CN113980535A - Protective film forming film, composite sheet for protective film formation, and method for manufacturing semiconductor chip with protective film - Google Patents

Protective film forming film, composite sheet for protective film formation, and method for manufacturing semiconductor chip with protective film Download PDF

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Publication number
CN113980535A
CN113980535A CN202111107427.8A CN202111107427A CN113980535A CN 113980535 A CN113980535 A CN 113980535A CN 202111107427 A CN202111107427 A CN 202111107427A CN 113980535 A CN113980535 A CN 113980535A
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protective film
film
film forming
forming
ultraviolet
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小桥力也
山本大辅
加太章生
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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
    • H01L21/67—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The protective film forming film contains an ultraviolet-curable component, and has a transmittance of 8% or more for light having a wavelength of 375nm and a transmittance of 12% or less for light having a wavelength of 550 nm. The protective film-forming film may further contain a colorant, and the colorant may be a red colorant.

Description

Protective film forming film, composite sheet for protective film formation, and method for manufacturing semiconductor chip with protective film
This application is a divisional application based on patent applications having an application date of 2015 year 10-23, a priority date of 2014 year 10-29, an application number of 201580058160.4 (international application number PCT/JP2015/079973), and an invention name of "protective film forming film and protective film forming composite sheet".
Technical Field
The present invention relates to a protective film forming film, a protective film forming sheet, and a protective film forming composite sheet capable of forming a protective film on a workpiece such as a semiconductor wafer or a processed product (for example, a semiconductor chip) obtained by processing the workpiece.
The present application claims priority of Japanese application No. 2014-220295 filed in Japan at 10/29 of 2014, the contents of which are hereby incorporated by reference.
Background
In recent years, semiconductor devices have been manufactured by a mounting method called a so-called flip-chip (face down) method. In this method, when a semiconductor chip having a circuit surface on which electrodes such as bumps are formed is mounted, the circuit surface side of the semiconductor chip is bonded to a chip mounting portion such as a lead frame. This exposes the back side of the semiconductor chip on which no circuit is formed.
Therefore, in order to protect the semiconductor chip, a protective film made of a hard organic material is often formed on the back surface side of the semiconductor chip. The protective film is formed using a film for semiconductor back surface or a dicing tape-integrated wafer back surface protective film as shown in patent document 1 or 2, for example.
Here, the protective film is generally formed of a thermosetting resin such as an epoxy resin. However, the curing temperature of the thermosetting resin exceeds 130 ℃ and the curing time is about 2 hours, which is an obstacle to the improvement of the production efficiency. For this reason, a protective film having a curing mechanism capable of shortening the processing time is desired.
In view of the above, patent document 3 discloses an energy ray-curable chip protection film having an energy ray-curable protective film-forming layer containing (a) a polymer component formed of an acrylic copolymer having no double bond, (B) an energy ray-curable component, (C) a dye and/or a pigment, (D) an inorganic filler, and (E) a photopolymerization initiator that absorbs light in a long wavelength range of 350nm or more. Such an energy ray-curable film for protecting a chip can be cured in a short time mainly by irradiation with ultraviolet rays, and therefore, a protective film can be formed easily, which contributes to improvement of production efficiency.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-28396
Patent document 2: japanese patent laid-open publication No. 2012-235168
Patent document 3: japanese laid-open patent publication No. 2009-138026
Disclosure of Invention
Problems to be solved by the invention
However, the component (C) used in the examples of patent document 3 is a black pigment, and the chip protection film containing the black pigment has low ultraviolet transmittance. Therefore, when ultraviolet rays are irradiated to cure the die-protecting film, the ultraviolet rays cannot sufficiently reach the inside of the film and the surface opposite to the ultraviolet-irradiated surface, and the curing of the die-protecting film may be insufficient. If the curing of the film for protecting a chip is insufficient in this way, the obtained protective film is likely to be peeled off by heat or the like, and there is a problem in the function as the protective film.
On the other hand, grinding marks generated by back grinding of the semiconductor wafer are usually left on the back surface of the semiconductor chip. From the viewpoint of the appearance of the semiconductor chip, it is desirable that such grinding marks are not visually observed, and are desirably shielded by the protective film.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a protective film forming film, a protective film forming sheet, and a protective film forming composite sheet which have excellent ultraviolet curability and are capable of forming a protective film in which grinding marks existing on a workpiece or a processed object are not observed with the naked eye.
Means for solving the problems
In order to achieve the above object, the first invention provides a protective film forming film containing an ultraviolet curable component, having a transmittance of 8% or more with respect to light having a wavelength of 375nm and a transmittance of 12% or less with respect to light having a wavelength of 550nm (invention 1).
The protective film forming film according to the above invention (invention 1) can be sufficiently cured by ultraviolet rays, and can form a protective film in which grinding marks existing on a workpiece or a processed object are not observed with the naked eye after ultraviolet rays are cured.
In the above invention (invention 1), a colorant (invention 2) may be further contained.
In the above invention (invention 2), the colorant may be a red colorant (invention 3).
In the above inventions (inventions 2 and 3), the colorant may be an organic colorant (invention 4).
In the above inventions (inventions 2 to 4), a value W/T obtained by dividing a content W (mass%) of the colorant in the protective film forming film by a thickness T (μm) of the protective film forming film may be 0.01 to 0.5 (invention 5).
In the above inventions (inventions 1 to 5), the protective film-forming film was irradiated from one side with 3 times an illuminance of 215mW/cm2Light quantity 187mJ/cm2In the case of the ultraviolet ray of (1), the ratio P2/P1 of the peak P2 of the probe viscosity (プローブタック, probe tack) of the surface opposite to the ultraviolet ray irradiated surface to the peak P1 of the probe viscosity of the ultraviolet ray irradiated surface may be 0.1 to 7 (invention 6).
In the above inventions (inventions 1 to 6), the transmittance for light having a wavelength of 1600nm may be 25% or more (invention 7).
The second aspect of the present invention provides a protective film-forming sheet (invention 8) comprising the protective film-forming film (inventions 1 to 7) and a release sheet laminated on one or both surfaces of the protective film-forming film. In this specification, "sheet" is a concept including a tape.
The third invention provides a composite sheet for forming a protective film (invention 9) comprising a support sheet and the protective film forming film laminated on one surface side of the support sheet (inventions 1 to 7).
In the invention (invention 9), the support sheet may be formed of a base material and a pressure-sensitive adhesive layer laminated on the protective film forming film side of the base material, or may be formed of a base material (invention 10).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the protective film forming film, the protective film forming sheet and the protective film forming composite sheet of the present invention, a protective film which is sufficiently cured by ultraviolet rays and in which grinding marks existing on a workpiece or a processed object are not observed with the naked eye can be formed.
Drawings
FIG. 1 is a sectional view of a protective film-forming sheet according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention.
Fig. 4 is a cross-sectional view showing an example of use of the composite sheet for forming a protective film according to the embodiment of the present invention.
FIG. 5 is a graph showing the measurement results of light transmittance in test example 1.
Description of the symbols
1 … protective film forming film
2 … sheet for forming protective film
21 … Release sheet
3. Composite sheet for forming 3A … protective film
4 … supporting sheet
41 … base material
42 … adhesive layer
5 … adhesive layer for clip
6 … semiconductor wafer
7 … Ring frame
Detailed Description
Hereinafter, embodiments of the present invention will be described.
[ protective film Forming film ]
The protective film forming film of the present embodiment is used for forming a protective film on a workpiece or a workpiece obtained by processing the workpiece. Examples of the workpiece include a semiconductor wafer, and examples of the processed object obtained by processing the workpiece include a semiconductor chip, but the present invention is not limited to these. When the workpiece is a semiconductor wafer, the protective film is formed on the back surface side of the semiconductor wafer (the side of the bumps on which the electrodes are not formed).
1. Physical Properties
The protective film forming film of the present embodiment has a transmittance of 8% or more for light having a wavelength of 375nm and a transmittance of 12% or less for light having a wavelength of 550 nm. In the present specification, the light transmittance is a value measured by using an integrating sphere, and a spectrophotometer is used as a measuring instrument.
As described later, the protective film forming film of the present embodiment contains an ultraviolet curable component. When the transmittance for light having a wavelength of 375nm is 8% or more as described above, the ultraviolet ray easily transmits through the protective film forming film, and thus the ultraviolet ray curable component in the protective film forming film is easily cured. Therefore, even when the ultraviolet ray is irradiated to the protective film forming film from one side, the entire protective film forming film is sufficiently cured, and insufficient curing can be effectively prevented from occurring in the interior of the protective film forming film and the surface opposite to the ultraviolet ray irradiation surface.
From the viewpoint of curability of the protective film forming film, the protective film forming film preferably has a transmittance of 10% or more, more preferably 13% or more, further preferably 15% or more, particularly preferably 17% or more, and further preferably 20% or more, with respect to light having a wavelength of 375 nm. The upper limit of the transmittance for light having a wavelength of 375nm is not particularly limited, and can be naturally determined by setting the transmittance for light having a wavelength of 550nm to 12% or less. Specifically, the protective film forming film preferably has a transmittance of 35% or less with respect to light having a wavelength of 375 nm.
On the other hand, for example, a grinding trace generated by back grinding of the semiconductor wafer usually remains on the back surface of the semiconductor chip. When the transmittance of light having a wavelength of 550nm is 12% or less as described above, the protective film forming film hardly transmits visible light. Therefore, the grinding traces are shielded by the protective film forming film (protective film) and are hardly observed by the naked eye. This improves the appearance of the processed product such as a semiconductor chip.
From the viewpoint of the grinding mark shielding property, the transmittance of the protective film forming film to light having a wavelength of 550nm is preferably 11% or less, particularly preferably 8% or less, and still more preferably 5% or less. The lower limit of the transmittance for light having a wavelength of 550nm is not particularly limited, and can be naturally determined by setting the transmittance for light having a wavelength of 375nm to 8% or more. Specifically, the transmittance of the protective film forming film to light having a wavelength of 375nm is preferably 0% or more.
The transmittance of the protective film forming film of the present embodiment to light having a wavelength of 1600nm is preferably 25% or more, more preferably 40% or more, particularly preferably 45% or more, and still more preferably 50% or more. In a semiconductor chip or the like obtained by dicing a semiconductor wafer, a crack or the like may be generated by a stress generated during processing. When the transmittance of light having a wavelength of 1600nm is 25% or more as described above, the transmittance of infrared rays becomes good, and infrared inspection for obtaining infrared rays can be performed from the side of the protective film forming film (or the protective film formed by the protective film forming film). Thus, cracks and the like in a work such as a semiconductor chip can be found through the protective film forming film (protective film), and the product yield can be improved.
The upper limit of the transmittance for light having a wavelength of 1600nm is not particularly limited, and can be naturally determined by setting the transmittance for light having a wavelength of 550nm to 12% or less. In addition, when a work (such as a semiconductor chip) having a protective film formed thereon is used, the protective film forming film has a transmittance of 90% or less with respect to light having a wavelength of 1600nm, whereby it is possible to prevent malfunction of the work which is easily affected by infrared rays from the outside.
The protective film forming film of the present embodiment may be formed of a single layer or a plurality of layers, and is preferably formed of a single layer in terms of ease of controlling light transmittance and manufacturing cost. When the protective film forming film is formed of a plurality of layers, it is preferable that the light transmittance as described above is satisfied as the whole of the plurality of layers in view of easiness of controlling the light transmittance.
In the protective film forming film of the present embodiment, when the protective film forming film is irradiated with ultraviolet light from one side, the ratio P2/P1 between the peak P2 of the probe viscosity on the side opposite to the ultraviolet light irradiation surface (hereinafter, sometimes referred to as "the side opposite to the ultraviolet light irradiation surface") and the peak P1 of the probe viscosity on the ultraviolet light irradiation surface is preferably 0.1 to 7, particularly preferably 0.5 to 4, and still more preferably 1 to 2. For example, P2/P1 can be made to be a value lower than 1 by: the protective film-forming film is formed of a plurality of layers, and more ultraviolet-curable components (a) described later are blended in the layer to be formed with the opposite side to ultraviolet irradiation with respect to the layer to be formed with the ultraviolet-irradiated side. The method for measuring the probe tack is based on JIS Z10231999, and is specifically shown in the test examples described later.
By making P2/P1 within the above range, the protective film forming film (protective film) is cured not only on the side of the ultraviolet ray irradiation surface but also on the side opposite to the ultraviolet ray irradiation surface, that is, the protective film forming film can be sufficiently cured in the entire thickness direction.
When the probe viscosity is expressed by an energy value, the ratio E2/E1 of the energy value E2 of the probe viscosity on the side opposite to the ultraviolet irradiation to the energy value E1 of the probe viscosity on the ultraviolet irradiation side is preferably 0.1 to 10, particularly preferably 0.5 to 5, and more preferably 1 to 2.5. For example, E2/E1 may be set to a value lower than 1 by: the protective film-forming film is formed of a plurality of layers, and more ultraviolet-curable components (a) described later are blended in the layer to be formed with the opposite side to ultraviolet irradiation with respect to the layer to be formed with the ultraviolet-irradiated side.
The peak P1 of the probe viscosity on the ultraviolet irradiation surface is preferably 0.05 to 1.5, particularly preferably 0.1 to 1, and further preferably 0.15 to 0.75. The energy value E1 of the probe viscosity on the ultraviolet irradiation surface is preferably 0.005 to 0.3, more preferably 0.008 to 0.15, and still more preferably 0.01 to 0.1. By setting the peak value P1 of the probe tack and/or the energy value E1 on the ultraviolet ray irradiated face in the above range, at least the ultraviolet ray irradiated face side of the protective film forming film (protective film) can be cured to a high degree.
2. Material
The protective film forming film of the present embodiment contains an ultraviolet curable component (a). The ultraviolet-curable component (a) is preferably an uncured ultraviolet-curable component, and particularly preferably an uncured ultraviolet-curable component having adhesiveness.
The protective film forming film is formed by laminating the protective film forming film and a work such as a semiconductor wafer, and then curing the protective film forming film by ultraviolet irradiation, thereby forming a durable protective film on a chip or the like. Since the protective film forming film is cured in a short time, the production efficiency is excellent. In addition, if the protective film forming film has adhesiveness, the protective film forming film and the semiconductor wafer can be bonded to each other when a workpiece such as the semiconductor wafer is stacked on the protective film forming film as described above. Therefore, positioning can be reliably performed before curing the protective film forming film. The protective film forming film may have adhesiveness at normal temperature or may exert adhesiveness by heating.
Here, the light transmittance of the protective film forming film does not substantially change before and after curing. Therefore, if the transmittance of the protective film forming film before curing is 8% or more for light having a wavelength of 375nm and 12% or less for light having a wavelength of 550nm, the transmittance of the protective film forming film (protective film) after curing is also 13% or more for light having a wavelength of 375nm and 12% or less for light having a wavelength of 550 nm.
The protective film forming film of the present embodiment preferably contains a colorant (B) in addition to the ultraviolet-curable component (a). The protective film forming film contains the colorant (B), and thus the transmittance of light having a wavelength of 375nm and a wavelength of 550nm (further, a wavelength of 1600nm) can be easily controlled to the above range.
In addition, the protective film forming film of the present embodiment preferably contains a filler (C) in addition to the colorant (B). This makes it easy to control the light transmittance at the wavelength of 375nm and 550nm (further, at the wavelength of 1600nm) to the above range. In addition, if the protective film forming film contains a filler, the moisture resistance can be improved while maintaining high hardness of the cured protective film. Further, the thermal expansion coefficient of the protective film after curing can be made close to that of the semiconductor wafer, whereby the warp of the semiconductor wafer during processing can be reduced.
The protective film forming film of the present embodiment preferably further contains a thermosetting component (D). By heating the protective film forming film further containing the thermosetting component (D), the adhesion of the protective film forming film to the workpiece and the strength of the cured protective film can be improved.
When the protective film forming film contains the ultraviolet-curable component (a) and the colorant (B), the ratio of the ultraviolet-curable component (a) and the ratio of the colorant (B) are set so that the total of the ratio of the ultraviolet-curable component (a) and the ratio of the colorant (B) is 100% by mass. Similarly, when the protective film forming film contains the ultraviolet-curable component (a), the colorant (B), and the filler (C), the proportions of the ultraviolet-curable component (a), the colorant (B), and the filler (C) are set so that the total of the proportion of the ultraviolet-curable component (a), the proportion of the colorant (B), and the proportion of the filler (C) is 100% by mass. When the protective film forming film contains the ultraviolet-curable component (a), the colorant (B), the filler (C), and the thermosetting component (D), the proportions of the ultraviolet-curable component (a), the colorant (B), the filler (C), and the thermosetting component (D) are set so that the total of the proportions of the ultraviolet-curable component (a), the colorant (B), the filler (C), and the thermosetting component (D) is 100 mass%.
(1) Ultraviolet ray curing component (A)
The ultraviolet-curable component (a) may be the polymer (a1) into which an ultraviolet-curable group has been introduced, or may be a component containing an ultraviolet-curable compound (A3) other than the polymer (a1) into which an ultraviolet-curable group has been introduced. When the ultraviolet-curable component (a) of the present embodiment contains the ultraviolet-curable compound (A3), it preferably further contains a polymer such as a polymer (a2) that is not ultraviolet-curable. In this specification, "polymer" is a concept including "copolymer" as well.
(1-1) ultraviolet-curable group-introduced Polymer (A1)
When the ultraviolet-curable component (a) in the present embodiment contains the polymer (a1) having an ultraviolet-curable group introduced therein, the polymer (a1) may be contained as it is in the protective film-forming film, or may be contained as a crosslinked product formed by crosslinking reaction of at least a part thereof with a crosslinking agent.
Examples of the ultraviolet-curable group-introduced polymer (a1) include an acrylic polymer that is a reaction product of a functional group-containing acrylic polymer (a1-1) and a curable group-containing compound (a1-2), wherein the functional group-containing acrylic polymer (a1-1) contains a functional group-containing monomer as a constituent component, and the curable group-containing compound (a1-2) has a substituent that reacts with the functional group and an ultraviolet-curable carbon-carbon double bond.
The functional group-containing acrylic polymer (a1-1) is preferably a copolymerization product of a functional group-containing acrylic monomer, a functional group-free acrylic monomer, and if necessary, a monomer other than the acrylic monomer. That is, the functional group-containing monomer is preferably a functional group-containing acrylic monomer.
In the present specification, the terms "polymer" and "resin" used for a substance obtained by polymerizing a monomer refer to a "polymer" and a "resin" containing a structural unit (also referred to as a repeating unit) derived from the above monomer.
As the functional group of the functional group-containing acrylic monomer (functional group of the functional group-containing monomer), a functional group capable of reacting with the substituent group of the curable group-containing compound (a1-2) can be selected. Examples of such functional groups include: hydroxyl group, carboxyl group, amino group, substituted amino group, epoxy group and the like, and among them, hydroxyl group is preferable. When the ultraviolet-curable component (a) of the present embodiment contains a crosslinking agent, the functional group-containing acrylic polymer (a1-1) preferably contains, as a constituent component, a functional group-containing monomer having a functional group reactive with the crosslinking agent, and the functional group-containing monomer may also serve as a functional group-containing monomer having a functional group reactive with a substituent group of the curable group-containing compound.
Examples of the hydroxyl group-containing acrylic monomer (hydroxyl group-containing monomer) include: hydroxyalkyl (meth) acrylates such as 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. Among these, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of reactivity with the curable group-containing compound (A1-2). These hydroxyl group-containing acrylic monomers may be used alone or in combination of 2 or more.
As the acrylic monomer having no functional group, an alkyl (meth) acrylate monomer is preferably contained. Examples of the alkyl (meth) acrylate monomer include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. Among the alkyl (meth) acrylate monomers, alkyl (meth) acrylates in which the alkyl group has 1 to 18 carbon atoms are preferable, and alkyl (meth) acrylates in which the alkyl group has 1 to 4 carbon atoms are particularly preferable. These acrylic monomers having no functional group may be used alone, or 2 or more kinds thereof may be used in combination.
The acrylic monomer having no functional group may include, for example, (meth) acrylic acid esters having an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and (meth) acrylic acid esters having an aromatic ring such as phenyl (meth) acrylate, non-crosslinkable acrylamides such as acrylamide and methacrylamide, (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate, in addition to the above-mentioned alkyl (meth) acrylate monomers.
Examples of the monomer other than the acrylic monomer include olefins such as ethylene and norbornene, vinyl acetate, and styrene.
In the functional group-containing acrylic polymer (A1-1), the ratio of the mass of the moiety derived from the functional group-containing monomer to the total mass of the functional group-containing acrylic polymer (A1-1) is preferably 0.1 to 50 mass%, particularly preferably 1 to 40 mass%, and further preferably 3 to 30 mass%. Thus, the amount of the curable group introduced from the curable group-containing compound (a1-2) (and the amount of reaction with the crosslinking agent) can be adjusted to a desired amount, and the degree of curing (degree of crosslinking) of the obtained protective film can be controlled to a preferred range.
The acrylic polymer having a functional group (A1-1) can be obtained by copolymerizing the above-mentioned monomers by a conventional method. The polymerization system of the functional group-containing acrylic polymer (A1-1) may be a random copolymer or a block copolymer.
The curable group-containing compound (A1-2) has a substituent reactive with the functional group of the functional group-containing acrylic polymer (A1-1) and an ultraviolet-curable carbon-carbon double bond. Examples of the substituent reactive with the functional group of the functional group-containing acrylic polymer (a1-1) include an isocyanate group, an epoxy group, and a carboxyl group, and among them, an isocyanate group having high reactivity with a hydroxyl group is preferable.
The curable group-containing compound (A1-2) preferably contains 1 to 5 ultraviolet-curable carbon-carbon double bonds, and particularly preferably contains 1 to 2 ultraviolet-curable carbon-carbon double bonds, per 1 molecule of the curable group-containing compound (A1-2), on average.
Examples of the curable group-containing compound (a1-2) include: 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1-bis (bisacryloxymethyl) ethyl isocyanate; an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate; and acryloyl monoisocyanate compounds obtained by the reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate. Of these, 2-methacryloyloxyethyl isocyanate is particularly preferable. The curable group-containing compound (a1-2) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The ultraviolet-curable group-introduced polymer (a1) preferably contains 20 to 120 mol%, particularly preferably 35 to 100 mol%, and even more preferably 50 to 100 mol%, of the curable group derived from the curable group-containing compound (a1-2) relative to the functional group (functional group that reacts with the substituent of the curable group-containing compound (a 1-2)) of the polymer (a 1). When the curable group-containing compound (a1-2) is monofunctional, the upper limit is 100 mol%, and when the curable group-containing compound (a1-2) is polyfunctional, the upper limit may exceed 100 mol%. When the ratio of the curable group to the functional group is in the above range, the protective film after ultraviolet curing can have very excellent adhesion.
The weight average molecular weight (Mw) of the ultraviolet-curable group-introduced polymer (a1) is preferably 10 to 200 ten thousand, more preferably 30 to 150 ten thousand. The weight average molecular weight in the present specification is a value measured by a Gel Permeation Chromatography (GPC) method and converted to standard polystyrene.
(1-2) Polymer not having ultraviolet-curing Properties (A2)
When the ultraviolet-curable component (a) of the present embodiment contains the polymer (a2) having no ultraviolet curability, the polymer (a2) may be contained as it is in the protective film-forming film, or may be contained as a crosslinked product formed by crosslinking reaction of at least a part thereof with a crosslinking agent. Examples of the polymer (a2) include phenoxy resins, acrylic polymers (a2-1), urethane resins, polyester resins, rubber resins, and acrylic urethane resins. The case of using the acrylic polymer (A2-1) among these will be described in detail.
As the acrylic polymer (A2-1), conventionally known acrylic polymers can be used. The acrylic polymer (a2-1) may be a homopolymer formed from 1 type of acrylic monomer, a copolymer formed from a plurality of types of acrylic monomers, or a copolymer formed from 1 or more types of acrylic monomers and a monomer other than the acrylic monomer. Specific types of compounds as the acrylic monomer are not particularly limited, and specific examples thereof include (meth) acrylic acid, (meth) acrylic acid esters, and derivatives thereof (acrylonitrile, itaconic acid, and the like). Specific examples of the (meth) acrylic acid ester include (meth) acrylic acid esters having a chain skeleton such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (meth) acrylates having a cyclic skeleton such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and imide acrylate; (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (meth) acrylates having reactive functional groups other than hydroxyl groups, such as glycidyl (meth) acrylate and N-methylaminoethyl (meth) acrylate. Examples of the monomer other than the acrylic monomer include olefins such as ethylene and norbornene, vinyl acetate, and styrene. When the acrylic monomer is an alkyl (meth) acrylate, the number of carbon atoms in the alkyl group is preferably in the range of 1 to 18.
When the ultraviolet-curable component (a) of the present embodiment contains a crosslinking agent, the acrylic polymer (a2-1) preferably has a reactive functional group that reacts with the crosslinking agent. The type of the reactive functional group is not particularly limited, and can be determined as appropriate based on the type of the crosslinking agent and the like.
For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group of the acrylic polymer (a2-1) include a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the reactive functional group of the acrylic polymer (a2-1) include a carboxyl group, an amino group, and an amide group, and among them, a carboxyl group having high reactivity with an epoxy group is preferable. The carboxyl group is preferably 12 wt% or less based on the total reactive functional groups of the acrylic polymer (A2-1).
The method for introducing the reactive functional group into the acrylic polymer (a2-1) is not particularly limited, and examples thereof include the following: the acrylic polymer (A2-1) is formed using a monomer having a reactive functional group, and the polymer has a structural unit based on the monomer having a reactive functional group in the backbone. For example, when a hydroxyl group is introduced into the acrylic polymer (A2-1), the acrylic polymer (A2-1) can be formed using a monomer having a hydroxyl group such as 2-hydroxyethyl acrylate.
When the acrylic polymer (A2-1) has a reactive functional group, the ratio of the mass of the structural moiety derived from the monomer having a reactive functional group to the total mass of the acrylic polymer (A2-1) is preferably about 1 to 20 mass%, more preferably 2 to 10 mass%, from the viewpoint of achieving a good crosslinking degree.
From the viewpoint of film-forming properties at the time of coating, the weight average molecular weight (Mw) of the acrylic polymer (a2-1) is preferably 1 to 200 ten thousand, more preferably 10 to 150 ten thousand.
(1-3) ultraviolet curable Compound (A3)
The ultraviolet-curable component (a) may contain an ultraviolet-curable compound (A3) other than the polymer (a1) into which an ultraviolet-curable group has been introduced, and in this case, it is preferable to contain the above-mentioned polymer (a2) which does not have ultraviolet-curing properties together. Further, instead of the polymer (a2) having no ultraviolet curability, the polymer (a1) having an ultraviolet curability group introduced thereinto may be contained, or both the polymer (a1) having an ultraviolet curability group introduced thereinto and the polymer (a2) having no ultraviolet curability may be contained. The ultraviolet-curable compound (a3) has an ultraviolet-curable group and is a compound that polymerizes when irradiated with ultraviolet light.
The ultraviolet-curable group of the ultraviolet-curable compound (a3) is, for example, a group containing an ultraviolet-curable carbon-carbon double bond, and specifically, a (meth) acryloyl group, a vinyl group, or the like can be exemplified.
The ultraviolet-curable compound (a3) is not particularly limited as long as it has the above-mentioned ultraviolet-curable group, but a low-molecular weight compound (monofunctional or polyfunctional monomer or oligomer) is preferable from the viewpoint of versatility. Specific examples of the low-molecular-weight ultraviolet-curable compound (a3) include: acrylic compounds such as acrylic esters having a cyclic aliphatic skeleton, e.g., trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, dicyclopentadiene dimethoxy diacrylate, isobornyl acrylate, polyethylene glycol diacrylate, oligoester acrylates, urethane acrylate oligomers, epoxy-modified acrylates, polyether acrylates, and itaconic acid oligomers.
Examples of the ultraviolet-curable compound (a3) include an epoxy resin having an ultraviolet-curable group, a phenol resin having an ultraviolet-curable group, and the like. As such a resin, for example, the resin described in Japanese patent laid-open publication No. 2013-194102 can be used. Such a resin also corresponds to a resin constituting the thermosetting component (C) described later, but since it contributes to ultraviolet curing, it is treated as the ultraviolet-curable compound (a) in the present invention.
The molecular weight of the ultraviolet-curable compound (A3) is usually about 100 to 30000, preferably about 300 to 10000. Generally, the ultraviolet-curable compound (A3) is used in an amount of about 10 to 400 parts by mass, preferably about 30 to 350 parts by mass, based on 100 parts by mass of the total amount of the polymer (a1) and the polymer (a 2).
The protective film forming film of the present embodiment preferably contains 5 to 89 mass% of the ultraviolet-curable component (a), particularly preferably 10 to 80 mass%, and further preferably 20 to 70 mass%, based on the mass of the protective film forming film. When the content of the ultraviolet curable component (a) is within the above range, the composition can be sufficiently cured by ultraviolet irradiation.
(2) Colorant (B)
As the colorant (B), for example, known colorants such as inorganic pigments, organic dyes, and the like can be used, but from the viewpoint of improving controllability of light transmittance, the colorant (B) is preferably an organic colorant. As described above, the characteristics of the protective film forming film of the present embodiment or the preferable characteristics of the protective film forming film of the present embodiment are: the light transmittance at a wavelength of 375nm is 8% or more, the light transmittance at a wavelength of 550nm is 12% or less, and the like, and the light transmittance is lower in a certain wavelength range than in a wavelength range lower than the wavelength range. In the case where only the inorganic colorant is used, the light transmittance tends to increase as a linear function as the wavelength of light increases (see the results of test example 1 and fig. 5 described later). Therefore, when the protective film forming film of the present embodiment contains only the inorganic colorant, it is not always easy to impart the above-described characteristics to the protective film forming film of the present embodiment. On the other hand, when the protective film forming film of the present embodiment contains an organic colorant, the protective film forming film of the present embodiment can easily satisfy the above-described characteristics. In addition, from the viewpoint of improving the chemical stability of the colorant (specifically, the ease of dissolution, the ease of occurrence of color migration, and the small change with time can be exemplified), it is preferable that the colorant (B) is composed of a pigment. Therefore, the colorant (B) contained in the protective film forming film of the present embodiment is preferably composed of an organic pigment. The colorant (B) contained in the protective film forming film of the present embodiment may be composed of a plurality of materials.
Examples of the organic pigment and the organic dye as the organic colorant include: ammonium dye, cyanine dye, merocyanine dye, croconic acid dye, and squaric acid
Figure BDA0003273020230000131
Series pigment, azulene (azulene) series pigment, polymethine series pigment, naphthoquinone series pigment, and pyran
Figure BDA0003273020230000132
Dye series, phthalocyanine dye series, naphthalocyanine dye series, naphthalimide dye series, azo lake dye series, condensed azo dye series, indigo dye series, perinone dye series, perylene dye series, and perylene dye series
Figure BDA0003273020230000141
Oxazine-based coloring matter, quinacridone-based coloring matter, isoindolinone-based coloring matter, quinophthalone-based coloring matter, pyrrole-based coloring matter, thioindigo-based coloring matter, metal complex-based coloring matter (metal complex salt dye), dithiol metal complex-based coloring matter, indophenol-based coloring matter, triallylmethane-based coloring matter, anthraquinone-based coloring matter, and dioxanone-based coloring matter
Figure BDA0003273020230000142
Oxazine-based pigments, naphthol-based pigments, azomethine-based pigments, benzimidazolone-based pigments, pyranthrone-based pigments, and threne-based pigments.
Examples of the inorganic pigment include: carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide) -based pigments, ATO (antimony tin oxide) -based pigments, and the like.
The colorant (B) in the protective film forming film of the present embodiment may be composed of an organic colorant and an inorganic colorant.
In addition, the protective film forming film of the present embodiment preferably contains a red colorant. The protective film forming film contains a red colorant, and thus the transmittance of light having a wavelength of 375nm and 550nm (and further a wavelength of 1600nm) can be controlled more easily within the above range. The red colorant may be a pigment or a dye. Examples of the red colorant include: monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, pyrrolopyrroledione-based, condensed azo-based, anthraquinone-based, quinacridone-based colorants, and the like. These colorants may be used alone in 1 kind, or in combination with 2 or more kinds.
Among the above, pyrrolopyrroledione-based red colorants are preferable. With such a red colorant, the transmittance of light having a wavelength of 375nm and 550nm can be easily controlled within the above-mentioned range.
The content of the colorant (B) in the protective film forming film is preferably determined in accordance with the thickness of the protective film forming film, and the light transmittance is made to be in the above range. Specifically, the value W/T obtained by dividing the content W (mass% relative to the total mass of the protective film forming film) of the colorant (B) in the protective film forming film by the thickness T (μm) of the protective film forming film is preferably 0.01 to 0.5, particularly preferably 0.03 to 0.3, and further preferably 0.05 to 0.25. When W/T is 0.5 or more, the transmittance for light having a wavelength of 550nm can be easily controlled to 12% or less, and when W/T is 0.01 or less, the transmittance for light having a wavelength of 375nm can be easily controlled to 13% or more.
(3) Filler (C)
Examples of the filler (C) include silica such as crystalline silica, fused silica, and synthetic silica, and inorganic fillers such as alumina and glass spheres. Among these, silica is preferable, synthetic silica is more preferable, and particularly, synthetic silica of a type in which a radiation source of α rays, which is a factor causing malfunction of a semiconductor device, is removed as much as possible is most preferable. The shape of the filler (C) may be spherical, needle-like, amorphous, or the like, but is preferably spherical, and particularly preferably spherical. When the filler is spherical or spherical, diffuse reflection of light is less likely to occur, and the infrared inspection can be performed satisfactorily. The amorphous as used herein means a shape having an irregular surface shape. The amorphous surface may be multi-faceted or may be a curved surface. When the surface is a polygon, each surface may be a plane or a curved surface, or both a plane and a curved surface may be present in a mixed manner. In addition, when the surface is a multi-surface, the area of each surface may be different. The surface shape may be convex or concave.
In addition, in the protective film forming film, a functional filler may be blended in addition to the inorganic filler. Examples of functional fillers include: gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramics, or an electrically conductive filler obtained by coating nickel, aluminum, or the like with silver for the purpose of imparting electrical conductivity after die bonding, a metal material such as gold, silver, copper, nickel, aluminum, stainless steel, silicon, germanium, or the like for the purpose of imparting thermal conductivity, an alloy, an oxide, a nitride, a hydroxide, or the like thereof, and a thermally conductive filler such as boron nitride, or the like.
The average particle diameter of the filler (C) (particularly, a silica filler) is preferably 0.01 to 10 μm, more preferably 0.01 to 3 μm, particularly preferably 0.03 to 2 μm, and further preferably 0.05 to 1 μm. When the average particle diameter of the filler (C) is 0.01 μm or more, the transmittance of light having a wavelength of 550nm can be easily controlled to 13% or less so that grinding marks in the semiconductor chip or the like are not visually observed. On the other hand, when the average particle diameter of the filler (C) is 10 μm or less, the surface state of the protective film-forming film can be kept good. In addition, if the average particle diameter of the filler (C) is 3 μm or less, diffuse reflection of infrared rays can be suppressed, and infrared ray inspection can be performed satisfactorily.
The average particle diameter of the filler (C) of less than 1 μm in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring apparatus (manufactured by Nikkiso K., Nanotrac Wave-UT 151). The average particle diameter of the filler (C) of 1 μm or more is a value measured by a laser diffraction/scattering method using a particle size distribution measuring apparatus (manufactured by japan electronics corporation, Microtrac MT3000 II).
The content of the filler (C) (particularly, silica filler) in the protective film forming film is preferably 10 to 80 mass%, particularly preferably 20 to 70 mass%, and further preferably 30 to 65 mass% with respect to the mass of the protective film forming film. When the amount of the filler is 10% by mass or more, the transmittance of light having a wavelength of 550nm is easily controlled to 13% or less so that grinding marks in a semiconductor chip or the like are not visually observed. On the other hand, when the amount of the filler (C) is 80% by mass or less, the protective film-forming film can be sufficiently cured by the ultraviolet irradiation.
(4) Thermosetting component (D)
Examples of the thermosetting component (D) include: epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, and benzo
Figure BDA0003273020230000161
Oxazine resins, and the like, and mixtures thereof. Of these, epoxy resins, phenol resins, and mixtures thereof are preferably used.
Epoxy resins have the property of forming a strong coating film by forming a three-dimensional network upon heating. As such an epoxy resin, various conventionally known epoxy resins can be used, and an epoxy resin having a molecular weight of about 300 to 2000 is generally preferable, and an epoxy resin having a molecular weight of 300 to 500 is particularly preferable. The epoxy resin composition is preferably used in the form of a blend of an epoxy resin having a molecular weight of 330 to 400 and being liquid in the normal state and an epoxy resin having a molecular weight of 400 to 2500, particularly 500 to 2000 and being solid at normal temperature. 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, phenol 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; glycidyl-type or alkyl glycidyl-type epoxy resins obtained by substituting active hydrogens bonded to nitrogen atoms such as aniline isocyanurate with glycidyl groups; so-called alicyclic epoxy oxides in which an epoxy group is introduced by, for example, oxidation of a carbon-carbon double bond in the molecule, such as vinylcyclohexane diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-bicyclohexane formate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-dioxane. Further, an epoxy resin having a biphenyl skeleton, a dicyclohexyldiene skeleton, a naphthalene skeleton, or the like can also be used.
Among these, bisphenol glycidyl epoxy resins, o-cresol novolac epoxy resins, and phenol novolac epoxy resins are preferably used. These epoxy resins may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
When an epoxy resin is used, it is preferable to use a thermally active latent epoxy resin curing agent in combination as an auxiliary agent. The heat-active latent epoxy resin curing agent is a curing agent which does not react with an epoxy resin at room temperature, and is activated by heating to a temperature higher than a certain temperature to react with the epoxy resin. The method for activating the heat-active latent epoxy resin curing agent comprises the following steps: a method of generating active species (anion, cation) by a chemical reaction based on heating; a method of stably dispersing the epoxy resin in the epoxy resin at around room temperature and initiating a curing reaction by dissolving or compatibilizing the epoxy resin at a high temperature; a method of causing a curing reaction by dissolving out a molecular sieve-blocked curing agent at a high temperature; a method using a microcapsule, and the like.
Specific examples of the heat-reactive latent epoxy resin curing agent include various types
Figure BDA0003273020230000171
Salts, or high melting point active hydrogen compounds such as dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, imidazole compounds, and the like. These heat-reactive latent epoxy resin curing agents may be used alone in 1 kind or in combination of 2 or more kinds. The thermally active latent epoxy resin curing agent is preferably used in combination with the above-mentioned curing agentThe epoxy resin is used in a proportion of 0.1 to 20 parts by weight, particularly preferably 0.2 to 10 parts by weight, and further preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.
The phenol resin may be, but is not particularly limited to, a condensate of a phenol such as an alkylphenol, a polyphenol, or naphthol, and an aldehyde. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, t-butylphenol novolac resin, dicyclopentadiene cresol resin, poly-p-vinylphenol resin, bisphenol a-type novolac resin, or modified products thereof 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 may be used in combination with the phenol resin.
The content of the thermosetting component (D) in the protective film forming film is preferably 1 to 85 mass%, particularly preferably 2 to 75 mass%, and further preferably 5 to 70 mass% with respect to the mass of the protective film forming film. When the content of the thermosetting component (D) is within the above range, the adhesion of the protective film forming film to the workpiece due to thermosetting and the strength of the cured protective film can be effectively improved, and ultraviolet curability is not inhibited.
(5) Other ingredients
The protective film forming film of the present embodiment may contain a photopolymerization initiator. By containing a photopolymerization initiator, the curing time and the amount of light irradiation of the ultraviolet-curable component (a) can be reduced. The photopolymerization initiator is preferably 0.1 to 15% by mass relative to the mass of the ultraviolet-curable component (a).
Specific examples of the photopolymerization initiator include: benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoylbenzoic acid methyl ester, benzoin dimethyl ether, 2, 4-diethyl thiazolone, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzil, bibenzyl, butanedione, beta-chloroanthraquinone, (2,4, 6-trimethylbenzyldiphenyl) phosphine oxide, N, 2-benzothiazolyl N-diethyldithiocarbamate, oligo { 2-hydroxy-2-methyl-1- [4- (1-propenyl) phenyl ] propanone }, 2-dimethoxy-1, 2-diphenylethan-1-one, and the like. These compounds may be used alone, or 2 or more of them may be used in combination.
In addition, the protective film forming film of the present embodiment may contain a chain transfer agent. The chain transfer agent is contained, whereby an effect that ultraviolet curing is easily performed in the inside of the protective film forming film thickness direction can be expected. As the chain transfer agent, for example, the chain transfer agent described in Japanese patent laid-open No. 2012-207179 can be used.
In addition, the protective film forming film of the present embodiment may contain a coupling agent. By containing the coupling agent, after the protective film forming film is cured, the adhesiveness and the close adhesion of the protective film to the workpiece can be improved, and the water resistance (moisture-heat resistance) can be improved without impairing the heat resistance of the protective film. As the coupling agent, a silane coupling agent is preferable in view of its versatility, cost advantage, and the like.
Examples of the silane coupling agent 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) tetrasulfide, beta-3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, beta-3-glycidoxypropyl-ethyltrimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, beta-glycidoxypropyl-trimethoxysilane, gamma-glycidoxypropyl-tert-trimethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, gamma-tert-dribby-butyl-tert-styrene, gamma-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like. These silane coupling agents may be used alone in 1 kind, or in a mixture of 2 or more kinds.
The protective film forming film of the present embodiment may further 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 film may contain an antistatic agent in order to suppress static electricity and improve chip reliability. In addition, the protective film forming film may contain a flame retardant such as a phosphoric acid compound, a bromine compound, or a phosphorus compound in order to improve the flame retardant property of the protective film and to improve the reliability as a package.
3. Thickness of
In order to effectively function as a protective film, the thickness of the protective film forming film is preferably 3 to 300 μm, particularly preferably 5 to 200 μm, and further preferably 7 to 100 μm. Here, the thickness of the protective film forming film is a value measured at arbitrary 5 sites of the protective film forming film by a contact thickness meter and represented by an average value thereof. When the thickness of the protective film-forming film is measured, it is difficult to directly use a contact thickness gauge, and the thickness of the entire film is measured in the same manner as described above in a state where a base film and another film such as a release material described later are laminated, and the difference between the measured thickness and the thickness of the laminated film (measured in the same manner as described above) can be calculated.
[ sheet for Forming protective film ]
Fig. 1 is a sectional view of a protective film forming sheet according to an embodiment of the present invention. As shown in fig. 1, the protective film forming sheet 2 of the present embodiment includes a protective film forming film 1 and a release sheet 21 laminated on one surface (lower surface in fig. 1) of the protective film forming film 1. The peeling sheet 21 is peeled off when the protective film forming sheet 2 is used.
The release sheet 21 may or may not protect the protective film forming film 1 until the protective film forming sheet 2 is used. The structure of the release sheet 21 is arbitrary, and examples thereof include: the film itself is a plastic film having releasability from the protective film forming film 1, and a film obtained by peeling a plastic film with a peeling agent or the like. Specific examples of the plastic film include: polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicones, fluorine-containing compounds, long-chain alkyl compounds and the like can be used, and among them, silicones which are inexpensive and can obtain stable performance are preferable. The thickness of the release sheet 21 is not particularly limited, and is usually about 20 to 250 μm.
The release sheet 21 may be laminated on the other surface (upper surface in fig. 1) of the protective film forming film 1. That is, the protective film forming film 1 may be sandwiched between the 1 st peeling sheet 21 and the 2 nd peeling sheet 21. In this case, it is preferable that the peeling force of one peeling sheet 21 is increased to be a heavy peeling sheet and the peeling force of the other peeling sheet 21 is decreased to be a light peeling sheet.
In order to manufacture the protective film forming sheet 2 of the present embodiment, the protective film forming film 1 is formed on the release surface (surface having releasability; generally, surface subjected to a release treatment, but not limited thereto) of the release sheet 21. Specifically, a coating agent for forming a protective film, which contains a curable adhesive agent constituting the protective film forming film 1 and, if necessary, a solvent, is prepared, applied to the release surface of the release sheet 21 by a coater such as a roll coater, a knife coater, a roll coater, an air knife coater, a die coater, a bar coater, a gravure coater, a curtain coater, or the like, and dried to form the protective film forming film 1.
As an example, a method for producing a chip with a protective film from a semiconductor wafer as a workpiece by using the protective film forming sheet 2 of the present embodiment will be described below. First, a circuit is formed on the front surface, and the protective film forming film 1 of the protective film forming sheet 2 is attached to the back surface of the semiconductor wafer subjected to back grinding. In this case, the protective film forming film 1 may be heated to exhibit adhesiveness as necessary.
Next, the release sheet 21 is peeled from the protective film forming film 1. Then, the protective film forming film 1 is irradiated with ultraviolet rays, and the protective film forming film 1 is cured to form a protective film, thereby obtaining a semiconductor wafer with a protective film. The protective film forming film 1 may be heated before or after the ultraviolet irradiation as needed. The curing of the protective film forming film 1 may be performed after the dicing step.
The protective film forming film 1 of the present embodiment has excellent ultraviolet curability by having a transmittance of 8% or more for light having a wavelength of 375nm, and therefore, the whole is sufficiently cured by the irradiation with the ultraviolet rays. The amount of ultraviolet irradiation to be applied to the protective film forming film 1 is preferably 50 to 1000mJ/cm in light amount2Particularly preferably 100 to 500mJ/cm2。
After the semiconductor wafer with the protective film is obtained as described above, the protective film may be irradiated with laser light as necessary to perform laser printing. The laser printing may be performed before the curing of the protective film forming film 1.
Next, the semiconductor wafer with the protective film is diced by a usual method using a desired dicing sheet to obtain chips with the protective film (chips with the protective film). Then, the dicing sheet is expanded in the planar direction as necessary, and the chip with the protective film is picked up by the dicing sheet.
In the chip with a protective film obtained as described above, when the transmittance of the protective film forming film 1 (protective film) for light having a wavelength of 550nm is 12% or less, a grinding mark due to back grinding is shielded by the protective film and is not visually observed, and thus the chip with a protective film is excellent in appearance.
When the transmittance of the protective film forming film 1 to light having a wavelength of 1600nm is 25% or more, the infrared transmittance of the protective film forming film 1 (protective film) is good, and the chip with the protective film and the semiconductor wafer with the protective film can be subjected to infrared inspection through the protective film. Therefore, cracks and the like can be found by infrared inspection, and the product yield can be improved.
The infrared inspection is an inspection using infrared rays, and can be performed by obtaining infrared rays from a work with a protective film such as a semiconductor wafer with a protective film or a work such as a chip with a protective film through a protective film. The wavelength of the infrared ray to be obtained is usually 800 to 2800nm, preferably 1100 to 2100 nm. As the apparatus for infrared inspection, a known apparatus, for example, an apparatus having an infrared camera, an infrared microscope, or the like can be used.
[ composite sheet for Forming protective film ]
Fig. 2 is a sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. As shown in fig. 2, the composite sheet 3 for forming a protective film according to the present embodiment includes a support sheet 4, a protective film forming film 1, and a pressure-sensitive adhesive layer 5 for a jig, the support sheet 4 being formed by laminating a pressure-sensitive adhesive layer 42 on one surface of a base material 41, the protective film forming film 1 being laminated on the pressure-sensitive adhesive layer 42 side of the support sheet 4, and the pressure-sensitive adhesive layer 5 for a jig being laminated on an edge portion of the protective film forming film 1 on the opposite side to the support sheet 4. In other words, the composite sheet 3 for forming a protective film includes: a substrate 41, an adhesive layer 42 on the substrate 41, a protective film forming film 1 on the adhesive layer 42, and a pressure-sensitive adhesive layer 5 for a jig on the protective film forming film 1. The adhesive layer 5 for a jig is located at the edge portion of the protective film forming film 1 when viewed from the normal direction of the surface of the protective film forming film 1. The jig adhesive layer 5 is a layer for bonding the composite sheet 3 for forming a protective film to a jig such as an annular frame.
The composite sheet 3 for forming a protective film of the present embodiment is used for attaching to and holding a workpiece when processing the workpiece, and forming a protective film on the workpiece or a processed product obtained by processing the workpiece. The protective film is constituted by a protective film forming film 1, and preferably, is constituted by the cured protective film forming film 1.
As an example, the composite sheet 3 for forming a protective film of the present embodiment is used for holding a semiconductor wafer when the semiconductor wafer as a workpiece is cut, and for forming a protective film on the semiconductor wafer obtained by cutting, but is not limited thereto. The support sheet 4 of the composite sheet 3 for forming a protective film in this case is generally called a dicing sheet.
1. Support sheet
The support sheet 4 of the composite sheet 3 for forming a protective film according to the present embodiment may be configured to include a base material 41 and an adhesive layer 42 laminated on one surface side of the base material 41, and the support sheet 4 is preferably configured only by the base material 41. In this case, when the protective film forming film 1 of the present embodiment is cured by ultraviolet irradiation, in an example of a method of using a composite sheet for forming a protective film described later, there is an advantage that a chip with a protective film can be easily picked up from the support sheet 4. When the support sheet 4 is composed of only the base material 41, an undercoat layer, an antistatic layer, a heat-resistant layer, a stress relaxation layer, and the like may be provided on the base material 41.
1-1. base material
The base material 41 of the support sheet 4 is not particularly limited as long as it is suitable for processing a workpiece, for example, dicing and expanding a semiconductor wafer, and is generally made of a film (hereinafter referred to as a "resin film") mainly made of a resin material.
Specific examples of the resin film include: polyolefin-based films such as polyethylene films including low-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, and high-density polyethylene (HDPE) films, polypropylene films, polybutylene films, butadiene films, polymethylpentene films, ethylene-norbornene copolymer films, and norbornene resin films; ethylene copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylate copolymer films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; polyester-based films such as polyethylene terephthalate films and polybutylene terephthalate films; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; fluororesin films, and the like. Further, modified films such as crosslinked films and ionomer films can also be used. The substrate 41 may be a film formed of 1 of the above-mentioned materials, or a laminated film obtained by combining 2 or more of them. In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Other similar terms are also the same. Among the above, polyolefin-based films are preferable from the viewpoint of environmental safety, cost, and the like.
The resin film may be subjected to surface treatment by an oxidation method, a roughening method, or the like, or undercoating treatment on one surface or both surfaces as required, in order to improve adhesion to the pressure-sensitive adhesive layer 42 laminated on the surface thereof. Examples of the oxidation method include: corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet method), flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, and the like, and examples of the method of forming concavities and convexities include sandblasting, thermal spraying, and the like.
The substrate 41 may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the resin film.
The thickness of the substrate 41 is not particularly limited as long as it can properly function in each step using the composite sheet 3 for forming a protective film, and is preferably in the range of 20 to 450 μm, more preferably 25 to 400 μm, and particularly preferably 50 to 350 μm. Here, the thickness of the base material 41 is a value represented by an average value of thicknesses measured at arbitrary 5 positions of the base material 41 by a contact thickness gauge.
In the present embodiment, the elongation at break of the base material 41 of the support sheet 4 is preferably 100% or more, and particularly preferably 200 to 1000% as measured at 23 ℃ and a relative humidity of 50%. Here, the elongation at break is in the range of from JIS K7161: 1994(ISO 527-11993) standard, elongation of the test piece length at break relative to the initial length. The base material 41 having the elongation at break of 100% or more is not easily broken in the sheet expanding step, and is easily separated from the chips formed by cutting the workpiece.
In addition, the base material 41 of the support sheet 4 of the present embodiment preferably has a tensile stress at 25% strain of 5 to 15N/10mm, and a maximum tensile stress of 15 to 50 MPa. Here, the tensile stress at 25% strain and the maximum tensile stress are determined by the following method based on JIS K7161: 1994, by tests performed in the standard. If the tensile stress at 25% strain is 5N/10mm or more and the maximum tensile stress is 15MPa or more, the base material 2 can be suppressed from being loosened and the occurrence of a conveyance error can be prevented when the work is fixed to a frame such as an annular frame after being stuck to the support sheet 4. On the other hand, if the tensile stress at 25% strain is 15N/10mm or less and the maximum tensile stress is 50MPa or less, the support sheet 4 itself can be prevented from peeling off from the annular frame in the sheet expanding step. The elongation at break, tensile stress at 25% strain, and maximum tensile stress are values measured in the longitudinal direction of the raw material roll of the substrate 41.
1-2 adhesive layer
The pressure-sensitive adhesive layer 42 included in the support sheet 4 of the composite sheet 3 for forming a protective film according to the present embodiment is preferably composed of a type of pressure-sensitive adhesive that is not cured by ultraviolet rays (ultraviolet non-curable pressure-sensitive adhesive) or a type of pressure-sensitive adhesive that is cured by ultraviolet rays in advance. In the case of an adhesive (ultraviolet-curable adhesive) of a type which is not cured in advance and is cured by ultraviolet rays, if the protective film forming composite sheet 3 is irradiated with ultraviolet rays when the protective film forming film 1 is cured, ultraviolet-curable groups which are usually possessed by one or more components contained in the adhesive layer 42 react with ultraviolet-curable groups possessed by the ultraviolet-curable component (a) of the protective film forming film 1, and there is a possibility that it becomes difficult to peel the adhesive layer 42 and the protective film forming film 1 from each other.
As the ultraviolet non-curable pressure-sensitive adhesive, a pressure-sensitive adhesive having desired adhesive strength and removability is preferable, and for example, an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, a polyvinyl ether pressure-sensitive adhesive, or the like can be used. Among these, an acrylic pressure-sensitive adhesive which has high adhesion to the protective film-forming film 1 and can effectively suppress the falling off of the work or the processed product in the dicing step or the like is preferable. In the case of using an adhesive obtained by previously curing an adhesive of the type that is cured by ultraviolet rays, the uncured adhesive layer 42 may be formed by a known adhesive of the type that is cured by ultraviolet rays, and the adhesive may be cured by irradiating ultraviolet rays at the time of manufacturing the uncured adhesive layer.
The thickness of the pressure-sensitive adhesive layer 42 is not particularly limited as long as it can properly function in each step in which the composite sheet for forming a protective film 3 is used. Specifically, the particle diameter is preferably 1 to 50 μm, particularly preferably 2 to 30 μm, and further preferably 3 to 20 μm. Here, the thickness of the adhesive layer 42 is a value represented by an average value of thicknesses measured at arbitrary 5 positions of the adhesive layer 42 by a contact thickness gauge. When it is difficult to directly use a contact type thickness gauge in measuring the thickness of the pressure-sensitive adhesive layer 42, the thickness of the entire pressure-sensitive adhesive layer may be measured in the same manner as described above in a state where a base film and another film such as a release material described later are laminated, and the difference between the measured thickness and the thickness of the laminated other film may be calculated (measured in the same manner as described above).
As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 5 for a jig, a pressure-sensitive adhesive having desired adhesive strength and removability is preferable, and for example, an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, a polyvinyl ether pressure-sensitive adhesive, or the like can be used. Among these, an acrylic adhesive which has high adhesion to a jig such as an annular frame and effectively suppresses peeling of the composite sheet for forming a protective film 3 from the annular frame or the like in a dicing step or the like is preferable. In addition, a base material as a core material may be interposed in the thickness direction of the jig adhesive layer 5.
On the other hand, the thickness of the pressure-sensitive adhesive layer 5 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 an annular frame.
As described in the method for manufacturing a chip with a protective film using the composite sheet for protective film formation 3 described later, after the composite sheet for protective film formation 3 is attached to a semiconductor wafer, ultraviolet rays may be irradiated to the protective film forming film 1 through the support sheet 4. Therefore, in such a case, in order to facilitate curing of the protective film forming film 1, it is preferable that the support sheet 4 has high ultraviolet transmittance.
2. Method for manufacturing composite sheet for forming protective film
The composite sheet 3 for forming a protective film is preferably produced by separately producing a1 st laminate including the protective film forming film 1 and a2 nd laminate including the support sheet 4, and then laminating the protective film forming film 1 and the support sheet 4 by using the 1 st laminate and the 2 nd laminate, but is not limited thereto.
In the production of the 1 st laminate, a protective film formation film 1 is formed on the release surface of the 1 st release sheet. Specifically, a coating agent for forming a protective film is prepared, and the coating agent for forming a protective film, which contains a curable adhesive agent constituting the protective film forming film 1 and, if necessary, a solvent, is applied to the release surface of the 1 st release sheet by a coater such as a roll coater, a knife coater, a roll coater, an air knife coater, a die coater, a bar coater, a gravure coater, or a curtain coater, and dried to form the protective film forming film 1. Next, the release surface of the 2 nd release sheet was laminated on the exposed surface of the protective film formation film 1 and pressure-bonded to obtain a laminate (1 st laminate) in which the protective film formation film 1 was sandwiched by the 2 nd release sheets.
The 1 st laminate may be half-cut as necessary to form the protective film formation film 1 (and the 2 nd release sheet) into a desired shape, for example, a circular shape. In this case, the unnecessary portions of the protective film forming film 1 and the 2 nd release sheet resulting from the half-cut can be appropriately removed.
On the other hand, in the production of the 2 nd laminate, the pressure-sensitive adhesive layer 42 is formed by applying a coating agent for a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 42 and, if necessary, a solvent to the release surface of the 3 rd release sheet and drying the coating agent. Then, the base material 41 was pressure-bonded to the exposed surface of the adhesive layer 42, and a laminate (2 nd laminate) comprising a support sheet 4 and a3 rd release sheet was obtained, the support sheet 4 being composed of the base material 41 and the adhesive layer 42. In the case of using an adhesive obtained by previously curing an adhesive of the type that is cured by ultraviolet rays, it is preferable to cure the adhesive by irradiating ultraviolet rays at a stage after the 2 nd laminate is obtained.
After the 1 st laminate and the 2 nd laminate are obtained as described above, the 2 nd release sheet of the 1 st laminate is peeled off, and the 3 rd release sheet of the 2 nd laminate is peeled off, and the protective film forming film 1 exposed in the 1 st laminate and the adhesive layer 42 of the supporting sheet 4 exposed in the 2 nd laminate are laminated and pressure-bonded. The support sheet 4 may be half-cut as necessary to have a desired shape, for example, a circular shape having a larger diameter than the protective film forming film 1. At this time, an unnecessary portion of the support sheet 4 resulting from the half-cut can be appropriately removed. In this case, the protective film forming sheet 3 of the form shown in fig. 3 was obtained.
As a result, the composite sheet 3 for forming a protective film is obtained, which comprises the support sheet 4, the protective film forming film 1 and the 1 st release sheet, wherein the support sheet 4 is formed by laminating the adhesive layer 42 on the substrate 41, the protective film forming film 1 is laminated on the adhesive layer 42 side of the support sheet 4, and the 1 st release sheet is laminated on the side opposite to the support sheet 4 of the protective film forming film 1. Finally, the 1 st release sheet is peeled off, and then the adhesive layer 5 for a jig is formed at the edge portion of the protective film forming film 1 on the opposite side to the support sheet 4. The jig adhesive layer 5 can be formed by coating in the same manner as the adhesive layer 42 described above.
3. Method for using composite sheet for forming protective film
A method for producing a chip with a protective film from a semiconductor wafer as a workpiece, which is an example of using the composite sheet 3 for forming a protective film according to the present embodiment, will be described below.
As shown in fig. 4, the protective film forming film 1 is attached to the semiconductor wafer 6, and the jig adhesive layer 5 is attached to the ring frame 7. When the protective film forming film 1 is attached to the semiconductor wafer 6, the protective film forming film 1 may be heated as necessary to exhibit adhesiveness.
Then, the protective film forming film 1 is irradiated with ultraviolet rays through the support sheet 4, and the protective film forming film 1 is cured to form a protective film, thereby obtaining a semiconductor wafer 6 with a protective film. The protective film forming film 1 may be heated before or after irradiation with ultraviolet rays as necessary. The curing of the protective film forming film 1 may be performed after the dicing step, or may be performed after the chip with the protective film forming film is picked up from the support sheet 4.
The protective film forming film 1 of the present embodiment has excellent ultraviolet curability by having a transmittance of 8% or more for light having a wavelength of 375nm, and therefore, the entire film is sufficiently cured by the above-described ultraviolet irradiation. The irradiation amount of ultraviolet ray with which the protective film forming film 1 is irradiated is preferably measured photometrically50 to 1000mJ/cm2Particularly preferably 100 to 500mJ/cm2。
After the semiconductor wafer 6 with the protective film is obtained as described above, the protective film is irradiated with laser light through the support sheet 4 as necessary to perform laser printing. The laser printing may be performed before the curing of the protective film forming film 1.
Next, the semiconductor wafer 6 with the protective film is diced in accordance with a usual method to obtain chips with the protective film (chips with the protective film). Then, the support sheet 4 is expanded in the planar direction as necessary, and the chip with the protective film is picked up from the support sheet 4.
In the chip with a protective film obtained as described above, when the transmittance of the protective film forming film 1 (protective film) for light having a wavelength of 550nm is 12% or less, grinding marks due to back grinding are blocked by the protective film and are not observed with the naked eye, and thus the chip with a protective film is excellent in appearance.
When the transmittance of the protective film forming film 1 to light having a wavelength of 1600nm is 25% or more, the protective film forming film 1 (protective film) has good infrared transmittance, and the chip with the protective film and the semiconductor wafer with the protective film can be subjected to infrared inspection via the protective film. Therefore, cracks and the like can be found by infrared inspection, and the product yield can be improved.
4. Other embodiment of the composite sheet for forming a protective film
Fig. 3 is a sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. As shown in fig. 3, the composite sheet 3A for forming a protective film of the present embodiment includes: a support sheet 4 in which the adhesive layer 42 is laminated on one surface of the substrate 41, and a protective film laminated on the adhesive layer 42 side of the support sheet 4 form a film 1. The protective film forming film 1 in the present embodiment is formed substantially the same as the workpiece in the plane direction or formed slightly larger than the workpiece, and is formed smaller than the supporting sheet 4 in the plane direction. The pressure-sensitive adhesive layer 42 of the portion where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.
The materials and thicknesses of the respective members of the composite sheet for forming a protective film 3A of the present embodiment are the same as those of the respective members of the composite sheet for forming a protective film 3.
In the adhesive layer 42 of the support sheet 4 of the composite sheet for forming a protective film 3A, an adhesive layer for a jig similar to the adhesive layer 5 for a jig of the composite sheet for forming a protective film 3 may be separately provided at the edge portion on the opposite side of the substrate 41. In other words, the composite sheet for forming a protective film 3A may have: the pressure-sensitive adhesive sheet includes a substrate 41, a pressure-sensitive adhesive layer 42 on the substrate 41, a protective film forming film 1 on the pressure-sensitive adhesive layer 42, and a pressure-sensitive adhesive layer 5 for a jig on the pressure-sensitive adhesive layer 42 and positioned at an edge portion of the protective film forming film 1. In this case, the support sheet 4 may be constituted only by the base material 41. That is, the composite sheet for forming a protective film 3A may have: a substrate 41, a protective film forming film 1 on the substrate 41, and a pressure-sensitive adhesive layer 5 for a jig on the substrate 41 and positioned at an edge portion of the protective film forming film 1.
In the configuration of fig. 3, when an adhesive obtained by previously curing an adhesive of a type that is cured by ultraviolet light is used for the adhesive layer 42, only the inner peripheral portion of the adhesive layer 42 when viewed from above may be previously cured. This makes it possible to maintain high adhesiveness at the outer periphery of the jig such as the ring frame, and to facilitate fixing of the support piece 4 to the jig.
Further, in fig. 3, a peeling force adjusting layer may be provided between the adhesive layer 42 and the protective film forming film 1. In other words, the composite sheet for forming a protective film 3A may have: the substrate 41, the pressure-sensitive adhesive layer 42 on the substrate 41, the peeling force adjusting layer on the pressure-sensitive adhesive layer 42, and the protective film on the peeling force adjusting layer form the film 1. This makes it easy to peel the peeling force adjusting layer and the protective film forming film 1 from each other. Further, strong adhesiveness can be given to the adhesive layer 42 which does not need to consider the influence on the process of picking up a chip with a protective film (protective film forming film), and fixing of the support sheet 4 to the jig can be facilitated. The peeling force adjusting layer may be formed of, for example, an adhesive having a lower adhesive force than the adhesive used for the adhesive layer 42, or may be formed of a resin film (including a film subjected to a peeling treatment).
The above-described embodiments are described for easy understanding of the present invention, and are not intended to limit the present invention. Therefore, each element disclosed in the above embodiments includes all design modifications and equivalents that fall within the technical scope of the present invention.
For example, a release sheet may be laminated on the side opposite to the support sheet 4 in the protective film forming film 1 of the protective film forming composite sheets 3 and 3A.
Examples
Hereinafter, some embodiments of the present invention will be described more specifically by examples and the like, but the scope of the present invention is not limited to these examples and the like.
[ example 1]
The following components were mixed at the mixing ratios (mass ratios; converted to solid contents) shown in table 1, and diluted with methyl ethyl ketone so that the solid content concentration became 54 mass%, to prepare a coating agent for forming a protective film.
(a) Ultraviolet-curable component: an acrylic polymer having a side chain to which an ultraviolet-curable group has been introduced (weight-average molecular weight: 40 ten thousand, glass transition temperature: -10 ℃) which is obtained by reacting 80 moles of methacryloyloxyethyl isocyanate per 100 moles of 2-hydroxyethyl acrylate-derived hydroxyl groups in an acrylic polymer obtained by copolymerizing 80 parts by mass of 2-hydroxyhexyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate.
(b1) Red colorant: pyrrolopyrrole dione type Red Pigment (Pigment Red 264, manufactured by Shanyang Pigment Co., Ltd.)
(b2) Black colorant: carbon black (Mitsubishi chemical corporation, # MA600B, average particle diameter 28nm)
(c) Filling: silica Filler (SC 2050MA, manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm)
(d) Heat-curable components: bisphenol A epoxy resin (manufactured by Mitsubishi chemical corporation, JER828, epoxy equivalent 183 ~ 194g/eq)
(e) Photopolymerization initiator: 1-Hydroxycyclohexyl phenyl ketone (IRGACURE 184, BASF Co.)
A1 st release sheet (SP-PET 3811, manufactured by Linekeko Co., Ltd., thickness 38 μm) having a silicone release agent layer formed on one surface of a polyethylene terephthalate (PET) film and a2 nd release sheet (SP-PET 381031, manufactured by Lineko Co., Ltd., thickness 38 μm) having a silicone release agent layer formed on one surface of a PET film were prepared.
The above coating agent for forming a protective film was applied to the release surface of the 1 st release sheet with a blade coater, and then dried in an oven at 120 ℃ for 2 minutes, to form a protective film forming film. The thickness of the obtained protective film-forming film was 25 μm. Subsequently, the release surfaces of the 2 nd release sheet were laminated on the protective film forming film, and the two were bonded to each other, thereby obtaining a protective film forming sheet composed of the 1 st release sheet (release sheet 21 in FIG. 1), the protective film forming film (protective film forming film 1 in FIG. 1) (thickness: 25 μm), and the 2 nd release sheet.
[ examples 2 to 3, comparative examples 1 to 2]
A protective film-forming sheet was produced in the same manner as in example 1, except that the kinds and loading of the components constituting the protective film-forming film were changed to those shown in table 1.
In each example, the value W/T obtained by dividing the content W (mass%) of the colorant by the thickness T (μm) of the protective film formation film was calculated and shown in table 1.
[ test example 1] measurement of light transmittance
The 2 nd release sheet was peeled from the protective film-forming sheets obtained in examples and comparative examples, and laminated on a glass plate by a roll laminator at 70 ℃ and 1.2 m/min. Then, the 1 st release sheet was peeled off and used as a sample for measurement.
The light transmittance of the above-mentioned measurement sample was measured by a spectrophotometer (UV-VIS-NIRSPERPHOTOMETER UV-3600, manufactured by SHIMADZU), and the light transmittance (%) at wavelengths of 375nm (ultraviolet light), 550nm (visible light) and 1600nm (infrared light) was extracted. The measurement was performed using an integrating sphere built in, and the results are shown in table 1. Fig. 5 shows the measurement results of the light transmittance in the form of a graph. As shown in table 1 and fig. 5, in comparative example 1, the transmittance of infrared light was high, but the transmittance of visible light was as high as 45.8%. For comparative example 2, the light transmittance at any wavelength was substantially 0%. On the other hand, in examples 1 to 3, the transmittance for light having a wavelength of 375nm was 8% or more, the transmittance for light having a wavelength of 550nm was 12% or less, and the transmittance for light having a wavelength of 1600nm was 25% or more.
[ test example 2] < evaluation of grinding-mark-covering Property >
The 2 nd release sheet was peeled from the protective film-forming sheets obtained in examples and comparative examples to expose the protective film-forming film. The protective film-forming film was bonded to a polished surface of a #2000 polished silicon wafer (diameter 200mm, thickness 350 μm) by using a tape bonder (Adwill RAD-3600F/12, manufactured by Lindcaceae) while heating the protective film-forming film to 70 ℃.
Next, the above-mentioned protective film-forming film was irradiated with ultraviolet rays using an ultraviolet irradiation apparatus (manufactured by Lindelke corporation, ADWILL RAD-2000) (irradiation conditions: at an illuminance of 215mW/cm2Light quantity 187mJ/cm2Irradiation 3 times without nitrogen purging) to cure the protective film-forming film to form a protective film. Then, the 1 st release sheet was peeled off to obtain a silicon wafer with a protective film.
With respect to the obtained silicon wafer with the protective film, whether or not grinding traces of the polished surface of the silicon wafer were seen through the protective film was visually observed. As a result, the one with no grinding marks was evaluated as good, and the one with grinding marks was evaluated as bad. The results are shown in Table 1.
[ test example 3] < measurement of Probe viscosity >
The protective film-forming sheets obtained in examples and comparative examples were irradiated with ultraviolet rays from the 1 st release sheet side thereof using an ultraviolet irradiation machine (manufactured by Lindco, Inc., ADWILL RAD-2000) (irradiation conditions: at an illuminance of 215 mW/cm)2Light quantity 187mJ/cm2Irradiation 3 times without nitrogen purging) to cure the protective film-forming film to form a protective film.
Next, the laminate including the protective film was cut into a square of 1cm square, and the 2 nd release sheet was peeled off. A polyethylene terephthalate film (thickness: 25 μm) as a base material was laminated on the exposed protective film at room temperature using a roll laminator at 70 ℃ and 1.2 m/min. Then, the 1 st release sheet on the side of the ultraviolet-irradiated surface was peeled off to prepare a1 st sample (for measurement of the ultraviolet-irradiated surface).
Similarly, the laminate including the protective film was cut into a square of 1cm square, and the 1 st release sheet was peeled off. A polyethylene terephthalate film (thickness: 25 μm) as a base material was laminated on the exposed protective film at room temperature using a roll laminator at 70 ℃ and 1.2 m/min. Then, the 2 nd release sheet on the side opposite to the side irradiated with ultraviolet light was peeled off to prepare a2 nd sample (for measurement of the side opposite to the side irradiated with ultraviolet light).
The PROBE tack values (peak P1 and energy value E1) of the exposed surface (ultraviolet-irradiated surface) of the protective film in the above sample 1 and the PROBE tack values (peak P2 and energy value E2) of the exposed surface (ultraviolet-irradiated opposite surface) of the protective film in the above sample 2 were measured using a tack tester (RHESCA PROBE TACK TESTER model RPT100, manufactured by RHESCA corporation). The measurement conditions are as follows. Further, from the measurement results, a ratio P2/P1 of the peak value P2 to the peak value P1 and a ratio E2/E1 of the energy value E2 to the energy value E1 were calculated. The results are shown in Table 1.
< measurement Condition for Probe tack value >
Velocity: 600mm/sec
Indentation load: 0.98N
Indentation time: 1 second
[ Table 1]
Figure BDA0003273020230000301
As is clear from table 1, the probe tack value of the ultraviolet irradiation surface in the protective film forming film (protective film) obtained in the examples was similar to the probe tack value of the surface opposite to the ultraviolet irradiation surface. As can be seen from this, the protective film of the example was cured in the entire thickness direction from the ultraviolet-irradiated surface to the surface opposite to the ultraviolet-irradiated surface. In addition, the protective film of the example also had excellent grinding mark shielding properties.
Industrial applicability
The protective film forming film, the protective film forming sheet and the protective film forming composite sheet of the present invention are suitable for manufacturing chips having a protective film from a conductor wafer.

Claims (17)

1. A protective film forming film which contains an ultraviolet-curable component and a filler having an average particle diameter of 0.01 [ mu ] m or more,
the protective film has a transmittance of 8% or more for a light having a wavelength of 375nm and a transmittance of 12% or less for a light having a wavelength of 550nm,
the protective film forming film is formed of a single layer.
2. The protective film forming film according to claim 1, further comprising a thermosetting component (D).
3. The protective film forming film according to claim 1 or 2, further containing a colorant.
4. The protective film forming film according to claim 1 or 2, which contains 30 to 65 mass% of the filler with respect to the mass of the protective film forming film.
5. The protective film forming film according to claim 3, wherein the colorant is a red colorant.
6. The protective film forming film according to claim 3 or 5, wherein the colorant is an organic-based colorant.
7. The protective film forming film according to claim 3 or 5, wherein a value W/T obtained by dividing a content W (mass%) of the colorant in the protective film forming film by a thickness T (μm) of the protective film forming film is 0.01 to 0.5.
8. The protective film forming film according to claim 1 or 2, whereinThe protective film-forming film was irradiated from one side with 3 times of illuminance of 215mW/cm2Light quantity 187mJ/cm2The ratio P2/P1 of the peak value P2 of the probe viscosity of the surface opposite to the ultraviolet irradiation surface to the peak value P1 of the probe viscosity of the ultraviolet irradiation surface is 0.1 to 7.
9. The protective film forming film according to claim 1 or 2, which has a transmittance of 25% or more for light having a wavelength of 1600 nm.
10. A protective film-forming sheet comprising:
the protective film forming film as claimed in any one of claims 1 to 9, and
and a release sheet laminated on one or both sides of the protective film forming film.
11. A composite sheet for forming a protective film, comprising:
support sheet, and
the protective film according to any one of claims 1 to 9 laminated on one surface side of the support sheet to form a film.
12. The composite sheet for forming a protective film according to claim 11, wherein the support sheet is formed of a substrate and an adhesive layer laminated on the protective film-forming film side of the substrate, or is formed of a substrate.
13. The composite sheet for forming a protective film according to claim 12, wherein the support sheet is formed of the base material and an adhesive layer laminated on the protective film-forming film side of the base material,
the adhesive layer is formed of an ultraviolet-non-curable adhesive or an ultraviolet-curable adhesive cured.
14. A method for manufacturing a semiconductor chip with a protective film, the method comprising:
a step of obtaining a semiconductor wafer with a protective film forming film by attaching a semiconductor wafer to the protective film forming film according to any one of claims 1 to 9; irradiating the protective film forming film with ultraviolet rays to obtain a semiconductor wafer with a protective film;
a step of obtaining a semiconductor chip with a protective film by dicing the semiconductor wafer with a protective film using a dicing sheet; and
and picking up the semiconductor chip with the protective film from the dicing sheet.
15. A method for manufacturing a semiconductor chip with a protective film, the method comprising:
a step of obtaining a semiconductor wafer with a protective film forming film by attaching a semiconductor wafer to the protective film forming film according to any one of claims 1 to 9;
a step of dicing the semiconductor wafer with the protective film forming film by using a dicing sheet to obtain a semiconductor chip with a protective film forming film;
irradiating the protective film forming film with ultraviolet rays to obtain a semiconductor chip with a protective film; and
and picking up the semiconductor chip with the protective film from the dicing sheet.
16. A method for manufacturing a semiconductor chip with a protective film, the method comprising:
a step of attaching a semiconductor wafer to the protective film forming film of the composite sheet for forming a protective film according to any one of claims 10 to 12;
irradiating the protective film forming film with ultraviolet rays to form the protective film forming film into a protective film;
dicing the protective film and the semiconductor wafer to obtain a semiconductor chip with a protective film; and
and picking up the semiconductor chip with the protective film from the support sheet.
17. A method for manufacturing a semiconductor chip with a protective film, the method comprising:
a step of attaching a semiconductor wafer to the protective film forming film of the composite sheet for forming a protective film according to any one of claims 10 to 12;
dicing the protective film forming film and the semiconductor wafer to obtain a semiconductor chip with a protective film forming film;
irradiating the protective film forming film with ultraviolet rays to form the semiconductor chip with the protective film forming film into a semiconductor chip with a protective film; and
and picking up the semiconductor chip with the protective film from the support sheet.
CN202111107427.8A 2014-10-29 2015-10-23 Protective film forming film, composite sheet for protective film formation, and method for manufacturing semiconductor chip with protective film Pending CN113980535A (en)

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