy resin curing agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The thermally active latent epoxy resin curing agent is used in an amount of preferably 0.1 to 20 parts by mass, particularly preferably 0.2 to 10 parts by mass, and more preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the epoxy resin.
The phenol resin is not particularly limited, and a polymer having a phenolic hydroxyl group such as a condensate of a phenol such as an alkylphenol, a polyphenol, or naphthol, and an aldehyde can be used. Specifically, phenol novolak-based resins, o-cresol novolak-based resins, p-cresol novolak-based resins, t-butylphenol novolak-based resins, dicyclopentadiene cresol-based resins, poly-p-vinylphenol-based resins, bisphenol a novolak-based resins, modified products thereof, and the like can be used.
The phenolic hydroxyl group contained in these phenolic resins can be easily subjected to an addition reaction with the epoxy group of the epoxy resin by heating, and a cured product having high impact resistance can be formed. Therefore, the epoxy resin and the phenol resin may be used together.
As the energy ray-curable component, for example, the energy ray-curable component described above as a material constituting the adhesive agent layer 20 can be used. Further, as the energy ray-curable component, an energy ray-curable monomer/oligomer may also be used. Further, as the binder polymer component to be combined with the energy ray-curable component, an acrylic polymer to which an energy ray-curable compound is added may also be used.
The binder polymer component is blended for the purpose of imparting appropriate tackiness to the protective film-forming layer 50, improving the handling properties of the semiconductor processing sheets 1c and 1e, and the like. The weight average molecular weight of the binder polymer is usually 30,000 to 2,000,000, preferably 50,000 to 1,500,000, and particularly preferably in the range of 100,000 to 1,000,000. By making the weight average molecular weight 30,000 or more, the film formation of the protective film forming layer 50 is sufficient. Further, by setting the weight average molecular weight to 2,000,000 or less, the compatibility with other components can be maintained well, and the film formation of the protective film forming layer 50 can be performed uniformly. Examples of the binder polymer include (meth) acrylic copolymers, polyester resins, phenoxy resins, urethane resins, silicone resins, and rubber copolymers, and (meth) acrylic copolymers are particularly preferably used.
Examples of the (meth) acrylic copolymer include a (meth) acrylate copolymer obtained by polymerizing a (meth) acrylate monomer and a (meth) acrylic acid derivative. Here, as the (meth) acrylate monomer, alkyl (meth) acrylates having an alkyl group of 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, are preferably used. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
Among the above, when glycidyl methacrylate or the like is used as a structural unit to introduce an glycidyl group into the (meth) acrylic copolymer, compatibility with the epoxy resin as the above-mentioned thermosetting component is improved, and the glass transition temperature (Tg) of the protective film forming layer 50 after curing is increased and heat resistance is improved. Among the above, when hydroxyl groups are introduced into the (meth) acrylic copolymer using hydroxyethyl acrylate or the like as a structural unit, adhesiveness and adhesive properties to a semiconductor wafer, a semiconductor chip or the like can be controlled. In addition, when glycidyl methacrylate or the like is used as a structural unit to introduce glycidyl groups into a (meth) acrylic copolymer, the (meth) acrylic copolymer or phenoxy resin having an epoxy group may have thermosetting properties. However, such a thermosetting polymer is not a thermosetting component in the present embodiment, but corresponds to a binder polymer component.
When a (meth) acrylic copolymer is used as the binder polymer, the weight average molecular weight of the (meth) acrylic copolymer is preferably 100,000 or more, and particularly preferably 150,000 to 1,000,000. The (meth) acrylic copolymer has a glass transition temperature of usually not more than 20 ℃ and preferably about-70 to 0 ℃ and has tackiness at ordinary temperature (23 ℃).
The blending ratio of the curable component and the binder polymer component is preferably 50 to 1500 parts by mass, particularly preferably 70 to 1000 parts by mass, and further preferably 80 to 800 parts by mass, based on 100 parts by mass of the binder polymer component. When the curable component and the binder polymer component are blended in such a ratio, appropriate tackiness is exhibited before curing, and the adhesive operation can be stably performed, and a protective film having excellent film strength is obtained after curing.
The protective film forming layer 50 may further contain a filler and/or a colorant. However, when the semiconductor processing sheets 1c and 1e are used for inspection of wafer shape, stealth dicing, or laser printing of a semiconductor wafer, the protective film forming layer 50 must have light transmittance. Therefore, in this case, it is necessary to contain a filler and/or a colorant to such an extent that the light transmittance is not hindered. On the other hand, when the semiconductor processing sheets 1c and 1e are used for laser printing of the protective film forming layer 50 or a protective film formed by dicing the protective film forming layer 50, the protective film forming layer 50 is not required to have light transmittance. In this case, the protective film forming layer 50 must block the laser beam in order to enable laser printing. Therefore, in order to perform laser printing efficiently, the protective film forming layer 50 preferably contains a filler and/or a colorant. Further, when the protective film forming layer 50 contains a filler, the moisture resistance can be improved while maintaining the hardness of the protective film after curing high. Further, the glossiness of the surface of the formed protective film can be adjusted to a desired value. Further, the thermal expansion coefficient of the cured protective film can be made close to that of the semiconductor wafer, whereby the warpage of the semiconductor wafer during processing can be reduced.
Examples of the filler include silica such as crystalline silica, fused silica and synthetic silica, and inorganic fillers such as alumina and glass balloons. Among these, synthetic silica is preferable, and particularly, synthetic silica of a type which removes a radiation source of α rays, which is a main cause of a failure of a semiconductor device, as much as possible is preferable. The filler may be in any shape of sphere, needle, or amorphous.
In addition, as the filler to be added to the protective film forming layer 50, a functional filler may be blended in addition to the inorganic filler. Examples of the functional filler include conductive fillers such as gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramics, silver-coated nickel, and aluminum for imparting antistatic properties; and a heat conductive filler such as a metal material, such as gold, silver, copper, nickel, aluminum, stainless steel, silicon, or germanium, or an alloy thereof, which is intended to impart heat conductivity.
As the colorant, known colorants such as inorganic pigments, organic pigments, and organic dyes can be used.
Examples of the inorganic pigments 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.
Examples of the organic pigment and the organic dye include amines
Figure BDA0001647796080000281
(aminium) type pigment, cyanine type pigment, merocyanine type pigment, croconic acid (croconium) type pigment, squarylium (squarylium) type pigment, azulene
Figure BDA0001647796080000282
(azulenium) pigments, polymethine pigments, naphthoquinone pigments, pyrans
Figure BDA0001647796080000283
Dye, phthalocyanine dye, naphthalocyanine dye, naphthalimide dyeAzo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinoline pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indophenol pigments, triallylmethane pigments, anthraquinone pigments, dioxazine pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, and the like. These pigments or dyes may be appropriately mixed and used in order to adjust the target light transmittance.
Among the above, inorganic pigments are preferably used as the pigment from the viewpoint of printability by laser irradiation. Among the inorganic pigments, carbon black is particularly preferable. Since carbon black is normally black, the portion shaved off by laser irradiation appears white, and the contrast difference increases, and therefore, the visibility of the laser-printed portion is very excellent.
The blending amount of the filler and the colorant in the protective film forming layer 50 may be appropriately adjusted so as to achieve a desired effect. Specifically, the amount of the filler is preferably 40 to 80% by mass, and more preferably 50 to 70% by mass. The amount of the colorant is preferably 0.001 to 5% by mass, particularly preferably 0.01 to 3% by mass, and further preferably 0.1 to 2.5% by mass.
The protective film forming layer 50 may also contain a coupling agent. By containing the coupling agent, after curing the protective film-forming layer 50, the adhesiveness and adherence between the protective film and the semiconductor wafer, semiconductor chip, or the like can be improved without impairing the heat resistance of the protective film, and the water resistance (moisture and heat resistance) can be improved. As the coupling agent, a silane coupling agent is preferable from the viewpoints of versatility, cost advantage, and the like. As the silane coupling agent, for example, the above-mentioned silane coupling agent can be used.
The protective film forming layer 50 may contain a crosslinking agent such as an organic polyisocyanate compound, an organic polyimine compound, or an organic metal chelate compound in order to adjust the cohesive force before curing. In addition, the protective film forming layer 50 may contain an antistatic agent in order to suppress static electricity and improve wafer reliability. Further, in order to improve the flame retardant property of the protective film and improve the reliability as a package, the protective film forming layer 50 may contain a flame retardant such as a phosphoric acid-based compound, a bromine-based compound, or a phosphorus-based compound.
In order to effectively function as a protective film, the thickness of the protective film forming layer 50 is preferably 3 to 300 μm, particularly preferably 5 to 250 μm, and further preferably 7 to 200 μm.
The first surface 501 of the protective film forming layer 50 preferably has a gloss value of 25 or more, and particularly preferably 30 or more. When the gloss value of the first surface 501 is 25 or more, the appearance is excellent when laser printing is performed on the surface, and the formed print has excellent visibility. The gloss value in the present specification is a value measured at a measurement angle of 60 ℃ using a gloss meter in accordance with JIS Z8741: 1997.
5. Adhesive layer for clip
The semiconductor processing sheet of the present embodiment may further include a jig adhesive layer. Fig. 8 is a sectional view showing a semiconductor processing sheet 2 of a second embodiment including a jig adhesive layer 60. In the semiconductor processing sheet 2, the adhesive layer 60 for a jig has a first surface 601 on the side close to the semiconductor adhesive layer 80 and a second surface 602 on the side close to the release film 30. The adhesive layer 60 for a jig is formed in a shape corresponding to the shape of a jig such as an annular frame (ring frame), and is usually formed in an annular shape. This makes it possible to attach and reliably fix the semiconductor processing sheet 2 to a jig such as an annular frame regardless of the adhesive force of the semiconductor adhesive layer 80.
In the semiconductor processing sheet 2 according to the second embodiment, as shown in fig. 8, the jig adhesive layer 60 contacts the first surface 301 of the release film 30. As shown in fig. 8, in the central portion of the semiconductor processing sheet 2 where the jig adhesive layer 60 is not present, the second surface 802 of the semiconductor adhesive layer 80 contacts the first surface 301 of the release film 30. Here, in the semiconductor processing sheet 2 of the second embodiment, when the semiconductor processing sheet 2 is wound in a roll shape, the rolling pressure is concentrated at the position where the adhesive layer 60 for a jig exists. With this, blocking is also likely to occur at the position where the adhesive layer 60 for a jig is present. Therefore, whether the semiconductor processing sheet 2 is properly unwound from the roll or not significantly affects the adhesion between the first surface 301 of the release film 30 and the second surface 602 of the jig adhesive 60. Therefore, in the semiconductor processing sheet 2, the peeling force at the interface between the second surface 602 of the jig adhesive layer 60 and the first surface 301 of the release film 30 is set to be the peeling force β. Specifically, the peel force β is the peel force of the release film 30 from the adhesive layer 60 for a jig after being stored at 40 ℃ for 3 days under predetermined conditions in a state in which the second surface 602 of the adhesive layer 60 for a jig and the first surface 301 of the release film 30 are laminated. On the other hand, the peeling force α is set to be a peeling force at the interface between the first surface 101 of the base 10 and the second surface 302 of the release film 30, as in the semiconductor processing sheet 1 of the first embodiment.
The adhesive agent layer 60 for a jig in the present embodiment may be composed of a single layer or a plurality of layers of 2 or more layers, and when composed of a plurality of layers, a configuration in which a core material is inserted into a space is preferable.
From the viewpoint of the adhesive force to the jig such as the annular frame, the adhesive constituting the jig adhesive layer 60 is preferably made of a non-energy ray-curable adhesive. The non-energy ray-curable adhesive is preferably an acrylic adhesive having desired adhesive force and removability, and for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, or the like can be used.
As the core material, a resin film is usually used, and among them, a polyvinyl chloride film such as a polyvinyl chloride film or a vinyl chloride copolymer film is preferable, and a polyvinyl chloride film is particularly preferable. The polyvinyl chloride film has a property of being easily restored when cooled even if softened when heated. The thickness of the core material is preferably 2 to 200 μm, and particularly preferably 5 to 100 μm.
The thickness of the adhesive layer 60 for a jig is preferably 5 to 200 μm, and particularly preferably 10 to 100 μm from the viewpoint of adhesiveness to a jig such as a ring frame.
The semiconductor processing sheet 2 having the adhesive layer 60 for a jig has a smooth surface and a high light transmittance to light of a desired wavelength at least in the substrate 10 by setting the arithmetic mean roughness Ra of the first surface 101 of the substrate 10 to 0.01 to 0.8 [ mu ] m. Further, when the ratio (α/β) of the peeling force α to the peeling force β is 0 or more and less than 1.0, excellent blocking resistance can be exhibited, the sheet 2 for semiconductor processing can be favorably unwound from the roll, and undesired peeling is not generated at the time of unwinding. Further, by setting the peeling force β to 10 to 1000mN/50mm, the laminate including the substrate 10, the semiconductor adhesive layer 80, and the adhesive agent layer 60 for a jig can be peeled from the peeling film 30 with an appropriate peeling force when the sheet 2 for semiconductor processing is used.
6. Precutting
The semiconductor processing sheet of the present embodiment may be a semiconductor processing sheet in which layers other than the release film 30 are cut and processed into a desired shape, that is, in a precut state. That is, the semiconductor processing sheet according to the present embodiment may be a semiconductor processing sheet in which a laminate having a shape different from that of the release film 30 in a plan view and including the base material 10 and the semiconductor adhesive layer 80 is laminated on the long release film 30. Fig. 9 is a plan view of the semiconductor processing sheet 3 according to the third embodiment, which is precut as described above, as viewed from the base material side. In the semiconductor processing sheet 3, a laminate (hereinafter, sometimes referred to as "main use portion") of the base material 10a and the semiconductor adhesive layer 80a cut into a circular shape is provided on the long release film 30. A plurality of main use portions are arranged in the longitudinal direction of the release film 30. A laminate of the base material 10b and the semiconductor adhesive layer 80b (hereinafter, sometimes referred to as "sheet remaining portion") cut so as not to contact a main use portion is provided on both end portions in the longitudinal direction of the release film 30. Fig. 10 is a cross-sectional view taken along line a-a of fig. 9.
The pre-cut semiconductor processing sheet 3 also satisfies the above-described physical properties and the like of the semiconductor processing sheet 1. As each layer constituting the semiconductor processing sheet 3, those described above with respect to the semiconductor processing sheet 1 can be used.
The semiconductor processing sheet 2 including the adhesive layer 60 for a jig may be a precut sheet. In this sheet, the adhesive layer 60 for a jig is provided at the peripheral edge of the main use portion.
In the semiconductor processing sheet 3, a main use portion is attached to a semiconductor wafer, a semiconductor chip, or the like after being peeled from the release film 30. On the other hand, the sheet residual portion prevents the winding pressure from concentrating on the main use portion when the semiconductor processing sheet 3 is wound into a roll.
In general, when a precut semiconductor processing sheet is unwound from a roll, for example, a main portion of the sheet is peeled from a release film, or the base material side of the peeled main portion is stuck to the second surface of the release film. However, according to the semiconductor processing sheet 3 of the third embodiment, the ratio (α/β) of the peeling force α to the peeling force β is set to 0 or more and less than 1.0, and thus occurrence of such a problem can be suppressed. Further, by setting the arithmetic average roughness Ra of the first surface 101 of the substrate 10 to 0.01 to 0.8 μm, the smoothness of the surface becomes good and at least the substrate 10 has high light transmittance to light of a desired wavelength. Further, by setting the peeling force β to 10 to 1000mN/50mm, the peeling film 30 can be peeled from the semiconductor adhesive layer 80 with an appropriate peeling force when the semiconductor processing sheet 3 is used.
7. Method for manufacturing semiconductor processing sheet
The method for producing the semiconductor processing sheet 1a including the adhesive layer 20 is not particularly limited, and a general method can be used. As a first example of the production method, first, an adhesive composition containing a material including the adhesive layer 20 and, further, a coating composition containing a solvent or a dispersion medium as necessary are prepared. Next, the coating composition is applied to the first surface 301 of the release film 30 using a die coater, a curtain coater, a spray coater, a slit coater, a blade coater, or the like, thereby forming a coating film. Further, the adhesive layer 20 can be formed by drying the coating film. Subsequently, the first surface 201 of the adhesive layer 20 and the second surface 102 of the substrate 10 are bonded to each other, whereby the semiconductor processing sheet 1a can be obtained. The properties of the coating composition are not particularly limited as long as the coating composition can be coated. The component for forming the adhesive layer 20 may be contained in the coating composition as a solute or may be contained in the coating composition as a dispersion medium.
When the coating composition contains the crosslinking agent (E), the drying conditions (temperature, time, etc.) described above may be changed or a heating treatment may be separately provided in order to form a crosslinked structure at a desired density. In order to sufficiently perform the crosslinking reaction, generally, the adhesive layer is laminated on the substrate by the above-mentioned method or the like, and then the obtained semiconductor processing sheet 1a is subjected to aging by standing for several days at 23 ℃ under an environment of a relative humidity of 50%, for example.
As a second example of the method for producing the semiconductor processing sheet 1a, first, the coating composition is applied to the second surface 102 of the substrate 10 to form a coating film. Then, the coating film is dried to form a laminate composed of the base material 10 and the adhesive layer 20. Further, the second surface 202 of the adhesive layer 20 of the laminate and the first surface 301 of the release film 30 are bonded to each other, thereby obtaining the semiconductor processing sheet 1 a.
The method for producing the semiconductor processing sheet 1b including the adhesive layer 40 is not particularly limited, and a general method can be used. For example, the adhesive layer 40 is formed by applying an adhesive composition containing a material of the adhesive layer 40 and, if necessary, a coating composition containing a solvent or a dispersion medium to the first surface 301 of the release film 30 and drying the composition. Subsequently, the first surface 401 of the adhesive layer 40 is bonded to the second surface 102 of the substrate 10, thereby obtaining the semiconductor processing sheet 1 b.
The semiconductor processing sheet 1c including the protective film formation layer 50 can be manufactured by referring to the manufacturing method of the semiconductor processing sheet 1 b. In particular, in the method for producing the sheet for semiconductor processing 1b, the adhesive composition containing the material of the adhesive layer 40 is replaced with the protective film forming layer composition containing the material of the protective film forming layer 50, whereby the sheet for semiconductor processing 1c can be obtained.
The method for producing the semiconductor processing sheet 1d including the adhesive layer 20 and the adhesive layer 40 is not particularly limited, and a conventional method can be used. For example, the adhesive layer 40 is formed by applying and drying an adhesive composition containing a material of the adhesive layer 40 and, if necessary, a coating composition of a solvent or a dispersion medium to the first surface 301 of the release film 30. This yields a laminate of the release film 30 and the adhesive layer 40. Next, the release film 30 is peeled off from the previously prepared semiconductor processing sheet 1a, and the exposed surface on the adhesive layer 20 side is bonded to the surface on the adhesive layer 40 side of the laminate, thereby obtaining a semiconductor processing sheet 1 d.
The semiconductor processing sheet 1e including the adhesive layer 20 and the protective film-forming layer 50 can be manufactured by referring to the manufacturing method of the semiconductor processing sheet 1 d. In particular, in the method for producing the sheet for semiconductor processing 1d, the adhesive composition containing the material of the adhesive layer 40 is replaced with the protective film forming layer composition containing the material of the protective film forming layer 50, whereby the sheet for semiconductor processing 1e can be obtained.
The semiconductor processing sheet 2 including the adhesive layer 60 for a jig can be manufactured by a conventional method. For example, the semiconductor processing sheet 2 can be manufactured by laminating the jig adhesive layer 60 formed into a desired shape on the surface of the laminate including the substrate 10, the semiconductor adhesive layer 80, and the like, which is opposite to the substrate 10.
When the semiconductor processing sheet 2 including the adhesive layer 60 for a jig is prepared as a precut sheet, it can be manufactured, for example, as follows. First, a clip adhesive for constituting the clip adhesive layer 60 is formed in a sheet shape on the release surface of the release film 30. Next, the sheet-like adhesive for a jig is cut (half-cut) so that the release film 30 remains on a portion of the sheet-like adhesive for a jig, which becomes the inner peripheral edge of the adhesive layer 60 for a jig, and the inner circular portion is removed. Next, the adhesive-side surface of the sheet-like jig of the laminate composed of the adhesive for sheet-like jig from which the circular portion was removed and the release film 30 was bonded to the separately prepared adhesive-side surface of the semiconductor bonding layer 80 of the laminate composed of the base material 10 and the semiconductor bonding layer 80. Thus, a laminate in which the release film 30, the sheet-like jig adhesive, the semiconductor adhesive layer 80, and the base material 10 are laminated in this order was obtained. Finally, the sheet-like jig adhesive, the semiconductor adhesive layer 80, and the base material 10 are cut (half-cut) so that the release film 30 remains in the laminate. At this time, the part to be the outer peripheral edge of the adhesive agent layer 60 for a jig is cut (half-cut) so as to leave the release film 30, and the unnecessary part is removed, whereby a main use part can be formed. Thus, the sheet-like adhesive for jigs becomes the annular adhesive layer 60 for jigs. Further, the sheet remaining portion can also be formed by appropriately half-cutting a portion other than the portion that is the main use portion.
The method for manufacturing the precut semiconductor processing sheet 3 is not particularly limited, and a general method can be used.
8. Method for using semiconductor processing sheet
The semiconductor processing sheets 1,2, and 3 of the present embodiment can be used as a back surface polishing sheet, a dicing sheet, or the like. When the sheets 1,2, and 3 are used, the sheet can be cut by irradiating the sheet with laser light from the back surface thereof. After the steps of back grinding, dicing, and the like, the shape of the wafer, chip, and the like can be inspected through the semiconductor processing sheets 1,2, and 3 of the present embodiment. Further, the back surface of a wafer, a chip, or the like can be laser-printed through the semiconductor processing sheet of the present embodiment.
In particular, the semiconductor processing sheets 1b and 1d including the adhesive layer 40 can be used as dicing die bonding sheets. That is, the wafers are cut into the semiconductor processing sheets 1b and 1d, and after the expanding step is performed as necessary, the obtained chips are picked up, whereby chips provided with an adhesive layer can be obtained. Further, by using the semiconductor processing sheets 1c and 1e including the protective film formation layer 50, a protective film can be formed on the back surface of the wafer. At this time, wafers are attached to the semiconductor processing sheets 1c and 1e including the protective film formation layer 50, and the protective film formation layer 50 is cured. Next, the semiconductor processing sheets 1c and 1e are cut into wafers, and if necessary, a stretching step is performed. Subsequently, by picking up the obtained wafer, a wafer having a protective film formed on the back surface can be obtained.
The semiconductor processing sheets 1,2, and 3 according to the present embodiment may be wound in a roll shape for storage or the like. Even if the semiconductor processing sheets 1,2, and 3 of the present embodiment are wound up in this manner, the adhesion between the semiconductor processing sheets 1,2, and 3 of the present embodiment is not higher than the adhesion between the layers constituting the semiconductor processing sheets 1,2, and 3 of the present embodiment because the ratio (α/β) of the peeling force α to the peeling force β is 0 or more and less than 1.0 as described above. Therefore, the sheet for semiconductor processing 1,2, or 3 of the present embodiment can be favorably unwound from the roll while exhibiting excellent blocking resistance, and furthermore, undesired delamination between layers during unwinding can be suppressed. Further, by setting the arithmetic average roughness Ra of the first surface of the substrate 10 to 0.01 to 0.8 μm, the smoothness of the surface becomes good and the substrate 10 has high light transmittance to light of a desired wavelength. As a result, the laser cutting, inspection, and laser printing by the back surface as described above can be performed satisfactorily. Further, since the peeling force β is 10 to 1000mN/50mm, when the wafer is bonded to the semiconductor processing sheets 1,2, and 3 of the present embodiment, the laminate including the base material 10 and the semiconductor adhesive layer 80 can be peeled from the peeling film 30 with an appropriate peeling force.
The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, the elements disclosed in the above embodiments are intended to include all design modifications and equivalents that fall within the technical scope of the present invention.
For example, another layer may be present between the substrate 10 and the semiconductor adhesive layer 80 of the semiconductor processing sheets 1,2, and 3 according to the present embodiment.
Examples
The present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
[ example 1]
(1) Manufacture of substrates
A polyvinyl chloride film was produced as a substrate by a calender film-making method. The first surface of the polyvinyl chloride film had an arithmetic average roughness Ra of 0.03. mu.m, a tensile modulus of elasticity (Young's modulus) in the MD direction at 23 ℃ of 250MPa measured according to JIS K7161:1994, and a thickness of 80 μm.
The arithmetic average roughness Ra in the present example is a value obtained by measuring 10 points in a plane in accordance with JIS B061:2013 using a touch surface roughness meter ("SURFTEST SV-3000" manufactured by Mitsutoyo Corporation) and calculating an average value thereof.
The substrate monomers were evaluated for the transmittance of the printing laser beam (wavelength: 532nm), the transmittance of the stealth dicing laser beam (wavelength: 1600nm), and the transmittance of the inspection infrared beam (wavelength: 1069nm), and as a result, all showed excellent transmittance.
(2) Preparation of Release film
A release film (manufactured by Lintec Corporation, product name "SP-PMF 381031H", thickness: 38 μm) obtained by peeling one surface (first surface) of a polyethylene terephthalate film with a silicone-based peeling agent was used as the release film. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the second surface of the release film had an arithmetic average roughness Ra of 0.3. mu.m.
(3) Preparation of adhesive composition (I)
18.5 parts by mass (same as below in terms of solid content) of 2-ethylhexyl acrylate, 75 parts by mass of vinyl acetate, 1 part by mass of acrylic acid, 5 parts by mass of methyl methacrylate, and 0.5 part by mass of 2 hydroxyethyl methacrylate were copolymerized to obtain an acrylic copolymer having a weight average molecular weight of 600,000.
The coating solution of the pressure-sensitive adhesive composition (I) was obtained by mixing 100 parts by mass of the obtained acrylic copolymer, 60 parts by mass of a 2-functional urethane acrylate oligomer (Mw 8000) as an energy ray-curable compound, 60 parts by mass of a 6-functional urethane acrylate oligomer (Mw 2000) as an energy ray-curable compound, 3 parts by mass of α -hydroxycyclohexyl phenyl ketone (manufactured by basf, product name "IRGACURE 184") as a photopolymerization initiator, and 1.6 parts by mass of trimethylolpropane-modified portoluene diisocyanate (manufactured by TOSOH CORPORATION, product name "CORONATE L") as a crosslinking agent in a solvent.
(4) Manufacture of semiconductor processing sheet
The coating solution of the adhesive composition (I) obtained in the above step (3) is coated on the first surface of the release film produced in the above step (2) using a blade coater. Subsequently, the coating film was dried and subjected to a crosslinking reaction while being treated at 100 ℃ for 1 minute, thereby obtaining a laminate composed of a release film and an adhesive layer having a thickness of 10 μm. Further, the first surface of the adhesive layer of the laminate is bonded to the second surface of the substrate produced in the step (1), thereby obtaining a semiconductor processing sheet in which the substrate, the adhesive layer, and the release film are sequentially laminated. Subsequently, the semiconductor processing sheet was aged at a temperature of 23 ℃ and a relative humidity of 50% for 7 days.
[ example 2]
(1) Manufacture of substrates
An ethylene-methacrylic acid copolymer film was produced as a substrate by a T-die film-forming method. The first surface of the ethylene-methacrylic acid copolymer film had an arithmetic average roughness Ra of 0.05. mu.m, a tensile modulus of elasticity (Young's modulus) in the MD direction at 23 ℃ of 130MPa measured according to JIS K7161:1994, and a thickness of 80 μm.
The substrate monomer was evaluated for the transmittance of a printing laser beam (wavelength: 532nm), the transmittance of a stealth dicing laser beam (wavelength: 1600nm), and the transmittance of an inspection infrared beam (wavelength: 1069nm), and as a result, all showed excellent transmittance.
(2) Preparation of adhesive composition (II)
99 parts by mass of butyl acrylate and 1 part by mass of acrylic acid were copolymerized to obtain an acrylic copolymer having a weight-average molecular weight of 600,000.
Then, 100 parts by mass of the obtained acrylic copolymer, 120 parts by mass of dipentaerythritol hexaacrylate (Nippon Kayaku co., ltd., product name "KAYARAD DPHA") as an energy ray-curable compound, 3 parts by mass of α -hydroxycyclohexyl phenyl ketone (IRGACURE 184) as a photopolymerization initiator, and 17 parts by mass of trimethylolpropane-modified toluene diisocyanate (TOSOH CORPORATION, product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain a coating solution of the pressure-sensitive adhesive composition (II).
(3) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 1, except that the substrate made of the ethylene-methacrylic acid copolymer produced in the above manner and the adhesive composition (II) were used.
[ example 3]
(1) Manufacture of substrates
An ethylene-vinyl acetate copolymer film was produced as a substrate by a T-die film-forming method. The first surface of the ethylene-vinyl acetate copolymer film had an arithmetic average roughness Ra of 0.06. mu.m, a tensile modulus of elasticity (Young's modulus) in the MD direction at 23 ℃ of 75MPa measured according to JIS K7161:1994, and a thickness of 100. mu.m.
Further, the substrate monomers were evaluated for the transmittance of a printing laser beam (wavelength: 532nm), the transmittance of a stealth dicing laser beam (wavelength: 1600nm), and the transmittance of an inspection infrared ray (wavelength: 1069nm), and as a result, all showed excellent transmittance.
(2) Preparation of adhesive composition (III)
An acrylic copolymer having a weight average molecular weight of 420,000 was obtained by copolymerizing 40 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of vinyl acetate, and 20 parts by mass of 2-hydroxyethyl acrylate.
Then, 100 parts by mass of the obtained acrylic copolymer and 30.2 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI) as the energy ray curable group-containing compound were reacted with each other to obtain an energy ray curable polymer having an energy ray curable group (methacryloyl) introduced into a side chain thereof.
The coating solution of the pressure-sensitive adhesive composition (III) was obtained by mixing 100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of α -hydroxycyclohexyl phenyl ketone (product name "IRGACURE 184", manufactured by basf CORPORATION) as a photopolymerization initiator, and 1.1 parts by mass of trimethylolpropane-modified toluene diisocyanate (product name "CORONATE L", manufactured by TOSOH CORPORATION) as a crosslinking agent in a solvent.
(3) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 1, except that the ethylene-vinyl acetate copolymer-based substrate produced in the above manner and the adhesive composition (III) were used.
[ example 4]
(1) Manufacture of substrates
A polypropylene film was produced as a substrate by a T-die film-forming method. The polypropylene film had an arithmetic average roughness Ra of 0.3 μm on the first surface, a tensile modulus of elasticity (Young's modulus) in the MD direction at 23 ℃ of 360MPa and a thickness of 100 μm as measured in accordance with JIS K7161: 1994.
The substrate monomer was evaluated for the transmittance of a printing laser beam (wavelength: 532nm), the transmittance of a stealth dicing laser beam (wavelength: 1600nm), and the transmittance of an inspection infrared beam (wavelength: 1069nm), and as a result, all showed excellent transmittance.
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 1, except that the base material made of polypropylene produced in the above manner and the adhesive composition (II) prepared in example 2 were used.
[ example 5]
(1) Production of release film
One side (first side) of a release film (product name "SP-PET 381031" manufactured by Lintec Corporation, thickness: 38 μm) obtained by peeling one side (first side) of a polyethylene terephthalate film using a silicone-based release agent was subjected to a peeling treatment using an alkyd-based release agent. As the alkyd based release agent, an alkyd based release agent for forming an alkyd based release agent layer of a release film (product name "SP-PET 38 AL-5" manufactured by Lintec Corporation) in which an alkyd based release agent layer was provided on one surface of a 38 μm thick polyethylene terephthalate film was used. Thus, a release film was obtained in which the first surface was subjected to a release treatment with a silicone-based release agent and the second surface was subjected to a release treatment with an alkyd-based release agent. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the second surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m.
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 1, except that the release film produced in the above manner was used, which was obtained by subjecting the first surface to a release treatment with a silicone-based release agent and subjecting the second surface to a release treatment with an alkyd-based release agent.
[ example 6]
A semiconductor processing sheet was produced in the same manner as in example 2, except that the release film produced in example 5 was used, which had a first surface subjected to a release treatment with a silicone-based release agent and a second surface subjected to a release treatment with an alkyd-based release agent.
[ example 7]
(1) Production of release film
The same alkyd based release agent as used in example 6 was used to release the other side (second side) of a release film (product name "SP-PET 382150" manufactured by Lintec Corporation, thickness: 38 μm) obtained by releasing one side (first side) of a polyethylene terephthalate film using a silicone based release agent. Thus, a release film was obtained in which the first surface was subjected to a release treatment with a silicone-based release agent and the second surface was subjected to a release treatment with an alkyd-based release agent. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the second surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m.
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 2, except that the release film produced in the above manner was used, which was obtained by subjecting the first surface to a release treatment with a silicone-based release agent and subjecting the second surface to a release treatment with an alkyd-based release agent.
[ example 8]
(1) Preparation of Release film
A release film (manufactured by Lintec Corporation, product name "SP-PET 301031", thickness: 30 μm) obtained by peeling one surface (first surface) of a polyethylene terephthalate film with a silicone-based peeling agent was used as the release film. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the second surface of the release film had an arithmetic average roughness Ra of 0.3. mu.m.
(2) Preparation of adhesive composition (IV)
80 parts by mass of butyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized to obtain an acrylic copolymer having a weight-average molecular weight of 700,000.
Then, 100 parts by mass of the obtained acrylic copolymer and 30.2 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI) as the energy ray curable group-containing compound were reacted with each other to obtain an energy ray curable polymer having an energy ray curable group (methacryloyl) introduced into a side chain thereof.
The coating solution of the pressure-sensitive adhesive composition (IV) was obtained by mixing 100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of α -hydroxycyclohexyl phenyl ketone (product name "IRGACURE 184", manufactured by basf CORPORATION) as a photopolymerization initiator, and 0.5 parts by mass of trimethylolpropane-modified toluene diisocyanate (product name "CORONATE L", manufactured by TOSOH CORPORATION) as a crosslinking agent in a solvent.
(3) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 2, except that the release film having a thickness of 30 μm and the adhesive composition (IV) produced in the above manner were used.
[ example 9]
(1) Preparation of Release film
A release film (manufactured by Lintec Corporation, product name "SP-PET 501031", thickness: 50 μm) obtained by peeling one surface (first surface) of a polyethylene terephthalate film with a silicone-based peeling agent was obtained as a release film. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the second surface of the release film had an arithmetic average roughness Ra of 0.3. mu.m.
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 8, except that the release film having a thickness of 50 μm produced in the above manner was used.
[ example 10]
(1) Production of a first laminate comprising an adhesive layer
After an adhesive composition was obtained by mixing the following acrylic polymer, thermosetting resin, filler, silane coupling agent, and crosslinking agent, the mixture was diluted with methyl ethyl ketone so that the solid content concentration became 20 mass%, thereby preparing a coating solution of the adhesive composition.
Acrylic acid polymer: 100 parts by mass of a copolymer (Mw: 500,000, Mw/Mn: 2.9, Tg: 9 ℃ C.) comprising 95 parts by mass of methyl acrylate and 5 parts by mass of 2-hydroxyethyl acrylate
Thermosetting resin:
30 parts by mass of an acryl-addition cresol novolak type epoxy resin (Nippon Kayaku Co., manufactured by Ltd., product name "CNA-147") was used
Thermal curing agent: 6 parts by mass of an aralkylphenol resin (product name "Milex XLC-4L" manufactured by Mitsui Chemicals, Inc.)
Filling: 35 parts by mass of a methacryloxy-modified silica filler (3-methacryloxypropyltrimethoxysilane treated product having an average particle diameter of 0.05 μm, manufactured by Yadmax Co., Ltd.)
Silane coupling agent: (manufactured by Mitsubishi Chemical corporation, product name "MKC SILICATE MSEP 2") 0.5 parts by mass
A crosslinking agent: aromatic polyisocyanate (product name "CORONATE L" manufactured by TOSOH CORPORATION) 1.5 parts by mass
A first release film (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a polyethylene terephthalate (PET) film, and a second release film (manufactured by Lintec Corporation, product name "SP-PET 381130", thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a PET film were prepared.
Next, the coating solution of the adhesive composition was applied onto the release surface of the first release film using a blade coater, and dried, thereby forming an adhesive layer having a thickness of 5 μm on the release surface of the first release film. Subsequently, the adhesive layer was laminated with the release surface of the second release film superposed thereon, to obtain a first laminate composed of the first release film, the adhesive layer (thickness: 5 μm), and the second release film. Subsequently, the first laminate was aged at a temperature of 23 ℃ and a relative humidity of 50% for 7 days.
(2) Production of second laminate comprising adhesive layer
After obtaining an adhesive composition (V) by mixing the following adhesive base material and a crosslinking agent, a coating solution of the adhesive composition (V) was prepared by diluting with methyl ethyl ketone so that the solid content concentration became 25 mass%.
An adhesion main agent: 100 parts by weight of a (meth) acrylate copolymer (a copolymer obtained by copolymerizing 60 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of methyl methacrylate, and 10 parts by weight of 2-hydroxyethyl acrylate, having a weight average molecular weight of 600,000, manufactured by Ltd., The Nippon Synthetic Chemical Industry Co., Ltd.)
A crosslinking agent: 20 parts by mass of a xylene diisocyanate adduct of trimethylolpropane (product name "TAKENATE D11 ON" manufactured by Mitsui Wuta chemical Co., Ltd.)
A release film (product name "SP-PET 381031" manufactured by Lintec Corporation, thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a PET film was prepared as a third release film.
Further, a polypropylene film was used as a substrate. The polypropylene film had an arithmetic average roughness Ra of 0.3 μm and a thickness of 100. mu.m on the first surface.
Next, the coating solution of the adhesive composition (V) was applied to the release surface of the third release film using a blade coater, and dried and subjected to a crosslinking reaction to obtain a laminate composed of the third release film and an adhesive layer having a thickness of 5 μm. Subsequently, the second surface of the substrate is bonded to the surface of the adhesive layer opposite to the third release film, thereby obtaining a second laminate composed of the substrate, the adhesive layer, and the third release film. It is aged at 23 deg.C and 50% relative humidity for 7 days.
(3) Production of third laminate comprising adhesive layer for jig
After the following components of the main adhesive agent and the crosslinking agent were mixed to obtain an adhesive composition for a jig, the composition was diluted with toluene so that the solid content concentration became 15 mass%, thereby preparing a coating solution of the adhesive composition for a jig.
An adhesion main agent: 100 parts by weight of a (meth) acrylate ester copolymer (a copolymer obtained by copolymerizing 69.5 parts by weight of butyl acrylate, 30 parts by weight of methyl acrylate, and 0.5 part by weight of 2-hydroxyethyl acrylate, weight average molecular weight: 500,000)
A crosslinking agent: aromatic polyisocyanate (product name "CORONATE L" manufactured by TOSOH CORPORATION) 5 parts by mass
Fourth and fifth release films (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a PET film and a polyvinyl chloride film (manufactured by Okamoto Industries, Inc., thickness: 50 μm) as a core material were prepared.
Next, the coating solution of the adhesive composition for a jig was applied to the release surface of the fourth release film using a blade coater and dried, thereby forming a first adhesive layer having a thickness of 5 μm on the release surface of the fourth release film. Subsequently, the core material was bonded to the first adhesive layer, thereby obtaining a laminate a composed of the core material, the first adhesive layer, and the fourth release film.
Next, the coating solution of the adhesive composition for a jig was applied to the release surface of the fifth release film using a blade coater and dried, thereby forming a second adhesive layer having a thickness of 5 μm on the release surface of the fifth release film. Subsequently, the surface of the laminate a on which the core material is exposed is bonded to the second adhesive layer, thereby obtaining a third laminate composed of a fourth release film/the first adhesive layer/the core material/the second adhesive layer/the fifth release film. Subsequently, the third laminate was aged at a temperature of 23 ℃ and a relative humidity of 50% for 7 days. In the third laminate, the first adhesive layer, the core material, and the second adhesive layer constitute a jig adhesive layer having a thickness of 60 μm.
(4) Production of fourth laminate
The second release film was peeled from the first laminate obtained in (1) above, and the adhesive layer was exposed. On the other hand, the third release film was peeled from the second laminate obtained in (2) above, and the adhesive layer was exposed. The first laminate and the second laminate are bonded so that the adhesive layer is in contact with the adhesive layer, thereby obtaining a fourth laminate in which a base material, the adhesive layer, and a first release film are laminated.
(5) Manufacture of semiconductor processing sheet
The fifth release film was peeled from the third laminate obtained in (3), and the inner peripheral edge of the adhesive layer for a jig was partially cut from the second adhesive layer side so that the fourth release film remained, and the inner circular portion was removed. In this case, the inner peripheral diameter of the adhesive layer for a jig was set to 230 mm.
The first release film was peeled off from the fourth laminate obtained in (4) above, and the exposed adhesive layer was overlapped with and pressure-bonded to the adhesive layer for a jig exposed on the third laminate. Subsequently, the outer peripheral edge portion of the semiconductor processing sheet is cut from the base material side so that the fourth release film of the third laminate remains, and the outer portion is removed. In this case, the diameter of the outer peripheral edge of the semiconductor processing sheet was set to 270 mm.
In the above manner, a semiconductor processing sheet was obtained which was composed of an adhesive layer (thickness: 5 μm), an adhesive layer laminated on the adhesive layer on the side opposite to the substrate, an annular adhesive layer for a jig laminated on the peripheral edge portion of the adhesive layer on the side opposite to the adhesive layer, and a fourth release film laminated on the adhesive layer for a jig on the side opposite to the adhesive layer, on the substrate. The surface (first surface) of the fourth release film on the side of the adhesive agent layer for a jig had an arithmetic mean roughness Ra of 0.03 μm, and the surface (second surface) opposite to the first surface had an arithmetic mean roughness Ra of 0.3 μm.
[ example 11]
(1) Production of first laminate comprising protective film-forming layer
After mixing the following binder polymer, thermosetting resin, heat-activated latent epoxy resin curing agent, curing accelerator, filler, colorant, and silane coupling agent to obtain a protective film-forming layer composition, the protective film-forming layer composition was diluted with methyl ethyl ketone so that the solid content concentration became 50 mass%, thereby preparing a coating solution of the protective film-forming layer composition.
Binder polymer: (meth) acrylate ester copolymer (copolymer 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, having a weight average molecular weight of 800,000 and a glass transition temperature of-1 ℃ C.) of 150 parts by mass
Heat-curable components:
60 parts by mass of bisphenol A type epoxy resin (product name "jER 828" manufactured by Mitsubishi Chemical corporation; epoxy equivalent 184-194 g/eq)
10 parts by mass of bisphenol A type epoxy resin (product name "jER 1055" manufactured by Mitsubishi Chemical corporation, epoxy equivalent of 800 to 900g/eq)
30 parts by mass of a dicyclopentadiene type epoxy resin (product name "Epiclon HP-7200 HH" manufactured by DIC CORPORATION, epoxy equivalent 255 to 260g/eq)
Thermally active latent epoxy curing agent: cyanoguanidine (product name "ADEKA HARDENER-EH3636 AS" manufactured by ADEKA CORPORATION, active hydrogen amount 21g/eq)2 parts by mass
Curing accelerator: 2 parts by mass of 2-phenyl-4, 5-dimethylol imidazole (product name "CUREZOLE 2 PHZ" manufactured by SHIKOKU CHEMICALS CORPORATION)
Filling: 320 parts by mass of a silica filler (product name "SC 2050 MA", average particle diameter: 0.5 μm, manufactured by Yadmax Co., Ltd.)
Colorant: carbon Black (manufactured by Mitsubishi Chemical corporation, product name "# MA 650", average particle diameter: 28nm)1.2 parts by mass
Silane coupling agent: (Shin-Etsu Chemical Co., Ltd., product name "KBM-403" manufactured by Ltd.) 2 parts by mass
A first release film (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a polyethylene terephthalate (PET) film, and a second release film (manufactured by Lintec Corporation, product name "SP-PET 381130", thickness: 38 μm) in which a silicone-based release agent layer was formed on one surface of a PET film were prepared.
First, a coating solution of the above-described protective film forming layer composition was applied on the release surface of the first release film using a blade coater and dried, thereby forming a protective film forming layer having a thickness of 25 μm on the release surface of the first release film. Subsequently, the protective film-forming layer was laminated with the release surface of the second release film, thereby obtaining a first laminate composed of the first release film, the protective film-forming layer (thickness: 25 μm), and the second release film. The first laminate was aged at a temperature of 23 ℃ and a relative humidity of 50% for 7 days.
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 10, except that the first laminate produced in the above-described manner was used.
[ example 12]
(1) Preparation of adhesive composition (VI)
An acrylic copolymer having a weight-average molecular weight of 620,000 was obtained by copolymerizing 68.5 parts by mass of butyl acrylate, 30 parts by mass of methacrylic acid, 0.5 part by mass of 2-hydroxyethyl acrylate, and 1 part by mass of acrylamide.
Then, 100 parts by mass of the obtained acrylic copolymer and 10 parts by mass of trimethylolpropane-modified toluene diisocyanate (product name "CORONATE L", manufactured by TOSOH CORPORATION) as a crosslinking agent were mixed in a solvent to obtain a coating solution of the adhesive composition (VI).
(2) Manufacture of semiconductor processing sheet
A semiconductor processing sheet was produced in the same manner as in example 1, except that the adhesive composition (VI) prepared in the above-described manner was used.
Comparative example 1
A sheet for semiconductor processing was produced in the same manner as in example 1, except that a release film (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) obtained by peeling one surface (first surface) of a polyethylene terephthalate film with a silicone-based peeling agent was used as the release film. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the other surface (second surface) had an arithmetic average roughness Ra of 0.05. mu.m.
Comparative example 2
A sheet for semiconductor processing was produced in the same manner as in example 3, except that a release film (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) obtained by peeling one surface (first surface) of a polyethylene terephthalate film with a silicone-based peeling agent was used as the release film. The first surface of the release film had an arithmetic average roughness Ra of 0.03. mu.m, and the other surface (second surface) had an arithmetic average roughness Ra of 0.05. mu.m.
Comparative example 3
A sheet for semiconductor processing was produced in the same manner as in example 2, except that a release film made of a polyethylene terephthalate film (manufactured by mitsubishi resin corporation, product name "diafil (registered trademark) T-10038", thickness: 38 μm) was used as the release film. Further, the arithmetic average roughness Ra of both surfaces of the release film was 0.05. mu.m.
[ test example 1] (measurement of peeling force. alpha.)
The semiconductor processing sheets manufactured in examples and comparative examples were cut into pieces having a width of 50mm × a length of 100 mm. At this time, the semiconductor processing sheet was cut so that the flow direction (MD direction) at the time of manufacturing was the longitudinal direction. The semiconductor processing sheets cut in this manner were stacked into 10 sheets with the substrate as the upper side, and the stacked body was sandwiched from the top and bottom by glass plates 75mm in width, 15mm in length, and 5mm in thickness. Then, the glass plate was stored for 3 days in a moist heat facilitator (manufactured by ESPEC CORP., product name "SH 641") set to a dry state at 40 ℃ with a 500g weight placed on the upper glass plate. When the semiconductor processing sheet contains an energy ray-curable material, the laminate is stored in a state where the laminate is shielded from light.
After the end of the storage, the 2 semiconductor processing sheets, which are the outermost semiconductor processing sheet and the adjacent semiconductor processing sheet, were separated from the laminate in a state of being stacked as a measurement sample. Subsequently, the release film positioned on the outermost layer of the measurement sample was peeled off, and the exposed adhesive surface was bonded to a stainless steel plate using a double-sided adhesive tape, and fixed to a universal tensile tester (orsientec co., LTD, product name: TENSILON UTM-4-100). Subsequently, the semiconductor processing sheet located farthest from the stainless steel plate was peeled from the semiconductor processing sheet stacked thereon at a stretching speed of 300 mm/min in a 180 ° direction at a temperature of 23 ℃ and a relative humidity of 50% RH. That is, the peeling was performed between the first surface of the substrate and the second surface of the release film. The force at this time was measured and recorded as the peel force α (mN/50 mm). The results are shown in Table 2. In addition, when the peel force α was so small that it could not be measured, or when the release film had peeled from the substrate before the measurement, the measurement result was evaluated as "no measurement (0)".
[ test example 2] (measurement of peeling force. beta.)
A laminate comprising 10 semiconductor processing sheets was produced in the same manner as in test example 1, and stored at 40 ℃ for 3 days. 1 semiconductor processing sheet was taken out of the laminate, and the first surface of the substrate was bonded to a stainless steel plate using a double-sided adhesive tape, and fixed to a universal tensile tester (orsientec co., LTD, product name: tenslon UTM-4-100). Subsequently, only the release film was peeled at a stretching speed of 300 mm/min in the 180 ℃ direction under the conditions of a temperature of 23 ℃ and a relative humidity of 50% RH. That is, the peeling was performed between the first surface of the release film and the second surface of the adhesive. The force at this time was measured and recorded as the peel force β (mN/50 mm). The results are shown in Table 2. Further, based on the peeling force β and the peeling force α measured in test example 1, a ratio (α/β) of the peeling force α to the peeling force β was calculated. In this case, when the measurement result of the peeling force α is "no measurement (0)", the ratio (α/β) is evaluated as "0". The results are shown in Table 2.
[ test example 3] (evaluation of unwinding from a coil)
The semiconductor processing sheets produced in examples and comparative examples were prepared as long sheets having a width of 290 mm. Then, a cut was cut from the base material side, and a circular main use portion and a sheet remaining portion were formed as shown in fig. 9. At this time, only the layers other than the release film were cut (half-cut), and the diameter of the main portion was 270 mm. Subsequently, the base material and the adhesive layer (or the adhesive layer or the protective film-forming layer when other components are present) are removed except for the main use portion and the sheet remaining portion. Thus, a semiconductor processing sheet having 100 main use portions was obtained. The semiconductor processing sheet is wound in a roll shape so that the base material side becomes the outer side.
The rolled semiconductor processing sheet thus obtained was stored in a moist heat promoter (manufactured by ESPEC corp, product name "SH 641") set to a dry state at 40 ℃ for 3 days. When the semiconductor processing sheet contains an energy ray-curable material, the laminate is stored in a state where it is shielded from light.
After the completion of the storage, the semiconductor processing sheet wound in a roll form was unwound using a wafer laminator (product name "RAD-2500 m/8" manufactured by Lintec Corporation). Then, it was checked whether or not unwinding was possible satisfactorily in the region where 20 main use portions at both ends in the longitudinal direction of the semiconductor processing sheet existed (i.e., the region where 20 main use portions existed in the outer portion of the roll and the region where 20 main use portions existed in the inner portion of the roll). At this time, when 20 sheets of the main used portions were continuously and satisfactorily unreeled in any one area, the evaluation was evaluated as ∘. On the other hand, even when a defect that the second surface of the release film was adhered to the main use portion overlapped therebelow and could not be unwound occurred in 1 main use portion, the evaluation was x. The results are shown in Table 2.
[ test example 4] (evaluation of adhesion)
A rolled semiconductor processing sheet was produced in the same manner as in test example 3 and stored at 40 ℃ for 3 days. Subsequently, the main use portion was peeled off from the release film of the roll using a wafer laminator (manufactured by Lintec Corporation, product name "RAD-2500 m/8"), and attached (laminated) to a semiconductor wafer. This operation was repeated 20 times in succession, and when well completed, it was rated as O. On the other hand, when a defective lamination occurred due to a defective peeling from the release film at a main portion, the evaluation was X. The results are shown in Table 2.
The structures of the semiconductor processing sheets produced in examples and comparative examples are shown in table 1. The abbreviations shown in Table 1 are as follows.
[ base Material ]
PVC: polyvinyl chloride
EMAA: ethylene-methacrylic acid copolymer
EVA: ethylene-vinyl acetate copolymer
PP: polypropylene
[ Release film ]
PET: polyethylene terephthalate
[ test example 5] (evaluation of light transmittance)
The semiconductor processing sheet having been stored for 3 days in test example 3 and the ring frame were attached to the mirror surface of a silicon wafer having a thickness of 350 μm using a wafer laminator (manufactured by Lintec Corporation, product name "RAD-2500 m/8"). Subsequently, silicon wafers were cut using a cutting apparatus (manufactured by DISCO inc., product name "DFD-651") under the following conditions.
Cutting conditions are as follows:
workpiece (cut object): silicon wafer (size: 6 inch, thickness: 350 μm, attachment surface: mirror surface)
Cutting blade: manufactured by DISCO Inc., product name "27 HECC"
Blade revolution number: 30,000rpm
Cutting speed: 10 mm/sec
Incision depth: a notch with a depth of 20 μm from the surface of the base material opposite to the cutting device table
Cut size: 5mm
The wafer bonded to the semiconductor processing sheet obtained by the dicing was visually checked through the semiconductor processing sheet from the side of the surface (second surface of the base material) of the semiconductor processing sheet opposite to the wafer to see whether the peripheral edge and the corner of the wafer could be recognized. In addition, in the case of using a semiconductor processing sheet provided with an adhesive layer, the peripheral edge and corner portions of the wafer with the adhesive were confirmed; in the case of using a semiconductor processing sheet provided with a protective film-forming layer, the peripheral edge and corner portions of the wafer with the protective film were confirmed. The case where the peripheral edge and the corner were confirmed was evaluated as good light transmittance (visible light transmittance) (o), and the case where the peripheral edge and the corner were not confirmed was evaluated as poor light transmittance (visible light transmittance) (x). The results are shown in Table 2.
[ Table 1]
Figure BDA0001647796080000511
[ Table 2]
Figure BDA0001647796080000521
As is apparent from table 2, the semiconductor processing sheets of the examples have excellent light transmittance and excellent evaluations in both unwinding from a roll and bonding. On the other hand, the semiconductor processing sheet of the comparative example had a problem in either unwinding from a roll or bonding.
Industrial applicability
The semiconductor processing sheet of the present invention is suitably used as a dicing sheet, a dicing die bonding sheet, a protective film forming layer integrated dicing sheet, and the like.
Description of the reference numerals
1.1 a, 1b, 1c, 1d, 1e, 2, 3: a semiconductor processing sheet;
10. 10a, 10 b: a substrate;
101: a first side;
102: a second face;
20: an adhesive layer;
201: a first side;
202: a second face;
30: stripping the film;
301: a first side;
302: a second face;
40: an adhesive layer;
401: a first side;
402: a second face;
50: a protective film forming layer;
501: a first side;
502: a second face;
60: an adhesive layer for a jig;
601: a first side;
602: a second face;
80. 80a, 80 b: a semiconductor attachment layer; 801: a first side;
802: a second face.

Claims (9)

1. A semiconductor processing sheet at least comprises: a base material having a first surface and a second surface located on the opposite side of the first surface; a semiconductor adhesive layer laminated on the second surface side of the base material, and having a first surface on a side close to the base material and a second surface on a side far from the base material; and a release film laminated on the second surface side of the semiconductor adhesion layer, the release film having a first surface on a side close to the semiconductor adhesion layer and a second surface on a side far from the semiconductor adhesion layer, wherein:
the base material is at least one selected from ethylene-methyl methacrylate copolymer film, polyvinyl chloride film and polypropylene film,
the arithmetic average roughness Ra of the first surface of the base material is 0.01 to 0.03 μm,
the second surface of the release film has an arithmetic mean roughness Ra of 0.3 to 0.8 μm,
a ratio (α/β) of α to β is 0 or more and less than 1.0, where α is a peeling force at an interface between the first surface of the substrate and the second surface of the release film after the first surface of the substrate and the second surface of the release film are laminated and stored at 40 ℃ for 3 days, and β is a peeling force at an interface between the second surface of the semiconductor adhesive layer and the first surface of the release film after the second surface of the semiconductor adhesive layer and the first surface of the release film are adhered and stored at 40 ℃ for 3 days,
the peeling force beta is 10-1000 mN/50 mm.
2. The sheet for semiconductor processing according to claim 1, wherein the release film has a release agent layer on each of the first surface side and the second surface side.
3. The sheet for semiconductor processing according to claim 1, wherein the semiconductor adhesive layer is an adhesive layer.
4. The sheet for semiconductor processing according to claim 1, wherein the semiconductor attachment layer is an adhesive layer.
5. The sheet for semiconductor processing according to claim 1, wherein the semiconductor adhesive layer is a protective film-forming layer.
6. The sheet for semiconductor processing according to claim 1, wherein the semiconductor adhesive layer comprises an adhesive layer and an adhesive layer located between the adhesive layer and the release film.
7. The sheet for semiconductor processing according to claim 1, wherein the semiconductor adhesive layer comprises an adhesive layer and a protective film forming layer located between the adhesive layer and the release film.
8. The sheet for semiconductor processing according to claim 1, wherein the sheet for semiconductor processing is formed by laminating a laminate on the long release film, the laminate having a shape different from that of the release film in a plan view and comprising the base material and the semiconductor adhesive layer.
9. A semiconductor processing sheet at least comprises: a base material having a first surface and a second surface located on the opposite side of the first surface; a semiconductor adhesive layer laminated on the second surface side of the base material, and having a first surface on a side close to the base material and a second surface on a side far from the base material; a jig adhesive layer which is laminated on the second surface side of the semiconductor adhesive layer, and which has a first surface on the side close to the semiconductor adhesive layer and a second surface on the side away from the semiconductor adhesive layer; and a release film that is laminated on at least a second surface side of the adhesive agent layer for a clip, and that has a first surface on a side close to the adhesive agent layer for a clip and a second surface on a side away from the adhesive agent layer for a clip, characterized in that:
the base material is at least one selected from ethylene-methyl methacrylate copolymer film, polyvinyl chloride film and polypropylene film,
the arithmetic average roughness Ra of the first surface of the base material is 0.01 to 0.03 μm,
the second surface of the release film has an arithmetic mean roughness Ra of 0.3 to 0.8 μm,
a ratio (α/β) of an α to a β is 0 or more and less than 1.0, where α is a peel force at an interface between the first surface of the substrate and the second surface of the release film after the first surface of the substrate and the second surface of the release film are laminated and stored at 40 ℃ for 3 days, and β is a peel force at an interface between the second surface of the adhesive layer for a jig and the first surface of the release film after the second surface of the adhesive layer for a jig and the first surface of the release film are attached and stored at 40 ℃ for 3 days,
the peeling force beta is 10-1000 mN/50 mm.
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