CN112625276A - Protective film-forming film and composite sheet for forming protective film - Google Patents

Protective film-forming film and composite sheet for forming protective film Download PDF

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Publication number
CN112625276A
CN112625276A CN202011053038.7A CN202011053038A CN112625276A CN 112625276 A CN112625276 A CN 112625276A CN 202011053038 A CN202011053038 A CN 202011053038A CN 112625276 A CN112625276 A CN 112625276A
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protective film
film
forming
meth
curable
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薄刃美玲
米山裕之
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Lintec Corp
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Lintec Corp
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • 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
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    • B32—LAYERED PRODUCTS
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Abstract

The invention provides a film for forming a protective film, which uses the minimum value X of absorbance of the protective film under the wavelength of 2000-3200 nm (excluding 2701-2999 nm)minSpecific heat S at 100 ℃ with protective film100And through Z100＝Xmin/S100Calculated Z100Is 0.27 or less. The present invention also provides a composite sheet for forming a protective film, which comprises a support sheet and the protective film-forming film provided on one surface of the support sheet.

Description

Protective film-forming film and composite sheet for forming protective film
Technical Field
The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film. The present application claims priority based on the application No. 2019-184721, filed in japan on 10/7/2019, and the contents thereof are incorporated herein.
Background
In a wafer such as a semiconductor wafer insulator wafer, a circuit is formed on one surface (circuit surface) thereof, and a protruding electrode such as a bump is provided on the surface (circuit surface). Such a wafer is divided into chips, and the chips are mounted on a circuit board by connecting the bump electrodes to connection pads on the circuit board.
In such a wafer or chip, in order to suppress the occurrence of damage such as cracking, a surface (back surface) opposite to the circuit surface may be protected with a protective film (see patent documents 1 to 2).
In order to form such a protective film, a protective film forming film for forming a protective film is attached to the back surface of a semiconductor wafer, and in this case, a protective film forming composite sheet including a support sheet and the protective film forming film provided on one surface of the support sheet can be used. When a wafer having a protective film-forming film or a protective film on the back surface thereof is divided into chips, the support sheet can be used as a dicing sheet for fixing the wafer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-32644
Patent document 2: international publication No. 2015/146936
Disclosure of Invention
Technical problem to be solved by the invention
As described above, the circuit board with the chip mounted thereon is used as a substrate device for various electronic components.
On the other hand, the chip before being mounted on the circuit board is usually held on a support sheet or a dicing sheet via a protective film provided on the back surface thereof. In addition, the chip may be held on the support sheet or the dicing sheet via the protective film as a wafer before dicing at this stage. The process up to this state will be described in detail later. In addition, the support sheet or the dicing sheet may be stretched along a surface parallel to the chip or the wafer side (extended). The expansion of the support sheet or the cut sheet is performed for several reasons.
For example, as a method of dividing a semiconductor wafer into semiconductor chips, Stealth Dicing (registered trademark) (Stealth Dicing) is known.
In steadh Dicing (registered trademark), first, a pre-division position is set in the semiconductor wafer, and a modified layer is formed in the semiconductor wafer by irradiating laser light so as to be focused on the position as a focal point. The modified layer of the semiconductor wafer is modified by laser irradiation and weakened in strength, unlike the other positions of the semiconductor wafer. Therefore, by applying a force to the semiconductor wafer, cracks extending in the direction of both surfaces of the semiconductor wafer are generated in the modified layer inside the semiconductor wafer, and these cracks become starting points for dividing (cutting) the semiconductor wafer. Then, a force is applied to the semiconductor wafer to divide the semiconductor wafer at the modified layer portion, thereby forming a semiconductor chip. In this case, for example, the semiconductor wafer on which the modification layer is formed, which is held by the support sheet or the dicing sheet with the protective film interposed therebetween, is stretched in a direction parallel to the surface of the semiconductor wafer together with the support sheet or the dicing sheet and the protective film, whereby a force is applied to the semiconductor wafer, whereby the semiconductor chip can be manufactured. That is, the support sheet or dicing sheet in this case is finally an expanded sheet holding a semiconductor chip having a protective film on the back surface (semiconductor chip with protective film).
As a method for dividing a semiconductor wafer into semiconductor chips, various dicing methods are known, such as blade dicing using a blade, laser dicing by laser irradiation, or water dicing by jetting water containing an abrasive. In these dicing, the semiconductor wafer held on the support sheet or dicing sheet with the protective film interposed therebetween is cut together with the protective film, and is divided into semiconductor chips.
In these cuts, the support sheet or the extension of the cut sheet is not generally performed. However, the semiconductor chip with the protective film held on the support sheet or the dicing sheet is separated from the support sheet or the dicing sheet and picked up later, and then loaded on the circuit substrate. In order to facilitate the pickup, the support sheet or the dicing sheet may be expanded when the semiconductor chip with the protective film is picked up. In addition, there is a case where a part of a plurality of semiconductor chips with a protective film held on one support sheet or dicing sheet is left on the support sheet or dicing sheet without picking up the part, and the support sheet or dicing sheet is directly stored in this state. That is, the support sheet or dicing sheet at this time is finally an expanded sheet holding the semiconductor chip with the protective film.
Here, although the case where the semiconductor chip having the protective film on the back surface (semiconductor chip with protective film) is held on the expanded support sheet or dicing sheet has been described as an example, there is a case where the semiconductor wafer having the protective film on the back surface (semiconductor wafer with protective film) is held on the expanded support sheet or dicing sheet.
The support sheet or dicing sheet holding the semiconductor chip with a protective film or the semiconductor wafer with a protective film in an expanded state is not limited to the support sheet or dicing sheet shown here.
After the expanded support sheet or dicing sheet holding the semiconductor chip with protective film or the semiconductor wafer with protective film is held, a region in the vicinity of the peripheral portion of the semiconductor chip with protective film or the semiconductor wafer with protective film, which is not held, may be heat-treated by using a heater. Since the region near the peripheral portion of the support sheet or the dicing sheet is stretched more than the other region by expansion and becomes slack, the heat treatment as described above, which is also called heat shrinkage (heat shrink), is performed to shrink the region and remove the slack state. The heat treatment during heat shrinkage is performed by irradiating the support sheet or the dicing sheet with near infrared rays or intermediate infrared rays at the position.
However, when heat shrinking is performed, near infrared rays or mid-infrared rays may be irradiated not only to the position of the support sheet or dicing sheet but also to a semiconductor chip with a protective film or a semiconductor wafer with a protective film located in the vicinity of the position. In this case, the protective film in the semiconductor chip with the protective film or the semiconductor wafer with the protective film is also heat-treated, which causes a problem of uneven discoloration. Such a protective film has a problem in appearance even if it can exhibit a desired protective function.
On the other hand, patent documents 1 to 2 do not disclose means for solving the above problems.
Although the case of using a semiconductor wafer has been described above, the above-described unintended heating problem of the protective film is not limited to a semiconductor wafer, and is present in all wafers.
The present invention provides a film for forming a protective film on the back surface of a chip, wherein when a dicing sheet, which holds a chip with a protective film having a chip and a protective film provided on the back surface of the chip or a wafer with a protective film provided on the back surface of the wafer and has been expanded, is subjected to heat treatment to thereby perform heat shrinkage, an unintended temperature increase of the protective film in the chip with a protective film or the wafer with a protective film can be suppressed.
Another object of the present invention is to provide a composite sheet for forming a protective film, which comprises the above-described film for forming a protective film and a support sheet.
Means for solving the problems
The invention provides a film for forming a protective film, which is used for forming a protective film on the back surface of a chip, wherein the minimum value X of absorbance under the wavelength of 2000-3200 nm (excluding 2701-2999 nm) of the protective film is utilizedminAnd the specific heat S of the protective film at 100 DEG C100And by the formula: z100＝Xmin/S100Calculated Z100Is 0.27 or less.
The protective film forming film of the present invention may be thermosetting or energy ray-curable.
The protective film-forming film of the present invention may contain two or more light absorbers capable of absorbing either or both of visible light and infrared light.
The protective film forming film of the present invention may contain a carbon material.
In the film for forming a protective film of the present invention, the minimum value T of the transmittance of the protective film to light having a wavelength of 400 to 750nmmPreferably 15% or less.
In the film for forming a protective film of the present invention, the protective film has a reflectance maximum value U for light having a wavelength of 2000 to 2600nmmPreferably 20% or less.
The present invention provides a composite sheet for forming a protective film, comprising a support sheet and a film for forming a protective film provided on one surface of the support sheet, wherein the film for forming a protective film is the film for forming a protective film of the present invention.
In the composite sheet for forming a protective film of the present invention, the support sheet includes a base material and an adhesive layer provided on one surface of the base material, and the adhesive layer may be disposed between the base material and the film for forming a protective film.
Effects of the invention
According to the present invention, there is provided a film for forming a protective film on the back surface of a chip, wherein when a dicing sheet, which holds a chip with a protective film including a chip and a protective film provided on the back surface of the chip or a wafer with a protective film provided on the back surface of the wafer and is expanded, is subjected to heat treatment to thereby perform heat shrinkage, an unintended temperature increase of the protective film in the chip with a protective film or the wafer with a protective film can be suppressed.
Further, the present invention provides a composite sheet for forming a protective film, which comprises the above-described film for forming a protective film and a support sheet.
Drawings
Fig. 1 is a cross-sectional view schematically showing an example of a film for forming a protective film according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 5 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 6 is a cross-sectional view schematically showing an example of a connection state between a chip with a protective film and a circuit board when the protective film forming film according to the embodiment of the present invention is used.
Description of the reference numerals
101. 102, 103, 104: a composite sheet for forming a protective film; 10. 11: a support sheet; 10a, 20 a: one face (first face) of the support sheet; 11: a substrate; 11 a: one face (first face) of the substrate; 12: an adhesive layer; 13. 23: a protective film-forming film; 130': a cut-off protective film; 9: a chip; 9 b: the back side of the chip.
Detailed Description
Protective film formation film
The film for forming a protective film according to one embodiment of the present invention is used for forming a protective film on the back surface of a chip, and utilizes the minimum value X of absorbance at a wavelength of 2000 to 3200nm (excluding 2701 to 2999nm) of the protective filmminAnd the specific heat S of the protective film at 100 DEG C100And by the formula: z100＝Xmin/S100Calculated Z100Is 0.27 or less.
As described later, the protective film forming film of the present embodiment can constitute a protective film forming composite sheet by, for example, being laminated with a support sheet.
The protective film forming film of the present embodiment is a film for providing a protective film on the back surface of a chip to protect the chip.
The protective film-forming film is soft and can be attached to a wafer before being divided into chips.
The protective film forming film of the present embodiment may be curable or non-curable. That is, the protective film-forming film may function as a protective film by curing the film, or may function as a protective film in an uncured state.
The curable protective film-forming film may be either thermosetting or energy ray-curable, and may have both thermosetting and energy ray-curable properties.
In the present specification, the "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam, and examples of the energy ray include ultraviolet rays, radiation, an electron beam, and the like. For example, the ultraviolet rays may be irradiated by using a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.
The term "non-curable" means that curing does not proceed by any means such as heating or irradiation with energy rays. A non-curable film for forming a protective film after a stage of being provided (formed) on a target object is regarded as a protective film.
In this specification, examples of the "wafer" include a semiconductor wafer made of an elemental semiconductor such as silicon, germanium, or selenium, or a compound semiconductor such as GaAs, GaP, InP, CdTe, ZnSe, or SiC; an insulator wafer made of an insulator such as sapphire or glass.
In this specification, a surface of the wafer on which the circuit is formed is referred to as a "circuit surface". The surface of the wafer opposite to the circuit surface is referred to as a "back surface".
The wafer is divided into chips by dicing or the like. In the present specification, as in the case of a wafer, a surface of a chip on which a circuit is formed is referred to as a "circuit surface", and a surface of the chip opposite to the circuit surface is referred to as a "back surface".
The circuit surface of the wafer and the circuit surface of the chip can be provided with protruding electrodes such as bumps and pillars (pilars). The bump electrode is preferably made of solder.
By using the protective film-forming film of the present embodiment or the protective film-forming composite sheet including the protective film-forming film, a chip having a protective film on the back surface (in this specification, sometimes referred to as a "chip with a protective film") can be manufactured. In this case, a wafer having a protective film on the back surface (in this specification, the wafer may be referred to as a "wafer with a protective film") may be produced.
Further, by using the chip with the protective film, a substrate device can be manufactured.
In the present specification, the term "substrate device" refers to a device in which a chip with a protective film is flip-chip connected to a connection pad on a circuit substrate at a bump electrode on a circuit surface of the chip. For example, when a semiconductor wafer is used as a wafer, a semiconductor device is used as a substrate device.
When using a protective film-forming composite sheet provided with a protective film-forming film, the following support sheet may be used before manufacturing a substrate device: the support sheet is a so-called spread support sheet which holds 1 or 2 or more (usually 2 or more) chips with a protective film or 1 wafer with a protective film on 1 support sheet, and is stretched in a direction parallel to the surface on the chip or wafer side. For the reason described above, after that, the support sheet may be subjected to a heat treatment (heat shrinkage) using a heater in a region around the peripheral edge of the wafer on which the chip with a protective film or the wafer with a protective film is not originally held. The heating treatment during the heat shrinkage is performed by irradiating the position of the support sheet with near infrared rays or intermediate infrared rays, for example, but the near infrared rays or intermediate infrared rays may be irradiated not only to the position of the support sheet but also to a chip with a protective film or a wafer with a protective film located in the vicinity of the position. In this case, the protective film in the chip with the protective film or the wafer with the protective film may be subjected to heat treatment, resulting in uneven discoloration, and even if such a protective film can exhibit the intended protective function, there is a problem in appearance.
On the other hand, when a protective film forming film not constituting the composite sheet for forming a protective film is used by being bonded to a dicing sheet, as in the case of using the above composite sheet for forming a protective film, before manufacturing a substrate device, there are cases where: 1 or 2 or more (usually 2 or more) chips with a protective film or 1 wafer with a protective film are held on 1 dicing sheet, and the dicing sheet is in a spread state.
Since the support sheet and the dicing sheet can be used in the same manner, when the dicing sheet is used, there is a problem in appearance due to discoloration of the protective film in the same manner as described above.
In contrast, Z of the protective film obtained from the protective film forming film of the present embodiment is used100The temperature is 0.27 or less, and even if near infrared rays or intermediate infrared rays are erroneously irradiated to the chip with the protective film or the wafer with the protective film during the heat treatment during heat shrinkage, an unintended temperature increase of the protective film in the chip with the protective film or the wafer with the protective film can be suppressed. And inhibit discoloration of these protective films.
That is, the film for forming a protective film of the present embodiment can perform heat shrinkage of the support sheet or the dicing sheet with suppressing unintended discoloration of the protective film.
Z of the protective film100(＝Xmin/S100) Z is an index showing the degree of difficulty of temperature rise of the protective film at 100 DEG C100Is 0.27 or less, preferably 0.24 or less, and may be in any range of, for example, 0.21 or less, 0.18 or less, 0.15 or less, and 0.12 or less. By bringing Z to100The effect of suppressing the temperature rise of the protective film during heating can be further improved when the temperature is not more than the upper limit value.
Z100The lower limit of (b) is not particularly limited. From easier formation of satisfying Z100Point of the protective film of the above conditions, Z100Preferably 0.01 or more.
Z100The adjustment can be appropriately performed within a range set by arbitrarily combining any of the upper limit values with the lower limit values. For example, in one embodiment, Z100Preferably 0.01 to 0.27, more preferably 0.01 to 0.24, and may be, for example, any one of 0.01 to 0.21, 0.01 to 0.18, 0.01 to 0.15, and 0.01 to 0.12. However, these ranges are only Z100An example of (1).
Wave of the protective filmMinimum value X of absorbance at a length of 2000 to 3200nm (excluding 2701 to 2999nm)minAs long as the above-mentioned Z is satisfied100The conditions of (3) are not particularly limited.
For example, in the flip chip connection step described later, the chip with the protective film can be appropriately heated and spot-emitted by irradiating near infrared rays or mid-infrared rays having a wavelength of 2000 to 3200nm using a reflow furnace equipped with a ceramic heater, and XminPreferably 0.01 or more, and may be, for example, 0.05 or more, 0.09 or more, 0.13 or more, or 0.17 or more.
XminPreferably 0.33 or less, more preferably 0.28 or less, and may be in any range of 0.24 or less, 0.20 or less, and 0.16 or less, for example.
XminAny combination of any of the lower limit values and any of the upper limit values may be appropriately adjusted within a range set as desired. For example, in one embodiment, XminPreferably 0.01 to 0.33, and may be, for example, any one of 0.01 to 0.28, 0.01 to 0.24, 0.01 to 0.20, and 0.01 to 0.16. However, these ranges are only XminAn example of (1).
In determining XminThe reason why the absorbance at the wavelength of 2701 to 2999nm is not targeted at this time is that the atmosphere easily absorbs light in this wavelength region, and it is difficult to accurately measure the absorbance of the protective film in this wavelength region.
XminIs the minimum value of the absorbance of the protective film in a wavelength region of 2000nm or more and less than 2701nm and of 2999nm and 3200nm or less.
Specific heat S of the protective film at 100 DEG C100As long as the above-mentioned Z is satisfied100The conditions of (3) are not particularly limited.
S100Preferably 1 or more, more preferably 1.1 or more, and may be, for example, 1.2 or more, 1.3 or more, or 1.4 or more.
S100Preferably 1.7 or less, more preferably 1.6 or less, and may be in any range of 1.5 or less, 1.4 or less, and 1.3 or less, for example.
S100Any combination of any of the lower limit values and any of the upper limit values may be appropriately adjusted within a range set as desired. For example, in one embodiment, S100Preferably 1 to 1.7, more preferably 1.1 to 1.7, and may be, for example, any one of 1.2 to 1.7, 1.3 to 1.7, and 1.4 to 1.7. However, these ranges are only S100An example of (1).
S100Can be prepared by mixing the following components in JIS K7123: 2012, a differential scanning calorimeter was used to calculate the measured value of the differential scanning heat of the protective film with the temperature increase rate set at 10 ℃/min.
The minimum value T of the transmittance of the protective film to light with the wavelength of 400-750 nmmThe content is not particularly limited, but is preferably 15% or less, more preferably 10% or less, still more preferably 7% or less, and particularly preferably 4% or less. By making TmIf the amount is less than the upper limit, the presence or absence of the protective film can be more easily confirmed.
TmThe lower limit of (B) is not particularly limited, e.g. TmMay be 0% or more.
The maximum value U of the reflectivity of the protective film to light with the wavelength of 2000-2600 nmmThe content is not particularly limited, but is preferably 20% or less, more preferably 15% or less, and still more preferably 12% or less. By making UmWhen the chip with the protective film is used, the occurrence of failure of a device using near infrared rays or intermediate infrared rays, such as a near infrared ray or intermediate infrared ray reflection sensor, can be suppressed.
UmThe lower limit of (B) is not particularly limited, e.g., UmMay be 0% or more. From easier formation to satisfy UmPoint out of the protective film of the above conditions, UmPreferably 0.2% or more, more preferably 0.5% or more, and further preferably 1% or more.
The reflectance of the protective film against light can be measured by the method described in the examples described below.
In the present embodiment, when the protective film-forming film is thermosetting, X is defined as aboveminAnd S100The protective film (C) is preferably 145 DEG CThe protective film forming film is heat-treated for 2 hours to obtain a cured product, and when the protective film forming film is energy ray-curable, the above-mentioned definition XminAnd S100The protective film (C) is preferably at an illuminance of 280mW/cm2The quantity of light was 260mJ/cm2The protective film-forming film was irradiated with energy rays 2 times to obtain a cured product.
On the other hand, when the film for forming a protective film is non-curable, X is defined as aboveminAnd S100The protective film (2) is the protective film forming film itself.
In the present embodiment, the above Z is calculated100When is taken as XminAnd S100The values measured using the same protective film were used.
When the protective film is formed by thermally curing the protective film-forming film, unlike the case of curing by irradiation with an energy ray, the protective film can be sufficiently cured by heating even when the protective film-forming film is thick, and therefore, a protective film having high protective performance can be formed. Further, the plurality of protective film-forming films can be collectively heated and thermally cured by using a usual heating means such as a heating oven.
When the protective film is formed by curing the protective film-forming film by irradiation with an energy ray, the protective film-forming composite sheet does not need to have heat resistance unlike the case of heat curing, and a wide range of protective film-forming composite sheets can be configured. Further, by irradiation with an energy ray, the curing can be performed in a short time.
When the protective film-forming film is used as a protective film without curing, the curing step can be omitted, and thus a chip with a protective film can be manufactured by a simplified step.
The protective film-forming film is preferably thermosetting or energy ray-curable.
The protective film-forming film may be composed of one layer (single layer) or a plurality of two or more layers regardless of whether the protective film-forming film is curable or non-curable, and when the protective film-forming film is curable, the protective film-forming film may be composed of one layer (single layer) or a plurality of two or more layers regardless of whether the protective film-forming film is thermosetting or energy ray-curable. When the protective film-forming film is composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
When the protective film-forming film is composed of two or more layers, the protective film may be warped due to poor adhesion between the layers or difference in difficulty of expansion and contraction of the layers, and the protective film may be peeled off from the back surface of the chip.
In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all the layers may be the same or different from each other, or only a part of the layers may be the same", and "a plurality of layers are different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other".
The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm, and may be any range of, for example, 10 to 50 μm, 15 to 40 μm, 17 to 38 μm, and 20 to 30 μm, regardless of whether the protective film-forming film is curable or non-curable, and when the protective film-forming film is curable, the thickness of the protective film-forming film is also preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm, and may be any range of, for example, 10 to 50 μm, 15 to 40 μm, 17 to 38 μm, and 20 to 30 μm, regardless of whether the protective film-forming film is thermosetting or energy ray curable. When the thickness of the protective film forming film is not less than the lower limit value, a protective film having higher protective performance can be formed. When the thickness of the protective film-forming film is not more than the upper limit, the thickness can be prevented from becoming too thick.
The "thickness of the protective film-forming film" refers to the thickness of the entire protective film-forming film, and for example, the thickness of the protective film-forming film composed of a plurality of layers refers to the total thickness of all the layers constituting the protective film-forming film.
Composition for Forming protective film
The protective film-forming film can be formed using a protective film-forming composition containing the constituent material thereof. For example, the protective film-forming film can be formed by applying the protective film-forming composition to the surface to be formed, and drying the composition as needed. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming a protective film is generally the same as the content ratio of the components in the film for forming a protective film. In the present specification, "normal temperature" means a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and includes, for example, a temperature of 15 to 25 ℃.
The film for forming a thermosetting protective film can be formed using the composition for forming a thermosetting protective film, the film for forming an energy ray-curable protective film can be formed using the composition for forming an energy ray-curable protective film, and the film for forming a non-curable protective film can be formed using the composition for forming a non-curable protective film. In the present specification, when the protective film-forming film has both properties of thermosetting and energy ray-curable properties, and when the contribution of thermosetting of the protective film-forming film is larger than the contribution of energy ray-curing with respect to the formation of the protective film, the protective film-forming film is regarded as a thermosetting film. In contrast, when the contribution of energy ray curing of the protective film forming film is larger than the contribution of thermal curing with respect to the formation of the protective film, the protective film forming film is regarded as an energy ray-curable film.
The coating of the composition for forming a protective film may be carried out by a known method, and examples thereof include methods using various coating machines such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the protective film forming composition are not particularly limited, regardless of whether the protective film forming film is curable or non-curable, and when the protective film forming film is curable, the drying conditions of the protective film forming composition are not particularly limited, regardless of whether the protective film forming film is thermosetting or energy ray curable. However, when the protective film-forming composition contains a solvent described later, it is preferably dried by heating. The solvent-containing composition for forming a protective film is preferably dried by heating at 70 to 130 ℃ for 10 seconds to 5 minutes, for example. However, it is preferable to heat-dry the thermosetting protective film-forming composition so that the thermosetting protective film-forming composition itself and the thermosetting protective film-forming film formed from the composition are not thermally cured.
The film for forming a thermosetting protective film, the film for forming an energy ray-curable protective film, and the film for forming a non-curable protective film will be described in this order.
Film for forming very high thermosetting protective film
The curing conditions for forming the protective film by thermally curing the film for forming a thermosetting protective film are not particularly limited as long as the protective film has a curing degree of a degree sufficient to exhibit its function, and may be appropriately selected depending on the kind of the film for forming a thermosetting protective film.
For example, the heating temperature of the thermosetting protective film forming film at the time of thermosetting is preferably 100 to 200 ℃, more preferably 110 to 170 ℃, and particularly preferably 120 to 150 ℃. The heating time during the heat curing is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours, and particularly preferably 1 to 3 hours.
The protective film formed by thermal curing is preferably slowly cooled to normal temperature after formation. The method of slow cooling is not particularly limited, and cooling may be performed.
The film for forming a protective film after heating-cooling is prepared by heating a film for forming a protective film at normal temperature to a temperature higher than normal temperature and then cooling to normal temperature, and when the hardness of the film for forming a protective film after heating-cooling is compared with the hardness of the film for forming a protective film before heating at the same temperature, the film for forming a protective film after heating-cooling is thermosetting when the film for forming a protective film after heating-cooling is harder.
Examples of preferable thermosetting protective film-forming films include a thermosetting protective film-forming film containing a polymer component (a) and a thermosetting component (B), and may further contain a light absorbing agent (I).
The polymer component (a) is a component obtained by polymerization of a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction using heat as a reaction inducer (trigger). The polymerization reaction in the present specification also includes a polycondensation reaction.
< composition for Forming thermosetting protective film (III-1) >
Examples of a preferable thermosetting protective film-forming composition include a thermosetting protective film-forming composition (III-1) (in the present specification, it may be abbreviated as "composition (III-1)") containing the polymer component (A) and the thermosetting component (B). The composition (III-1) may further contain a light absorber (I).
[ Polymer component (A) ]
The polymer component (a) is a component for imparting film formability, flexibility, toughness, ductility and the like to the thermosetting protective film forming film, and imparting flexibility, toughness, ductility and the like to the protective film.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins, and acrylic resins are preferred.
As the acrylic resin in the polymer component (a), a known acrylic polymer can be mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000. By setting the weight average molecular weight of the acrylic resin to be not less than the lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. Further, by setting the weight average molecular weight of the acrylic resin to be not more than the upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and generation of voids (void) and the like between the adherend and the film for forming a thermosetting protective film can be further suppressed.
In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The glass transition temperature (Tg) of the acrylic resin is preferably-60 to 70 ℃, and more preferably-30 to 50 ℃. When the Tg of the acrylic resin is not less than the lower limit, for example, the adhesion between the cured product of the protective film-forming film and the supporting sheet can be suppressed, and the releasability of the supporting sheet can be appropriately improved. Further, by setting Tg of the acrylic resin to the upper limit value or less, the adhesive force between the thermosetting protective film-forming film and the cured product thereof and the adherend is improved.
When the acrylic resin has m kinds of structural units (m is an integer of 2 or more), and m kinds of monomers from which the structural units are derived are assigned arbitrary non-repeating numbers from 1 to m, respectively, and are designated as "monomers m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox formula shown below.
[ mathematical formula 1]
Figure BDA0002710114310000151
Wherein Tg is the glass transition temperature of the acrylic resin; m is an integer of 2 or more; tg ofkThe glass transition temperature of a homopolymer of monomer m; wkIs the mass fraction of structural units m derived from the monomer m in the acrylic resin, wherein WkSatisfying the following formula.
[ mathematical formula 2]
Figure BDA0002710114310000152
In the formula, m and WkAnd m and WkThe same is true.
As said TgkThe values described in the Polymer data Handbook (polymers データ and ハンドブック), the adhesion Handbook (adhesion ハンドブック), or the Polymer Handbook, etc., can be used. For example, the Tg of a homopolymer of methyl acrylatekTg of a homopolymer of methyl methacrylate at 10 ℃kTg of homopolymer of 2-hydroxyethyl acrylate at 105 deg.CkIs-15 ℃.
Examples of the acrylic resin include polymers of one or two or more kinds of (meth) acrylic acid esters; one or more (meth) acrylates, and copolymers of one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
Examples of the (meth) acrylic ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is1 to 18 carbon atoms, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate);
cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylic acid imide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate; hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
and substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate. Wherein "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio thereof may be arbitrarily selected.
The acrylic resin may have a functional group capable of bonding with other compounds, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, and isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described later, or may be directly bonded to another compound without the crosslinking agent (F). By bonding the acrylic resin to another compound through the functional group, the reliability of a package (package) obtained by using the composite sheet for forming a protective film tends to be improved.
In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter, may be simply abbreviated as "thermoplastic resin") may be used alone without using an acrylic resin, or an acrylic resin and a thermoplastic resin other than an acrylic resin may be used together. By using the thermoplastic resin, the releasability of the protective film from the support sheet is improved, or the film for forming a thermosetting protective film is made to easily follow the uneven surface of the adherend, and the generation of a void or the like between the adherend and the film for forming a thermosetting protective film may be further suppressed.
The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, and more preferably 3000 to 80000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150 ℃, and more preferably-20 to 120 ℃.
Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutylene, polybutadiene, and polystyrene.
The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1), the proportion of the content of the polymer component (a) relative to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) in the film for forming a thermosetting protective film relative to the total mass of the film for forming a thermosetting protective film) is preferably 5 to 80 mass%, more preferably 8 to 70 mass%, further preferably 11 to 60 mass%, particularly preferably 14 to 50 mass%, and may be, for example, 17 to 45 mass%, and 20 to 40 mass%, regardless of the type of the polymer component (a).
Since the protective film-forming film and the protective film are generally thin, when a protective film-forming film or a protective film having low toughness and being brittle is used, cracks (gaps) are generated in the protective film-forming film or the protective film when a chip with the protective film is manufactured. However, when the ratio is not less than the lower limit, the toughness of the protective film forming film and the protective film becomes higher, and the effect of suppressing these defects becomes high.
The polymer component (A) may be a thermosetting component (B). In the present invention, when the composition (III-1) contains such a component belonging to both the polymer component (A) and the thermosetting component (B), it is regarded that the composition (III-1) contains the polymer component (A) and the thermosetting component (B).
[ thermosetting component (B) ]
The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include epoxy thermosetting resins, polyimide resins, unsaturated polyester resins, and the like, and epoxy thermosetting resins are preferable.
(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.
As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can be used.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of the epoxy group of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. The compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene group (vinyl group), a 2-propenyl group (allyl group), (meth) acryloyl group, and (meth) acrylamido group, with acryloyl group being preferred.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, and particularly preferably 300 to 3000, in view of curability of the thermosetting protective film-forming film and strength and heat resistance of the protective film as a cured product thereof.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 150 to 950 g/eq.
The epoxy resins (B1) may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
Heat-curing agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenol curing agent having a phenolic hydroxyl group as the thermal curing agent (B2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.
As the heat curing agent (B2), an amine curing agent having an amino group includes, for example, dicyandiamide and the like.
The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
The number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000, as the heat-curing agent (B2).
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 to 500, for example.
The heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 0.1 to 200 parts by mass, still more preferably 0.1 to 100 parts by mass, particularly preferably 0.5 to 50 parts by mass, and may be, for example, any one of 0.5 to 25 parts by mass, 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass, based on 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the lower limit or more, it becomes easier to cure the thermosetting protective film-forming film. When the content of the thermosetting agent (B2) is not more than the upper limit, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.
In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and may be, for example, any one of 30 to 100 parts by mass, 40 to 80 parts by mass, and 50 to 70 parts by mass, relative to 100 parts by mass of the content of the polymer component (A). When the content of the thermosetting component (B) is in the above range, for example, the adhesion between the cured product of the protective film-forming film and the supporting sheet is suppressed, and the releasability of the supporting sheet is improved.
[ light absorbing agent (I) ]
When the composition (III-1) and the film for forming a thermosetting protective film contain the light absorber (I) in an appropriate amount, the transmittance of the protective film against light having a wavelength of 400 to 750nm is small, and T ismBecomes small, whereby the presence or absence of the protective film can be easily confirmed.
Examples of the light absorbing agent (I) include organic pigments. Inorganic pigments, and the like.
Examples of the organic pigments include diimmonium pigments, aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarylium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalimide pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt pigments), dithiol metal complex pigments, indole pigments, triarylmethane pigments, anthraquinone pigments, diphenol pigments, naphthol pigments, naphthoquinone pigments, squarylium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, naphthoylium pigments, and the like pigments, Azomethine pigments, benzimidazolone pigments, Spilon pigments, pyranthrone pigments, threne pigments, and the like.
Examples of the inorganic pigment include carbon materials such as carbon black; a lanthanum-based material; a tin-based material; antimony-based materials; tungsten-based materials, and the like. The lanthanum-based material, the tin-based material, the antimony-based material and the tungsten-based material respectively refer to a lanthanum-containing material, a tin-containing material, an antimony-containing material and a tungsten-containing material.
Among these, the inorganic pigment is preferably a carbon material, and more preferably carbon black, from the viewpoint of having relatively excellent dispersibility and little change in properties due to heat.
The light absorber (I) may be capable of absorbing either or both of visible light and infrared light.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of light absorber (I), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected. For example, the composition (III-1) and the film for forming a thermosetting protective film may contain only one or two or more organic pigments as the light absorbing agent (I), may contain only one or two or more inorganic pigments, or may contain both of one or two or more organic pigments and inorganic pigments.
The composition (III-1) and the film for forming a thermosetting protective film may contain two or more types of light absorbers (I) capable of absorbing either or both of visible light and infrared light, and for example, may contain 2 to 7 types of light absorbers (I) capable of absorbing either or both of visible light and infrared light.
When the composition (III-1) and the film for forming a thermosetting protective film contain an inorganic pigment as the light absorber (I), they may contain a carbon material, and in this case, for example, they may contain both a carbon material and an organic pigment.
When the light absorber (I) is used, the content of the light absorber (I) in the composition (III-1) is preferably 0.1 to 20% by mass, more preferably 0.3 to 17.5% by mass, even more preferably 0.5 to 16% by mass, and particularly preferably 1 to 15% by mass, relative to the total content of all the components except the solvent (i.e., the content of the light absorber (I) in the film for forming a thermosetting protective film relative to the total mass of the film for forming a thermosetting protective film). By setting the ratio to the lower limit or more, the effect of using the light absorbing agent (I) can be more remarkably obtained. By setting the ratio to the upper limit or less, the excessive use of the light absorbing agent (I) can be suppressed.
[ curing Accelerator (C) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III-1).
Examples of the preferable curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which one or more hydrogen atoms are replaced with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with an organic group); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylphosphonate and triphenylphosphine tetraphenylboronate.
The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, based on 100 parts by mass of the thermosetting component (B) in the composition (III-1) and the film for forming a thermosetting protective film. By setting the content of the curing accelerator (C) to the lower limit or more, the effect of using the curing accelerator (C) can be more remarkably obtained. When the content of the curing accelerator (C) is not more than the above upper limit, for example, the effect of suppressing the occurrence of segregation due to the highly polar curing accelerator (C) moving to the side of the adhesive interface with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions becomes high. As a result, the reliability of the chip with the protective film obtained by using the composite sheet for forming a protective film is further improved.
[ Filler (D) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By incorporating the filler (D) into the thermosetting protective film-forming film, it becomes easy to adjust the thermal expansion coefficient between the thermosetting protective film-forming film and the cured product thereof (i.e., the protective film), and by optimizing the thermal expansion coefficient for the object to be protected, the reliability of the chip with the protective film obtained by using the composite sheet for protecting film formation is further improved. Further, by incorporating the filler (D) into the thermosetting protective film-forming film, the moisture absorption rate of the protective film can be reduced, and the heat dissipation can be improved.
The filler (D) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.
Examples of preferable inorganic fillers include powders of silica, stainless steel, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
Among them, the inorganic filler is preferably silica or alumina, and particularly preferably silica. S of protective film when using silica or alumina100The adjustment of (a) becomes easier, and when the protective film is required to have insulation, the protective film is more easily given insulation.
The average particle diameter of the filler (D) is not particularly limited, but is preferably 10 to 4000nm, more preferably 30 to 3500 nm. By setting the average particle diameter of the filler (D) within the above range, the effects of using the filler (D) can be more remarkably obtained.
For example, the amount of the filler (D) in the composition (III-1) and the film for forming a thermosetting protective film can be easily increased, and the S of the protective film can be easily adjusted100The filler (D) preferably has an average particle diameter of 10 to 2500nm, more preferably 20 to 1000nm, and still more preferably 30 to 600 nm. On the other hand, in any case, the filler (D) having an average particle diameter of not less than the lower limit is excellent in handling property, and therefore, the composition (III-1) is advantageous in that the effect of using the protective film can be stably obtained.
Unless otherwise specified, the term "average particle diameter" as used herein refers to a particle diameter (D) at which the cumulative value is 50% in a particle size distribution curve obtained by a laser diffraction scattering method50) The value of (c).
The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the filler (D) is used, the content of the filler (D) in the composition (III-1) is preferably 5 to 70% by mass, for example, 8 to 65% by mass, relative to the total content of all the components except the solvent (i.e., the content of the filler (D) in the film for forming a thermosetting protective film relative to the total mass of the film for forming a thermosetting protective film)Any one of the ranges of% by mass, 11 to 60% by mass, 14 to 55% by mass and 17 to 50% by mass. When the ratio is within the above range, the thermal expansion coefficient of the film for forming a thermosetting protective film and the cured product thereof (i.e., the protective film) can be adjusted, and the S of the protective film can be adjusted100The adjustment of (a) becomes easier.
[ coupling agent (E) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adherence of the thermosetting protective film-forming film to an adherend can be improved. Further, by using the coupling agent (E), the water resistance of the cured product of the film for forming a thermosetting protective film is improved without impairing the heat resistance.
The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.
Examples of the preferable silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). When the content of the coupling agent (E) is not less than the lower limit, the effects of using the coupling agent (E) such as improvement of dispersibility of the filler (D) in the resin and improvement of adhesion between the thermosetting protective film-forming film and the adherend can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of outgassing (outgas) can be further suppressed.
[ crosslinking agent (F) ]
When a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which can be bonded to another compound, such as the acrylic resin, is used as the polymer component (a), the composition (III-1) and the film for forming a thermosetting protective film may contain the crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and by crosslinking in this way, the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted.
Examples of the crosslinking agent (F) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
When an acrylic resin or the like having the above functional group is used as the polymer component (a), the composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent which reacts with the functional group by heating as the crosslinking agent (F). Examples of the crosslinking agent that reacts with the functional group by heating include a blocked isocyanate compound obtained by blocking an isocyanate group of an organic polyisocyanate compound, and a polyfunctional compound having ester exchange reactivity.
The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer component (A). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. Further, by making the content of the crosslinking agent (F) the upper limit value or less, the excessive use of the crosslinking agent (F) is suppressed.
[ energy ray-curable resin (G) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain an energy ray-curable resin (G). By incorporating the energy ray-curable resin (G) into the film for forming a thermosetting protective film, the properties can be changed by irradiation with an energy ray.
The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate compound include (meth) acrylates having a chain-like aliphatic skeleton such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; cyclic aliphatic skeleton-containing (meth) acrylates such as dicyclopentyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; a urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylates; a polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30000, more preferably 300 to 10000.
The energy ray-curable compound used for polymerization may be one kind only, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
The energy ray-curable resin (G) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the composition (III-1).
[ photopolymerization initiator (H) ]
When the composition (III-1) and the film for forming a thermosetting protective film contain the energy ray-curable resin (G), a photopolymerization initiator (H) may be contained in order to efficiently carry out the polymerization reaction of the energy ray-curable resin (G).
Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethoxy-1, 2-diphenylethan-1-one, and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as butanedione; benzil (benzil); dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Further, as the photopolymerization initiator (H), for example, a photosensitizer such as amine may be used.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of photopolymerization initiator (H), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable resin (G).
[ general additive (J) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain the general-purpose additive (J) within a range not to impair the effects of the present invention.
The general-purpose additive (J) may be a known additive, may be arbitrarily selected according to the purpose, and is not particularly limited, and preferable additives include, for example, a plasticizer, an antistatic agent, an antioxidant, a gettering agent (gelling agent), an ultraviolet absorber, a thickener, and the like.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of the general-purpose additive (J), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited and may be appropriately selected depending on the purpose.
[ solvent ]
The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent was excellent in handling properties.
The solvent is not particularly limited, and preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition (III-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
As a solvent contained in the composition (III-1), methyl ethyl ketone, toluene, ethyl acetate and the like are exemplified, since the components contained in the composition (III-1) can be more uniformly mixed.
The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on the kind of the components other than the solvent, for example.
< method for producing composition for forming thermosetting protective film >
The composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending the respective components constituting the composition.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When blending, the method for mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer (mixer); a method of mixing by applying ultrasonic waves, and the like.
The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.
Energy ray-curable protective film-forming film
The curing conditions for forming the protective film by curing the energy ray-curable protective film-forming film with an energy ray are not particularly limited as long as the protective film has a degree of curing sufficient to exert its function, and may be appropriately selected depending on the type of the energy ray-curable protective film-forming film.
For example, when the film for forming an energy ray-curable protective film is cured by an energy ray, the illuminance of the energy ray is preferably 60 to 320mW/cm2. The amount of the energy ray during curing is preferably 100 to 1000mJ/cm2。
Examples of the film for forming an energy ray-curable protective film include a film containing the energy ray-curable component (a), a film further containing a light absorbing agent, and a film containing both a light absorbing agent and a filler.
In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
< composition for Forming energy ray-curable protective film (IV-1) >
Examples of a preferable energy ray-curable composition for forming a protective film include an energy ray-curable composition for forming a protective film (IV-1) (in the present specification, it may be abbreviated as "composition (IV-1)") containing the energy ray-curable component (a). The composition (IV-1) may further contain a light absorbing agent.
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and is a component for imparting film formability, flexibility, and the like to the energy ray-curable protective film-forming film, and for forming a hard protective film after curing.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000. At least a portion of the polymer (a1) may or may not be crosslinked by a crosslinking agent.
(a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000.)
Examples of the polymer (a1) having energy-ray curable groups and a weight-average molecular weight of 80000 to 2000000 include an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound and an energy-ray curable compound (a12) having an energy-ray curable group such as a group reactive with the functional group and an energy-ray curable double bond.
Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a wafer, a chip, or the like. Among them, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a11)
Examples of the acrylic polymer (a11) having a functional group include polymers obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group, and polymers obtained by further copolymerizing a monomer other than an acrylic monomer (non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be used.
Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth) acryloyl skeleton).
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
It is preferable that the acrylic monomer having the functional group is a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth), And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearate (meth) acrylate).
Examples of the acrylic monomer having no functional group include (meth) acrylates containing an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and non-crosslinkable (meth) acrylic esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a11), the proportion (content) of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the polymer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio in the above range, the content of the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be adjusted to a preferable range of the degree of curing of the protective film.
The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV-1), the proportion of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (i.e., the proportion of the content of the acrylic resin (a1-1) in the energy ray-curable protective film-forming film to the total mass of the film) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.
Energy ray-curable compound (a12)
The energy ray-curable compound (a12) preferably has one or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and more preferably has an isocyanate group as the group. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
The number of the energy ray-curable groups of the energy ray-curable compound (a12) in one molecule thereof is not particularly limited, and may be appropriately selected in consideration of physical properties such as shrinkage ratio required for the intended protective film.
For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably has 1 to 3 energy ray-curable groups.
Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate;
an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate.
Among them, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in the above range, the adhesive strength of the cured product of the energy ray-curable protective film-forming film is further increased. In addition, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the proportion of the content is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the proportion of the content may exceed 100 mol%.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 1500000.
The "weight average molecular weight" is the weight average molecular weight described above.
The polymer (a1) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000.)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group, a vinyl group and the like.
As long as the above conditions are satisfied, the compound (a2) is not particularly limited, and examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, a phenol resin having an energy ray-curable group, and the like.
Examples of the low molecular weight compound having an energy ray-curable group in the compound (a2) include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypropyloxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and mixtures thereof, Bifunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acryloyloxypropane;
polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate;
and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the compound (a2), for example, the resins described in japanese patent application laid-open No. 2013-194102 "paragraph 0043 and the like can be used. The above-mentioned resin also belongs to the resins constituting the thermosetting component described later, but it is regarded as the compound (a2) in the composition (IV-1).
The weight average molecular weight of the compound (a2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a2) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition (IV-1) and the film for forming an energy ray-curable protective film contain the compound (a2) as the energy ray-curable component (a), it is preferable that the composition further contains a polymer (b) having no energy ray-curable group.
At least a part of the polymer (b) may or may not be crosslinked by a crosslinking agent.
Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, glycidyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, and substituted amino group-containing (meth) acrylates. Wherein "substituted amino group" is the previously described substituted amino group.
Examples of the alkyl (meth) acrylate include the same alkyl (meth) acrylates as those of the acrylic monomers having no functional group (e.g., alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms) constituting the acrylic polymer (a11) described above.
Examples of the (meth) acrylate having a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate, and the like.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate and the like.
Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked by a crosslinking agent, include polymers obtained by reacting a reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group is not particularly limited, and may be appropriately selected depending on the kind of the crosslinking agent. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among 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 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. However, the reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing the circuit of the wafer or chip from being corroded.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include polymers obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), a monomer having the reactive functional group may be used as either one or both of the acrylic monomer and the non-acrylic monomer exemplified as the monomer constituting the acrylic polymer (b-1). Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and polymers obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the above-mentioned acrylic monomer or non-acrylic monomer are substituted with the reactive functional group.
In the polymer (b) having a reactive functional group, the proportion (content) of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By setting the ratio in the above range, the degree of crosslinking in the polymer (b) becomes a more preferable range.
The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000, from the viewpoint of improving the film-forming property of the composition (IV-1). The "weight average molecular weight" is the weight average molecular weight described above.
The composition (IV-1) and the energy ray-curable protective film-forming film may contain only one kind of polymer (b) having no energy ray-curable group, or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) may be a composition containing either one or both of the polymer (a1) and the compound (a 2). When the composition (IV-1) contains the compound (a2), it preferably further contains a polymer (b) having no energy ray-curable group, and in this case, it further preferably contains the compound (a 1). The composition (IV-1) may contain the polymer (a1) and the polymer (b) having no energy ray-curable group, in addition to the compound (a 2).
When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the content of the compound (a2) in the composition (IV-1) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total mass of the film in the energy ray-curable protective film-forming film) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the ratio of the content of the energy ray-curable component is in the above range, the energy ray-curability of the energy ray-curable protective film-forming film is more preferable.
[ light absorbing agent ]
When the composition (IV-1) and the film for forming an energy ray-curable protective film contain a light absorber in an appropriate amount, the protective film has a low transmittance for light having a wavelength of 400 to 750nm, and T ismBecomes small, whereby it can be easily determined whether or not the protective film is present.
The light absorbing agent contained in the composition (IV-1) and the energy ray-curable protective film-forming film is the same as the light absorbing agent (I) contained in the composition (III-1) and the thermosetting protective film-forming film described above.
The light absorber of the composition (IV-1) and the energy ray-curable film for forming a protective film may be contained in the same manner as the light absorber (I) of the composition (III-1) and the thermosetting film for forming a protective film.
For example, the light absorber contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be capable of absorbing either or both of visible light and infrared light.
The composition (IV-1) and the energy ray-curable protective film-forming film may contain only one kind of light absorber, or two or more kinds of light absorbers, and when two or more kinds of light absorbers are contained, the combination and ratio thereof may be arbitrarily selected. For example, the composition (IV-1) and the film for forming an energy ray-curable protective film may contain only one or two or more organic pigments, only one or two or more inorganic pigments, or one or two or more organic pigments and inorganic pigments as a light absorber.
The composition (IV-1) and the energy ray-curable protective film-forming film may contain two or more kinds of light absorbers capable of absorbing either or both of visible light and infrared light, and for example, may contain 2 to 7 kinds of light absorbers capable of absorbing either or both of visible light and infrared light.
When the composition (IV-1) and the film for forming an energy ray-curable protective film contain an inorganic pigment as a light absorber, they may contain a carbon material, or may contain both a carbon material and an organic pigment.
When the light absorber is used, the proportion of the content of the light absorber to the total content of all the components except the solvent (i.e., the proportion of the content of the light absorber in the energy ray-curable protective film-forming film to the total mass of the energy ray-curable protective film-forming film) in the composition (IV-1) may be 0.1 to 20% by mass. When the ratio is not less than the lower limit, the effect of using the light absorbing agent can be more remarkably obtained. By setting the ratio to the upper limit or less, the excessive use of the light absorbing agent can be suppressed.
The composition (IV-1) and the film for forming an energy ray-curable protective film may contain, if necessary, one or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, and a general-purpose additive, which are not included in any of the energy ray-curable component (a), the polymer (b), and the light absorber.
Examples of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator and the general-purpose additive in the composition (IV-1) include the same components as those of the thermosetting component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H) and the general-purpose additive (J) in the composition (III-1), respectively.
For example, when the composition (IV-1) contains a thermosetting component, the adhesion of the formed film for forming an energy ray-curable protective film to an adherend is improved by heating by using such a composition (IV-1), and the strength of the protective film formed from the film for forming an energy ray-curable protective film is also improved.
In the composition (IV-1), the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator and the general-purpose additive may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The contents of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator and the general additive in the composition (IV-1) are not particularly limited as long as they are appropriately adjusted according to the purpose.
The composition (IV-1) is preferably further containing a solvent because the handling properties are improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The composition (IV-1) may contain only one solvent, or may contain two or more solvents.
The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent.
< method for producing composition for forming energy ray-curable protective film >
The energy ray-curable composition for forming a protective film, such as the composition (IV-1), can be obtained by blending the components constituting the composition.
The energy ray-curable composition for forming a protective film can be prepared, for example, by the same method as the thermosetting composition for forming a protective film described above, except that the kinds of the blend components are different.
Non-curable protective film-forming film
The film for forming a non-curable protective film is preferably a film containing a thermoplastic resin, and may further contain a light absorber and a filler.
< composition for Forming non-curable protective film (V-1) >
Examples of a preferable composition for forming a non-curable protective film include a composition (V-1) for forming a non-curable protective film (hereinafter, abbreviated as "composition (V-1)") containing the thermoplastic resin. The composition (V-1) may further contain a light absorber and a filler.
[ thermoplastic resin ]
The thermoplastic resin is not particularly limited.
More specifically, the thermoplastic resin may be the same as the non-curable resin such as the acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. mentioned as the component contained in the composition (III-1).
The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (V-1), the proportion of the content of the thermoplastic resin with respect to the total content of the components other than the solvent (i.e., the proportion of the content of the thermoplastic resin in the non-curable protective film-forming film with respect to the total mass of the non-curable protective film-forming film) is preferably 25 to 75% by mass.
[ light absorbing agent ]
When the composition (V-1) and the film for forming a non-curable protective film contain a light absorber in an appropriate amount, the protective film has a low transmittance to light having a wavelength of 400 to 750nm, and T ismBecomes small, whereby the presence or absence of the protective film can be easily confirmed.
The light absorber contained in the composition (V-1) and the non-curable protective film-forming film is the same as the light absorber (I) contained in the composition (III-1) and the thermosetting protective film-forming film described above.
The light absorber of the composition (V-1) and the film for forming a non-curable protective film may be contained in the same manner as the light absorber (I) of the composition (III-1) and the film for forming a thermosetting protective film.
For example, the light absorber contained in the composition (V-1) and the non-curable protective film-forming film can absorb either or both of visible light and infrared light.
The composition (V-1) and the non-curable protective film-forming film may contain only one kind of light absorber, or two or more kinds of light absorbers, and when two or more kinds of light absorbers are contained, the combination and ratio thereof may be arbitrarily selected. For example. As the light absorbing agent, the composition (V-1) and the film for forming a non-curable protective film may contain only one or two or more organic pigments, may contain only one or two or more inorganic pigments, and may contain one or two or more organic pigments and inorganic pigments at the same time.
The composition (V-1) and the film for forming a non-curable protective film may contain two or more kinds of light absorbers capable of absorbing either or both of visible light and infrared light, and for example, may contain 2 to 7 kinds of light absorbers capable of absorbing either or both of visible light and infrared light.
When the composition (V-1) and the non-curable protective film-forming film contain an inorganic pigment as a light absorber, they may contain a carbon material, or may contain both a carbon material and an organic pigment.
In the composition (V-1), the proportion of the content of the light absorbing agent with respect to the total content of all the components except the solvent (i.e., the proportion of the content of the light absorbing agent in the non-curable protective film-forming film with respect to the total mass of the non-curable protective film-forming film) may be 0.1 to 20% by mass. When the ratio is not less than the lower limit, the effect of using the light absorbing agent can be more remarkably obtained. By making the ratio the upper limit value or less, excessive use of the light absorbing agent is suppressed.
[ Filler ]
The filler-containing film for forming a non-curable protective film exhibits the same effects as those of the filler-containing film for forming a thermosetting protective film.
Examples of the filler contained in the composition (V-1) and the non-curable film for forming a protective film include the same fillers as the filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film.
The composition (V-1) and the non-curable protective film-forming film may contain only one filler, or may contain two or more fillers, and when the amount of the filler is two or more, the combination and ratio thereof may be arbitrarily selected.
In the composition (V-1), the proportion of the content of the filler relative to the total content of all the components except the solvent (i.e., the proportion of the content of the filler in the non-curable protective film-forming film relative to the total mass of the non-curable protective film-forming film) is preferably 25 to 75% by mass. By setting the ratio within the above range, the thermal expansion coefficient of the non-curable protective film-forming film (i.e., the protective film) can be more easily adjusted as in the case of using the composition (III-1).
The composition (V-1) may contain other components not belonging to any of the thermoplastic resin, the light absorbing agent, and the filler, depending on the purpose.
The other components are not particularly limited and may be arbitrarily selected according to the purpose.
In the composition (V-1), the other components may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the other components of the composition (V-1) is not particularly limited as long as it is appropriately adjusted according to the purpose.
The composition (V-1) is preferably further containing a solvent because the handling properties are improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
The composition (V-1) may contain only one kind of solvent, or may contain two or more kinds of solvents.
The content of the solvent in the composition (V-1) is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.
< method for producing composition for forming non-curable protective film >
The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the respective components for constituting the composition.
The non-curable composition for forming a protective film can be prepared, for example, by the same method as the thermosetting composition for forming a protective film described above, except that the kind of the blend component is different.
Fig. 1 is a cross-sectional view schematically showing an example of a film for forming a protective film according to an embodiment of the present invention. For the sake of convenience, the drawings used in the following description may show important parts in an enlarged manner, and the dimensional ratios of the respective components are not necessarily the same as those in the actual case.
The protective film forming film 13 shown therein includes a first release film 151 on one surface (in this specification, sometimes referred to as a "first surface") 13a thereof, and a second release film 152 on the other surface (in this specification, sometimes referred to as a "second surface") 13b opposite to the first surface 13 a.
The film 13 for forming a protective film is suitably stored in a roll form, for example.
The protective film forming film 13 has the above-described characteristics.
The protective film forming film 13 can be formed using the above-described protective film forming composition.
Both the first release film 151 and the second release film 152 may be known release films. The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other in that, for example, the release forces required for releasing from the film-like pressure-sensitive adhesive 13 are different from each other.
In the protective film forming film 13 shown in fig. 1, an exposed surface formed by removing either one of the first release film 151 and the second release film 152 is a surface to be stuck to the back surface of a wafer (not shown). Then, an exposed surface formed by removing the remaining one of the first release film 151 and the second release film 152 is a surface to which a support sheet or a dicing sheet (also referred to as a "dicing tape" in this specification) described later is attached. For example, when the first surface 13a is a surface attached to the back surface of the wafer, the second surface 13b is an attachment surface of a support sheet or a dicing sheet.
Although fig. 1 shows an example in which the release film is provided on both surfaces (the first surface 13a and the second surface 13b) of the protective film forming film 13, the release film may be provided only on one surface of the protective film forming film 13, or may be provided only on the first surface 13a or only on the second surface 13 b.
The protective film forming film of the present embodiment may be attached to the back surface of the wafer so as not to be used together with a support sheet described later. In this case, a release film may be provided on the surface of the protective film-forming film opposite to the surface to be bonded to the wafer, and the release film may be removed at an appropriate timing. The chip with the protective film can be produced by attaching a dicing sheet to the exposed surface of the protective film forming film from which the release film has been removed, and dicing the same, that is, by dividing the wafer and cutting the protective film forming film or the protective film.
On the other hand, the protective film forming film of the present embodiment can be used together with a support sheet described later, whereby a composite sheet for forming a protective film, which can form a protective film and cut the protective film at the same time, can be configured. Hereinafter, such a composite sheet for forming a protective film will be described.
Diamond compact for forming protective film
The composite sheet for forming a protective film according to one embodiment of the present invention includes a support sheet and a film for forming a protective film provided on one surface of the support sheet, and the film for forming a protective film according to one embodiment of the present invention is the film for forming a protective film described above.
By using the composite sheet for forming a protective film of the present embodiment, the following intermediate structure can be obtained: the wafer holding apparatus holds 1 or 2 or more (usually 2 or more) chips with a protective film or 1 wafer with a protective film on 1 support sheet, and the support sheet is in a state of being extended in a direction parallel to the surface of the chip with a protective film or the wafer with a protective film. In obtaining such an intermediate structure, as described above, for example, there are cases where: a case where a modified layer is formed inside a wafer on a composite sheet for forming a protective film by means of Stealth Dicing (registered trademark), and then the wafer is spread together with a support sheet and a protective film, thereby being divided into chips; or a case where the wafer on the composite sheet for forming a protective film is divided into chips by various dicing such as dicing, laser cutting, or water cutting, and the support sheet is expanded so that the chip with the protective film can be picked up easily thereafter, and then the support sheet is stored with the chip with the protective film remaining.
Even if the protective film forming film of the present embodiment is not used together with the support sheet, the dicing sheet is attached to the protective film forming film and then the wafer is divided, so that an intermediate structure similar to that in the case of using the above-described composite sheet for forming a protective film can be obtained.
As described above, in the support sheet or the dicing sheet in the intermediate structure, a region in the vicinity of the peripheral edge portion of the wafer on which the chip with a protective film or the wafer with a protective film is not originally held may be subjected to heat treatment by irradiation with near infrared rays or intermediate infrared rays, and heat shrinkage may be performed. In this case, by using the film for forming a protective film of the present embodiment, even if the protective film formed of the film for forming a protective film is erroneously irradiated with near infrared rays or intermediate infrared rays, unintended temperature rise of the protective film can be suppressed, and discoloration of the protective film can be suppressed.
In the present specification, even after the protective film-forming film is cured, the laminated structure is referred to as a "protective film-forming composite sheet" as long as the laminated structure of the support sheet and the cured product of the protective film-forming film can be maintained.
Hereinafter, each layer constituting the composite sheet for forming a protective film will be described in detail.
Supporting piece
The support sheet may be formed of one layer (single layer) or may be formed of a plurality of layers of two or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.
The support sheet may be transparent or opaque, and may be colored according to the purpose.
For example, when the protective film-forming film has energy ray curability, the support sheet preferably transmits energy rays.
Examples of the support sheet include a support sheet having a base material and an adhesive layer provided on one surface of the base material; a support sheet composed only of a base material, and the like. When the support sheet includes the adhesive layer, the adhesive layer is disposed between the base material and the protective film-forming film in the protective film-forming composite sheet.
When a support sheet including a base material and an adhesive layer is used, the adhesion or adhesiveness between the support sheet and the film for forming a protective film can be easily adjusted in the composite sheet for forming a protective film.
When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.
Hereinafter, an example of the composite sheet for forming a protective film according to the present embodiment will be described with reference to the drawings, depending on the type of the support sheet.
Fig. 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
In the drawings subsequent to fig. 2, the same components as those shown in the already-described drawings are denoted by the same reference numerals as those in the already-described drawings, and detailed description thereof will be omitted.
The composite sheet 101 for forming a protective film shown therein is configured by including a support sheet 10 and a film 13 for forming a protective film provided on one surface (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10.
The support sheet 10 is configured by including a base material 11 and an adhesive layer 12 provided on one surface (i.e., a first surface) 11a of the base material 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is disposed between the base material 11 and the film 13 for forming a protective film.
That is, the composite sheet 101 for forming a protective film is configured by sequentially laminating the base material 11, the adhesive layer 12, and the film 13 for forming a protective film in the thickness direction thereof.
The surface (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10 on the side of the protective film forming film 13 is the same as the surface (in this specification, sometimes referred to as "first surface") 12a of the adhesive layer 12 on the side opposite to the substrate 11.
The composite sheet 101 for forming a protective film further includes a pressure-sensitive adhesive layer 16 for a jig and a release film 15 on the film 13 for forming a protective film.
In the composite sheet 101 for forming a protective film, the film 13 for forming a protective film is laminated over the entire or almost the entire first surface 12a of the adhesive agent layer 12, and the adhesive layer 16 for a jig is laminated on a part of the surface (in this specification, sometimes referred to as "first surface") 13a of the film 13 for forming a protective film, which is opposite to the adhesive agent layer 12 side, that is, a region near the peripheral edge portion. Further, a release film 15 is laminated on a region of the first surface 13a of the protective film forming film 13 on which the jig pressure-sensitive adhesive layer 16 is not laminated and a surface (in this specification, may be referred to as "first surface") 16a of the jig pressure-sensitive adhesive layer 16 opposite to the protective film forming film 13 side.
The composite sheet for forming a protective film of the present embodiment is not limited to the composite sheet 101 for forming a protective film, and the composite sheet for forming a protective film of the present embodiment may have any configuration of a release film (for example, the release film 15 shown in fig. 2).
In the composite sheet 101 for forming a protective film, a part of a gap may be generated between the release film 15 and a layer directly contacting the release film 15.
For example, although the release film 15 is shown in a state of being in contact with (laminated on) the side surface 16c of the pressure-sensitive adhesive layer 16 for a jig, the release film 15 may not be in contact with the side surface 16 c. Here, although the release film 15 is shown in a state of being in contact with (laminated on) the region near the jig pressure-sensitive adhesive layer 16 on the first surface 13a of the protective film forming film 13, the release film 15 may not be in contact with the region.
In addition, the boundary between the first surface 16a and the side surface 16c of the pressure-sensitive adhesive layer 16 for a jig may not be clearly distinguished.
The same applies to the composite sheet for forming a protective film of the other embodiment including the pressure-sensitive adhesive layer for a jig.
The jig adhesive layer 16 is used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame.
The pressure-sensitive adhesive layer 16 for a jig may have, for example, a single-layer structure containing a pressure-sensitive adhesive component, or may have a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.
As described above, Z of the protective film obtained from the composite sheet 101 for forming a protective film100Is 0.27 or less.
The composite sheet 101 for forming a protective film is used in the following manner: in the state where the release film 15 is removed, the back surface of the wafer is attached to the first surface 13a of the protective film forming film 13, and the first surface 16a of the jig adhesive layer 16 is further attached to a jig such as a ring frame.
Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
The composite sheet 102 for forming a protective film shown therein is the same as the composite sheet 101 for forming a protective film shown in fig. 2, except that the shape and size of the film for forming a protective film are different, and the adhesive layer for a jig is laminated on the first surface of the adhesive layer instead of the first surface of the film for forming a protective film.
More specifically, in the composite sheet for forming a protective film 102, the film for forming a protective film 23 is laminated on a partial region of the first surface 12a of the adhesive agent layer 12, that is, on a central region in the width direction (the left-right direction in fig. 3) of the adhesive agent layer 12. Further, the jig adhesive layer 16 is laminated on a region of the first surface 12a of the adhesive agent layer 12 where the protective film forming film 23 is not laminated, that is, a region near the peripheral edge portion. The release film 15 is laminated on a surface (in this specification, it may be referred to as a "first surface") 23a of the protective film forming film 23 opposite to the adhesive layer 12 side and a first surface 16a of the jig adhesive layer 16.
Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
The composite sheet 103 for forming a protective film shown therein is the same as the composite sheet 102 for forming a protective film shown in fig. 3, except that it does not have the pressure-sensitive adhesive layer 16 for a jig.
Fig. 5 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
The composite sheet 104 for forming a protective film shown therein is the same as the composite sheet 101 for forming a protective film shown in fig. 2, except that it is configured to include the back sheet 20 instead of the back sheet 10.
Support sheet 20 is composed of only substrate 11.
That is, the composite sheet 104 for forming a protective film is configured by laminating the substrate 11 and the film 13 for forming a protective film in the thickness direction thereof.
The surface (in this specification, may be referred to as "first surface") 20a of the support sheet 20 on the side of the protective film forming film 13 is the same as the first surface 11a of the base material 11.
The substrate 11 has adhesiveness at least on the first surface 11a thereof.
The composite sheet for forming a protective film of the present embodiment is not limited to the composite sheet for forming a protective film shown in fig. 2 to 5, and may be a sheet obtained by modifying or deleting a part of the configuration of the composite sheet for forming a protective film shown in fig. 2 to 5, or a sheet obtained by further adding another configuration to the composite sheet for forming a protective film described above, within a range not to impair the effects of the present invention. More specifically, as described below.
As the composite sheet for forming a protective film having a support sheet composed only of a base material, only the composite sheet 104 for forming a protective film shown in fig. 5 is shown, but as the composite sheet for forming a protective film having a support sheet composed only of a base material, for example, a composite sheet 102 for forming a protective film shown in fig. 3 or a composite sheet 103 for forming a protective film shown in fig. 4, a composite sheet for forming a protective film having no adhesive layer 12 can be cited. However, these are merely examples of composite sheets for forming other protective films provided with support sheets composed of only base materials.
As for the composite sheet for forming a protective film without a pressure-sensitive adhesive layer for a jig, only the composite sheet 103 for forming a protective film shown in fig. 4 is shown, but as the composite sheet for forming a protective film without a pressure-sensitive adhesive layer for a jig, for example, a composite sheet for forming a protective film without a pressure-sensitive adhesive layer 16 for a protective film in the composite sheet 101 for forming a protective film shown in fig. 2 can be cited; the composite sheet 104 for forming a protective film shown in fig. 5 does not include the pressure-sensitive adhesive layer 16 for a jig. However, these are only examples of other composite sheets for forming a protective film without a pressure-sensitive adhesive layer for a jig.
The base material, the adhesive layer, the film for forming the protective film, and the release film have been shown as the layers constituting the composite sheet for forming the protective film, but the composite sheet for forming the protective film may have other layers not belonging to any of the above members.
The type of the other layer is not particularly limited, and may be arbitrarily selected according to the purpose.
The arrangement position, shape, size, and the like of the other layers may be arbitrarily selected depending on the type thereof, and are not particularly limited.
Examples of the other layer include an intermediate layer disposed between the support sheet and the protective film-forming film, and the intermediate layer can provide the protective film-forming composite sheet with certain properties by adjusting the releasability of the protective film-forming film or a cured product thereof from the support sheet.
However, this is merely an example of the composite sheet for forming another protective film having another layer.
In the composite sheet for forming a protective film of the present embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.
Next, each layer constituting the support sheet will be described in further detail.
O base material
The substrate is in the form of a sheet or a film, and examples of the constituent material include various resins.
Examples of the resin include polyethylene such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and ethylene-norbornene copolymers; vinyl chloride resins (resins obtained using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; polystyrene; a polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; copolymers of two or more of said polyesters; poly (meth) acrylates; a polyurethane; a urethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.
Further, as the resin, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester can be cited. It is preferable that the amount of the resin other than polyester in the polymer alloy of the polyester and the resin other than polyester is smaller.
Examples of the resin include crosslinked resins obtained by crosslinking one or two or more of the above-exemplified resins; one or two or more kinds of modified resins such as ionomers among the above-exemplified resins are used.
The resin constituting the base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of one layer (single layer) or a plurality of layers of two or more layers, and when composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the base material is preferably 50 to 300 μm, and more preferably 60 to 100 μm. By setting the thickness of the base material to the above range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a wafer are further improved.
The "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.
The base material may contain various known additives such as a filler, a colorant, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer), in addition to the main constituent material such as the resin.
The base material may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited with other layers.
For example, when the protective film-forming film has energy ray curability, the substrate preferably transmits energy rays.
In order to adjust the adhesiveness between the substrate and a layer provided on the substrate (for example, an adhesive layer, a film for forming a protective film, or the other layer), the surface may be subjected to an embossing treatment by sandblasting, solvent treatment, or the like; oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; oleophylic treatment; hydrophilic treatment, etc. In addition, the surface of the substrate may be primed.
The substrate may have adhesiveness on at least one surface by containing a component (for example, a resin or the like) in a predetermined range.
The substrate can be manufactured by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
Adhesive layer
The adhesive layer is in a sheet or film shape and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins.
In the present specification, "adhesive resin" includes a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having adhesiveness itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive or a resin exhibiting adhesiveness due to the presence of a cause such as heat or water.
The adhesive layer may be composed of one layer (single layer) or a plurality of layers of two or more layers, and in the case of being composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100. mu.m, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer.
The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. That is, the adhesive layer may be either energy ray-curable or non-energy ray-curable. The energy ray-curable adhesive agent layer can be easily adjusted in physical properties before and after curing.
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive composition is applied to a surface of an adhesive layer to be formed, and dried as necessary, whereby the adhesive layer can be formed at a target site. The content ratio of the components that do not vaporize at ordinary temperature in the adhesive composition is generally the same as the content ratio of the components in the adhesive layer.
The adhesive composition can be applied, for example, by the same method as the coating of the above-described composition for forming a protective film.
When the adhesive layer is provided on the substrate, for example, the adhesive composition may be applied to the substrate and dried as necessary, thereby laminating the adhesive layer on the substrate. In addition, when the adhesive layer is provided on the substrate, for example, the adhesive layer may be laminated on the substrate by applying an adhesive composition on a release film, drying the adhesive composition as needed, thereby forming the adhesive layer on the release film and bonding an exposed surface of the adhesive layer to one surface of the substrate. The release film in this case may be removed at any time during the production process or the use process of the composite sheet for forming a protective film.
The drying conditions of the adhesive composition are not particularly limited, regardless of whether the adhesive layer is energy-ray curable or non-energy-ray curable. However, when the adhesive composition contains a solvent described later, it is preferable to perform drying by heating. The adhesive composition containing a solvent is preferably dried by heating at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
When the adhesive layer is energy ray-curable, examples of the energy ray-curable adhesive composition include: an adhesive composition (I-1) comprising a non-energy-ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1 a)") and an energy-ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") having an unsaturated group introduced into a side chain of a non-energy ray-curable adhesive resin (I-1 a); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.
When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include the adhesive composition (I-4) containing the non-energy ray-curable adhesive resin (I-1 a).
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) in the adhesive compositions (I-1), (I-2), (I-3) and (I-4) (hereinafter, these adhesive compositions are collectively abbreviated as "adhesive compositions (I-1) to (I-4)") is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.
In addition to having a structural unit derived from an alkyl (meth) acrylate, the acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer.
Examples of the functional group-containing monomer include a functional group-containing monomer which can introduce an unsaturated group into a side chain of an acrylic polymer by reacting the functional group with a crosslinking agent described later to form a starting point of crosslinking or by reacting the functional group with an unsaturated group in an unsaturated group-containing compound described later.
Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
In addition to having a structural unit derived from an alkyl (meth) acrylate and a structural unit derived from a functional group-containing monomer, the acrylic polymer may further have a structural unit derived from other monomers.
The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth) acrylate or the like.
Examples of the other monomer include styrene, α -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
In the adhesive compositions (I-1) to (I-4), the acrylic resin such as the acrylic polymer may have only one type of structural unit, or two or more types of structural units, and when two or more types of structural units are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass relative to the total amount of the structural units.
The adhesive resin (I-1a) contained in the adhesive composition (I-1) or the adhesive composition (I-4) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-1) or the adhesive composition (I-4).
[ adhesive resin (I-2a) ]
The adhesive resin (I-2a) in the adhesive compositions (I-2) and (I-3) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.
The unsaturated group-containing compound is a compound having, in addition to the energy ray-polymerizable unsaturated group, a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1 a).
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.
Examples of the group capable of bonding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding to a carboxyl group or an epoxy group.
Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2) or (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass based on the total mass of the adhesive composition (I-2) or (I-3).
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound in the adhesive compositions (I-1) and (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.
Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
The energy ray-curable compound may be an oligomer obtained by polymerizing the above-mentioned monomers, for example.
The energy ray-curable compound contained in the adhesive composition (I-1) or (I-3) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass relative to the total mass of the adhesive composition (I-1). In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the adhesive composition (I-1) or (I-4) preferably further contains a crosslinking agent.
Further, for example, when the acrylic polymer having the same structural unit as that derived from the functional group-containing monomer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the adhesive composition (I-2) or (I-3) may further contain a crosslinking agent.
The crosslinking agent reacts with the functional groups, for example, to crosslink the adhesive resins (I-1a) with each other or to crosslink the adhesive resins (I-2a) with each other.
Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa [1- (2-methyl) -aziridyl ] triphosphotriazine (hexa [1- (2-methyl) -aziridyl ] triphosphatriazine); metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelates; an isocyanurate crosslinking agent (a crosslinking agent having an isocyanuric acid skeleton), and the like.
The crosslinking agent contained in the adhesive composition (I-1), (I-2) or (I-4) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
In the adhesive composition (I-2) or (I-3), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive compositions (I-1), (I-2) and (I-3) (hereinafter, these adhesive compositions are collectively abbreviated as "adhesive compositions (I-1) to (I-3)") may further contain a photopolymerization initiator. The curing reaction can be sufficiently advanced even when the adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator are irradiated with a relatively low energy ray such as an ultraviolet ray.
Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as butanedione; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Further, as the photopolymerization initiator, for example, a photosensitizer such as amine may be used.
The photopolymerization initiators contained in the adhesive compositions (I-1) to (I-3) may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the energy ray-curable compound.
In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
[ other additives ]
The adhesive compositions (I-1) to (I-4) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is a component that suppresses unintended crosslinking reaction in the adhesive compositions (I-1) to (I-4) during storage, for example, by the action of a catalyst mixed in the adhesive compositions (I-1) to (I-4). Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by using a chelate of a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.
The other additives contained in the adhesive compositions (I-1) to (I-4) may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The content of the other additives in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be selected appropriately according to the kind thereof.
[ solvent ]
The adhesive compositions (I-1) to (I-4) may contain a solvent. By adding the solvent to the adhesive compositions (I-1) to (I-4), the applicability to the surface to be coated is improved.
The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
The adhesive compositions (I-1) to (I-4) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the solvent in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately adjusted.
Method for preparing O adhesive composition
The adhesive compositions such as the adhesive compositions (I-1) to (I-4) can be obtained by blending the adhesive and components other than the adhesive as required to constitute the adhesive composition.
The adhesive composition can be prepared, for example, by the same method as the thermosetting protective film-forming composition described above, except that the kind of the blending component is different.
As another example of a preferable protective film forming film of the present embodiment, the following protective film forming film can be cited: the film for forming a protective film is used for forming a protective film on the back surface of a chip, wherein the minimum value X of absorbance of the protective film at a wavelength of 2000-3200 nm (excluding 2701-2999 nm) is usedminAnd the specific heat S of the protective film at 100 DEG C100And by the formula: z100＝Xmin/S100Calculated Z100The film for forming a protective film contains a polymer component, a thermosetting component and a light absorbing agent, wherein the polymer component is an acrylic resin, the thermosetting component is an epoxy thermosetting resin, the light absorbing agent is one or more selected from the group consisting of organic pigments and inorganic pigments, the content of the polymer component in the film for forming a protective film is 5-80 mass% relative to the total mass of the film for forming a protective film, the content of the thermosetting component in the film for forming a protective film is 10-200 mass% relative to 100 mass parts of the content of the polymer component, and the content of the light absorbing agent in the film for forming a protective film is 0.1-20 mass% relative to the total mass of the film for forming a protective film.
Manufacturing method of composite sheet for protective film formation
The composite sheet for forming a protective film can be produced by laminating the above layers so as to have a corresponding positional relationship, and adjusting the shape of a part or all of the layers as required. The method of forming each layer is the method of forming described above.
For example, when an adhesive layer is laminated on a substrate in the production of a support sheet, the adhesive composition described above may be applied to the substrate and dried as necessary.
In addition, an adhesive layer can also be laminated on a substrate by a method in which an adhesive composition is applied to a release film and dried as necessary, thereby forming an adhesive layer on the release film and bonding an exposed surface of the adhesive layer to one surface of the substrate. In this case, the pressure-sensitive adhesive composition is preferably applied to the release-treated surface of the release film.
Although the case where the adhesive layer is laminated on the substrate has been described as an example, the above-described method can be applied to a case where an intermediate layer or the other layer is laminated on the substrate.
On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer laminated on a base material, the film for forming a protective film can be directly formed by applying a composition for forming a protective film on the adhesive layer. A layer other than the film for forming a protective film can be laminated on the adhesive layer by the same method using the composition for forming the layer. In this manner, when a new layer (hereinafter, abbreviated as "second layer") is formed on any one layer (hereinafter, abbreviated as "first layer") already laminated on the base material to form a continuous two-layer laminated structure (in other words, a laminated structure of the first layer and the second layer), a method of coating the composition for forming the second layer on the first layer and drying it as necessary can be applied.
However, it is preferable that the second layer is formed in advance on the release film using a composition for forming the layer, and an exposed surface of the formed second layer on the opposite side to the side in contact with the release film is bonded to an exposed surface of the first layer, thereby forming a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed as needed.
Here, although a case where a film for forming a protective film is laminated on an adhesive agent layer is exemplified as an example, a target laminated structure may be arbitrarily selected, for example, a case where an intermediate layer or the other layer is laminated on an adhesive agent layer.
In this manner, since all layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming the layers on the release film in advance and bonding the layers to the surface of the target layer, the composite sheet for forming a protective film can be produced by appropriately selecting the layers to be used in the above steps as needed.
The composite sheet for forming a protective film is generally stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) of the composite sheet on the side opposite to the support sheet. Therefore, the composite sheet for forming a protective film with a release film can be obtained by applying a composition for forming the outermost layer, such as a composition for forming a protective film, to the release film (preferably, the release-treated surface thereof) and drying the composition as necessary to form the outermost layer on the release film, and laminating the remaining layers on the exposed surface of the layer on the opposite side to the side in contact with the release film by any of the above-described methods, while maintaining the state in which the release film is bonded without removing the release film.
Manufacturing method of chip with protective film (protective film Forming film and Using method of protective film Forming composite sheet)
The film for forming a protective film and the composite sheet for forming a protective film can be used for producing the chip with a protective film.
Production method 1
Examples of a method for producing a chip with a protective film by attaching the protective film-forming film to a wafer so as not to be used simultaneously with a support sheet include:
a method for manufacturing a chip with a protective film (hereinafter referred to as "manufacturing method 1") includes:
a first laminating step of obtaining a laminate (1) including a wafer and a film for forming a protective film provided on the back surface of the wafer or obtaining a laminate (1') including a wafer and a protective film provided on the back surface of the wafer through a process of attaching the film for forming a protective film to the back surface of the wafer;
a second laminating step of obtaining a laminate (2) in which the dicing sheet, the protective film-forming film, and the wafer are laminated in this order in the thickness direction thereof, or obtaining a laminate (2 ') in which the dicing sheet, the protective film, and the wafer are laminated in this order in the thickness direction thereof, through a process of attaching a dicing sheet to a surface of the protective film-forming film in the laminate (1) opposite to the wafer side, or to a surface of the protective film in the laminate (1') opposite to the wafer side;
obtaining an aggregate of chips with a protective film forming film, which is obtained by holding a plurality of chips with a protective film forming film including the chips and the protective film forming film provided on the back surface of the chips on the dicing sheet after the cutting, through a process of dividing the wafer in the laminate (2) to produce chips and cutting the protective film forming film along the dividing positions of the wafer, or a dicing/cutting step of obtaining an aggregate of chips with a protective film, which is formed by holding a plurality of chips with a protective film on the dicing sheet, the chips being provided with the protective film after being cut and provided on the back surface of the chips, through a process of dicing the wafer in the laminate (2') to produce chips and cutting the protective film along the dicing positions of the wafer; and
a step of obtaining a chip with a protective film of the chip with a protective film by separating and picking up the chip with a protective film forming film in the aggregate of the chips with a protective film forming film or the chip with a protective film in the aggregate of the chips with a protective film from the dicing sheet,
when the protective film-forming film is curable, the method further includes, at any stage between the time when the protective film-forming film is attached to the back surface of the wafer in the first laminating step and the time when the picking-up of the chip with the protective film-forming film in the step of obtaining the chip with the protective film is completed: and a curing step of curing the laminate (1), the laminate (2), the aggregate of chips with a protective film forming film, or the protective film forming film in the chip with a protective film forming film to form a protective film, thereby producing the laminate (1 '), the laminate (2'), the aggregate of chips with a protective film, or the chip with a protective film.
The film for forming a protective film used in the first lamination step of the manufacturing method 1 is the film for forming a protective film according to the above-described embodiment of the present invention.
In the first laminating step of the production method 1, when the protective film-forming film is curable, the protective film-forming film can be attached to the back surface of the wafer and then the attached protective film-forming film can be cured, whereby the laminate (1') can be obtained. On the other hand, when the protective film-forming film is non-curable, the laminate (1') can be obtained immediately by attaching the protective film-forming film to the back surface of the wafer.
The dicing sheet used in the second lamination step of the manufacturing method 1 may be a known dicing sheet.
The curing step may be performed at any stage as long as the protective film forming film is attached to the back surface of the wafer in the first laminating step. For example, the curing step may be performed after the laminate (1) is obtained in the first lamination step; between the first lamination process and the second lamination process; obtaining a laminate (2) in the second lamination step; between the second laminating step and the dividing/cutting step; obtaining an aggregate of chips with a film for forming a protective film in a dividing/cutting step; between the dividing/cutting step and the step of obtaining the chip with the protective film; in the step of obtaining the chip with the protective film, any stage after picking up the chip with the film for forming the protective film is performed.
When the protective film-forming film is non-curable, the production method 1 does not include the curing step.
In the production method 1, the curing of the protective film-forming film is thermal curing or energy ray curing at any stage. The conditions for the thermal curing and the conditions for the energy ray curing at this time are the same as those described above.
The first lamination step, the second lamination step, the dividing/cutting step, the step of obtaining the chip with the protective film, and the curing step in the manufacturing method 1 can be performed by the same method as the conventional method of manufacturing the chip with the protective film, except that the film for forming the protective film of the present embodiment is used.
For example, the thickness of the wafer to be bonded with the film for forming the protective film is not particularly limited, but is preferably 20 to 600 μm, and more preferably 40 to 400 μm.
In the case where there is an intermediate structure in any of the steps of the production method 1, the production method 1 may include a step of thermally shrinking a region in the vicinity of the peripheral portion of the wafer having no protective film or the chip having a protective film held thereon in the intermediate structure, wherein 1 or 2 or more protective film-equipped chips or 1 protective film-equipped wafer are held on 1 dicing sheet, and the dicing sheet is in a state of being expanded in a direction parallel to the surface on the wafer side of the protective film-equipped chips or protective films.
As an example, when the wafer is divided by the step dividing (registered trademark) in the dividing/cutting step, the dividing/cutting step may include the steps of: irradiating the wafer with laser light so as to focus on a focal point set in the wafer to form a modified layer in the wafer, spreading the laminated body (2') on which the modified layer is formed in a direction parallel to the surface of the wafer to divide the wafer, and cutting the protective film.
When the laminate (2') is expanded in the above manner, the step of obtaining the chip with the protective film may include the steps of: and a step of heat-shrinking a region in the vicinity of the peripheral portion of the dicing sheet in the chip assembly with the protective film (corresponding to the intermediate structure) where the chip with the protective film is not held (corresponding to the "step of heat-shrinking").
In addition, as another example, when the dicing/cutting step is performed to obtain the protective film-attached chip assembly by dicing the wafer by various dicing such as blade dicing, laser dicing, or water dicing, the protective film-attached chip obtaining step may include: and a step of expanding the chip assembly with the protective film along a direction parallel to the surface of the wafer when picking up the chip with the protective film.
In the case where the chip assembly with the protective film is expanded in the above-described manner, the step of obtaining the chip with the protective film may further include the steps of: and a step (corresponding to the "heat shrinking step") of leaving a part of the chips with the protective film on the dicing sheet without picking up the part of the chips, storing the chip assembly with the protective film in this state, and then heat shrinking a region in the vicinity of the peripheral portion of the chips without the protective film held on the dicing sheet in the stored chip assembly with the protective film (corresponding to the intermediate structure).
The heat treatment during heat shrinkage can be performed by irradiating the cut piece with near infrared rays or intermediate infrared rays. In this case, the dicing sheet can be subjected to a heat treatment by irradiating the dicing sheet with light having any wavelength region or all wavelength regions of 2000 to 3200nm, for example, using a heater. When the cut piece is irradiated with light having any wavelength region of 2000 to 3200nm, only light having any wavelength region or all wavelength regions of 2000nm or more and less than 2701nm and 2999nm and 3200nm or less may be irradiated, only light having any wavelength region or all wavelength regions of 2701 to 2999nm may be irradiated, and light having any wavelength region of 2000nm or more and less than 2701nm and 2999nm and 3200nm or all wavelength regions of 2701 to 2999nm may be irradiated, and light having any wavelength region of 2000 to 3200nm is not irradiated.
By using the film for forming a protective film of the present embodiment, as described above, even when near infrared rays or intermediate infrared rays are erroneously irradiated to the protective film in the chip with a protective film or the wafer with a protective film in the step of performing heat shrinkage in the manufacturing method 1, unintended temperature rise of the protective film can be suppressed, and discoloration of the protective film can be suppressed.
In the manufacturing method 1, the order of dividing the wafer and cutting the protective film-forming film or the protective film in the dividing/cutting step may be changed. In the present specification, such a method for manufacturing a chip with a protective film is referred to as manufacturing method 2.
Production method 2
Namely, the production method 2 has: obtaining an aggregate of chips with a protective film forming film, which is obtained by holding a plurality of chips with a protective film forming film, each chip being provided with the chip and the protective film forming film provided on the back surface of the chip after cutting, on the dicing sheet, by a procedure of cutting the protective film forming film in the laminate (2) and dividing the wafer along the cutting position of the protective film forming film to produce chips, or a cutting/dividing step of obtaining an aggregate of chips with protective film, which is formed by holding a plurality of chips with protective film on the dicing sheet, the chips being provided with the protective film after cutting and being provided on the back surface of the chips, after a process of cutting the protective film in the laminated body (2') and dividing the wafer along the cutting position of the protective film to produce chips.
The manufacturing method 2 is the same as the manufacturing method 1 except that a cutting/dividing step is provided instead of the dividing/cutting step. That is, the manufacturing method 2 includes the first laminating step, the second laminating step, the cutting/dividing step, and the step of acquiring the chips with the protective films, and further includes, at an arbitrary stage from after the protective film forming film is attached to the back surface of the wafer in the first laminating step to when the protective film forming film is curable until the picking-up of the chips with the protective film forming film in the step of acquiring the chips with the protective films is completed: and a curing step of curing the laminate (1), the laminate (2), the aggregate of chips with a protective film forming film, or the protective film forming film in the chip with a protective film forming film to form a protective film, thereby producing the laminate (1 '), the laminate (2'), the aggregate of chips with a protective film, or the chip with a protective film.
Production method 3
Examples of a method for producing a chip with a protective film by attaching the protective film-forming film to a wafer as a protective film-forming composite sheet while using the protective film-forming film together with a support sheet, include:
a method for manufacturing a chip with a protective film (referred to as "manufacturing method 3" in the present specification), comprising:
a laminating step of obtaining a laminated body (3) in which a support sheet, a protective film forming film, and a wafer are laminated in this order in the thickness direction thereof, or obtaining a laminated body (3') in which a support sheet, a protective film, and a wafer are laminated in this order in the thickness direction thereof, by a process of attaching the protective film forming film of the protective film forming composite sheet to the back surface of the wafer;
obtaining an aggregate of chips with a protective film forming film, which is obtained by holding a plurality of chips with a protective film forming film including the chips and the protective film forming film provided on the back surface of the chips on the support sheet through a process of dividing the wafer in the laminate (3) to produce chips and cutting the protective film forming film along the dividing positions of the wafer, or a dicing/cutting step of obtaining an aggregate of chips with a protective film, which is formed by holding a plurality of chips with a protective film on the support sheet, the chips being provided with the protective film after dicing and being provided on the back surface of the chips, through a process of dicing the wafer in the laminated body (3') to produce chips, and cutting the protective film along the dicing positions of the wafer; and
a step of obtaining a chip with a protective film of the chip with a protective film by separating and picking up the chip with a protective film forming film in the aggregate of the chips with a protective film forming film or the chip with a protective film in the aggregate of the chips with a protective film from the support sheet,
when the protective film-forming film is curable, the method further includes, at any stage between the stage of attaching the protective film-forming film of the protective film-forming composite sheet to the back surface of the wafer in the laminating step and the stage of completing the picking up of the chip with the protective film-forming film in the step of obtaining the chip with the protective film, the method including: and a curing step of curing the laminate (3), the aggregate of chips with a protective film forming film, or the protective film forming film in the chip with a protective film forming film to form a protective film, thereby producing the laminate (3'), the aggregate of chips with a protective film, or the chip with a protective film.
The film for forming a protective film used in the lamination step of the production method 3 is the film for forming a protective film according to one embodiment of the present invention described above.
In the laminating step of the production method 3, when the protective film-forming composite sheet is curable, the protective film-forming film of the attached protective film-forming composite sheet may be cured after the protective film-forming composite sheet is attached to the back surface of the wafer, whereby the laminate (3') can be obtained.
On the other hand, when the protective film-forming film is non-curable, the laminate (3') can be obtained immediately by attaching the composite sheet for protective film formation to the back surface of the wafer.
The laminate (3) obtained in the lamination step of the production method 3 is basically the same as the laminate (2) obtained in the second lamination step of the production method 1.
Similarly, the laminate (3 ') obtained in the lamination step of the production method 3 is basically the same as the laminate (2') obtained in the second lamination step of the production method 1.
The curing step may be performed at any stage as long as the film for forming the protective film in the composite sheet for forming the protective film is attached to the back surface of the wafer in the laminating step. For example, the curing step may be performed after the laminate (3) is obtained in the laminating step; between the laminating step and the dividing/cutting step; obtaining an aggregate of chips with a film for forming a protective film in a dividing/cutting step; between the dividing/cutting step and the step of obtaining the chip with the protective film; in the step of obtaining the chip with the protective film, any stage after picking up the chip with the film for forming the protective film is performed.
When the protective film-forming film is non-curable, production method 3 does not have the curing step.
In the production method 3, the curing of the protective film-forming film is thermal curing or energy ray curing at any stage. The conditions for the thermal curing and the conditions for the energy ray curing at this time are the same as those described above.
The laminating step, the dividing/cutting step, the obtaining step of the chip with the protective film, and the curing step in the manufacturing method 3 can be performed by the same method as the conventional manufacturing method of the chip with the protective film, except that the composite sheet for forming a protective film of the present embodiment is used.
For example, the thickness of the wafer to be bonded with the composite sheet for forming a protective film is not particularly limited, but is preferably 20 to 600 μm, and more preferably 40 to 400 μm.
The production method 3 may include a step of heat-shrinking the support sheet, basically in the same manner as the production method 1.
That is, when there is an intermediate structure in any of the manufacturing methods 3, the manufacturing method 3 may include a step of thermally shrinking a region in the vicinity of the peripheral portion of the wafer not holding the chip with a protective film or the wafer with a protective film in the support sheet in the intermediate structure, the intermediate structure holding 1 or 2 or more chips with a protective film or 1 wafer with a protective film on 1 support sheet, and the support sheet being in a state of being expanded in a direction parallel to the surface on the wafer side of the chip with a protective film or the wafer with a protective film.
As an example, when the wafer is divided by the step dividing (registered trademark) in the dividing/cutting step, the dividing/cutting step may include the steps of: irradiating the wafer with laser light so as to focus on a focal point set in the wafer to form a modified layer in the wafer, spreading the laminated body (3') on which the modified layer is formed in a direction parallel to the surface of the wafer to divide the wafer, and cutting the protective film.
When the laminate (3') is expanded in the above manner, the step of obtaining the chip with the protective film may include the steps of: and a step of heat-shrinking a region in the vicinity of the peripheral portion of the chip without the protective film held on the support sheet in the protective film-equipped chip assembly (corresponding to the intermediate structure) (corresponding to the "heat-shrinking step").
In addition, as another example, when the dicing/cutting step is performed to obtain the protective film-attached chip assembly by dicing the wafer by various dicing such as blade dicing, laser dicing, or water dicing, the protective film-attached chip obtaining step may include: and a step of expanding the chip assembly with the protective film along a direction parallel to the surface of the wafer when picking up the chip with the protective film.
In the case where the chip assembly with the protective film is expanded in the above-described manner, the step of obtaining the chip with the protective film may further include the steps of: and a step (corresponding to the "heat shrinking step") of leaving a part of the chips with the protective film on the dicing sheet without picking up the part of the chips, storing the chip assembly with the protective film in this state, and heat shrinking a region in the vicinity of the peripheral portion of the chips without the protective film held on the dicing sheet in the stored chip assembly with the protective film (corresponding to the intermediate structure).
As described above, by using the film for forming a protective film (composite sheet for forming a protective film) of the present embodiment, even if near infrared rays or intermediate infrared rays are erroneously irradiated to the protective film in the chip with a protective film or the wafer with a protective film in the step of performing heat shrinkage in the production method 3, unintended temperature rise of the protective film can be suppressed, and discoloration of the protective film can be suppressed.
< other Process >
In addition to the first laminating step, the second laminating step, the dividing/cutting step, the step of obtaining the chip with the protective film, and the curing step, the manufacturing method 1 may include other steps not belonging to any of the above steps within a range not to impair the effects of the present invention.
Similarly, the manufacturing method 2 may include other steps not belonging to any of the above-described steps, in addition to the respective steps of the first laminating step, the second laminating step, the cutting/dividing step, the step of obtaining the chip with the protective film, and the curing step, within a range not impairing the effect of the present invention.
Similarly, in addition to the respective steps of the laminating step, the dividing/cutting step, the step of obtaining the chip with the protective film, and the curing step, the manufacturing method 3 may have other steps not belonging to any of the above-described steps within a range not to impair the effect of the present invention.
In the production methods 1 to 3, the type of the other step and the timing of performing the other step are arbitrarily selected depending on the purpose, and are not particularly limited.
As described above, regardless of the method of using the film for forming a protective film of the present embodiment, it is possible to suppress an unintended temperature increase in the protective film due to irradiation with near infrared rays or intermediate infrared rays.
For example, as shown in the examples below, when a chip with a protective film is heated under the same conditions as those of the chip with a protective film for comparison, in addition to the fact that the protective film of the present embodiment is used instead of the other protective film forming films, the maximum temperature of the protective film in the chip with a protective film can be, for example, 165 ℃ or lower, and can be any one of 161 ℃ or lower, 157 ℃ or lower, 153 ℃ or lower, and 149 ℃ or lower, even when the chip with a protective film for comparison, which is made by using the other protective film forming film without using the protective film of the present embodiment, is heated, as a result, the maximum temperature of the protective film in the chip with a protective film is 191 ℃ or lower.
Manufacturing method of substrate device
After the chip with the protective film is obtained by the above-described manufacturing method, the substrate device can be manufactured by the same method as the conventional manufacturing method except that the chip with the protective film is used.
Examples of the method of manufacturing such a substrate device include a method of manufacturing a substrate device including a flip-chip bonding step: in the flip chip connection step, the chip with the protective film is disposed on the circuit board by bringing the bump electrode on the chip with the protective film obtained by using the film for forming the protective film into contact with the connection pad on the circuit board, and the bump electrode is electrically connected to the connection pad on the circuit board.
The flip-chip connection step in the manufacturing method may be performed by the same method as the manufacturing method of the conventional substrate device, except that the chip with the protective film is used.
Fig. 6 is a cross-sectional view schematically showing a state in which the chip with the protective film and the circuit board are electrically connected in the flip-chip connection step.
Here, a state in which the chip 901 with a protective film is electrically connected to the circuit board 8 is shown.
The chip 901 with a protective film includes the chip 9 and the protective film 130' provided on the back surface 9b of the chip 9 after cutting. The circuit surface 9a of the chip 9 is provided with a plurality of protruding electrodes 91.
A plurality of connection pads 81 are provided on the circuit surface 8a of the circuit substrate 8.
A bump electrode 91 on the chip 9 is in contact with a connection pad 81 on the circuit substrate 8.
The present invention is not limited to the above-described embodiments, and the present invention is not limited to the embodiments described above.
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
< raw materials for production of resin >
The following are formal names of the raw materials for producing the resins abbreviated in the examples and the reference examples.
BA: acrylic acid n-butyl ester
MA: acrylic acid methyl ester
HEA: 2-Hydroxyethyl acrylate
2 EHA: 2-ethylhexyl acrylate
< raw Material for preparation of composition for Forming protective film >
The raw materials used for preparing the composition for forming a protective film are shown below.
[ Polymer component (A) ]
(A) -1: an acrylic resin (weight-average molecular weight 500000, glass transition temperature-26 ℃) obtained by copolymerizing BA (45 parts by mass), MA (40 parts by mass) and HEA (15 parts by mass).
[ thermosetting component (B1) ]
(B1) -1: bisphenol A epoxy resin ("jER 828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184-194 g/eq)
(B1) -2: bisphenol A type epoxy resin ("jER 1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 800 to 900g/eq)
(B1) -3: dicyclopentadiene type epoxy resin ("EPICLON HP-7200 HH" manufactured by DIC CORPORATION, epoxy equivalent 255-260 g/eq)
[ Heat-curing agent (B2) ]
(B2) -1: dicyandiamide ("ADEKA HARDENER EH-3636 AS" manufactured by ADEKA CORPORATION, thermally active latent epoxy resin curing agent, active hydrogen equivalent 21g/eq)
[ curing Accelerator (C) ]
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole ("CURZOL 2 PHZ" manufactured by SHIKOKU CHEMICALS CORPORATION.)
[ Filler (D) ]
(D) -1: silica filler (ADMATECHS Co., Ltd. "SC 2050 MA", silica filler surface-modified with epoxy compound, average particle diameter 0.5 μm)
(D) -2: spherical alumina ("CB-P02J" manufactured by Showa Denko K.K., average particle diameter 3.0 μm)
(D) -3: silica filler (ADMATECHS Co., Ltd. "YA 050C-MJA", average particle diameter 50nm)
(D) -4: stainless steel particles (particles obtained by pulverizing SUS304 to an average particle diameter of 2.0. mu.m)
[ coupling agent (E) ]
(E) -1: 3-aminopropyltrimethoxysilane (Nippon Unicar Co., manufactured by Ltd. "A-1110")
[ light absorbing agent (I) ]
(I) -1: a Pigment obtained by mixing 32 parts by mass of a phthalocyanine-based Blue Pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based Yellow Pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based Red Pigment (Pigment Red177) and pigmenting the mixture so that the total amount of the 3 pigments/the amount of the styrene acrylic resin is 1/3 (mass ratio).
(I) -2: carbon Black (manufactured by Mitsubishi Chemical Corporation, "MA 600", average particle diameter 20nm)
(I) -3: 2,3,9,10,16,17,23, 24-octa (octyloxy) -29H, 31H-copper (II) phthalocyanine (manufactured by Sigma-Aldrich LLC)
(I) -4: 2,9,16, 23-tetra-tert-butyl-29H, 31H-copper (II) phthalocyanine (manufactured by Sigma-Aldrich LLC.)
(I) -5: 2,11,20, 29-tetra-tert-butyl-2, 3-naphthalocyanine (manufactured by Sigma-Aldrich LLC)
(I) -6: diimine pigments ("CIR-1085F", made by Japan Carlit Co., Ltd., visible and infrared light absorbers)
[ example 1]
Production of protective film-Forming film
< preparation of composition for Forming protective film (III-1) >
The polymer component (a) -1(150 parts by mass), the thermosetting component (B1) -1(60 parts by mass), (B1) -2(20 parts by mass), (B1) -3(20 parts by mass), (B2) -1(2.2 parts by mass), the curing accelerator (C) -1(2.2 parts by mass), the filler (D) -1(320 parts by mass), the coupling agent (E) -1(3 parts by mass), the light absorber (I) -1(10 parts by mass), and the light absorber (I) -2(2.7 parts by mass) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23 ℃. The amounts of the components other than the mixed solvent described herein are the amounts of the target product not including a solvent.
< production of film for Forming protective film >
The above-obtained composition (III-1) for forming a protective film was applied to the release-treated surface of a polyethylene terephthalate film using a release film (second release film, "SP-PET 501031" manufactured by linetec Corporation, thickness 50 μm) whose one surface was subjected to a release treatment by a silicone treatment, and dried at 100 ℃ for 2 minutes, thereby producing a thermosetting film for forming a protective film having a thickness of 25 μm.
Further, a release-treated surface of a release film (a first release film, "SP-PET 381031" manufactured by Lintec Corporation, having a thickness of 38 μm) was bonded to the exposed surface of the obtained protective film-forming film on the side not having the second release film, thereby obtaining a laminated film including the protective film-forming film, the first release film provided on one surface of the protective film-forming film, and the second release film provided on the other surface of the protective film-forming film.
Evaluation of protective film
<X of protective filmminMeasurement of (2)>
The first release film was removed from the laminated film obtained above.
Next, the protective film-forming film provided with the second release film from which the first release film was removed was subjected to heat treatment at 145 ℃ for 2 hours in an air atmosphere, and thereby thermally cured to form a protective film.
Then, the second release film was removed from the protective film, and a UV-Vis spectrophotometer (Shimadzu Corp) was used for the protective film"UV-VIS-NIR SPECTROPROPHO TOMETER UV-3600" manufactured by corporation) measures absorbance at intervals of 1nm in a wavelength region of 1400 to 3200nm including a near infrared region and a mid infrared region without using an integrating sphere attached thereto. Then, X is determined from the measurement results in the wavelength region of 2701 to 2999nm excluding the Xmin. The results are shown in Table 1.
<S of protective film100Measurement of (2)>
The first release film was removed from the laminated film obtained above.
Next, the protective film-forming film provided with the second release film from which the first release film was removed was heat-treated at 145 ℃ for 2 hours using an oven manufactured by ESPEC corp.
Next, the second release film was removed from the protective film, and the differential scanning calorimetry of the protective film was measured at a temperature of 40 to 250 ℃ under atmospheric pressure with a differential scanning calorimetry (PYRIS 1 manufactured by PerkinElmer) in accordance with JIS K7123: 2012 at a temperature rise rate of 10 ℃/min. Then, the heat flux at each temperature is calculated from the obtained heat flux graph, and the amount of the protective film used is taken into consideration to calculate S of the protective film100. The results are shown in Table 1.
<Z of protective film100Is calculated by>
X obtained by the aboveminAnd S100Calculating Z from the value of100. The results are shown in Table 1.
<T of protective filmmMeasurement of (2)>
The first release film was removed from the laminated film obtained above.
Next, the protective film-forming film provided with the second release film from which the first release film was removed was subjected to heat treatment at 145 ℃ for 2 hours in an air atmosphere, and thereby thermally cured to form a protective film.
Then, the second release film was removed from the protective film, and with respect to the protective film, a UV-Vis SPECTROPHOTOMETER ("UV-VIS-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) was used,the transmittance of light is measured at intervals of 1nm in a wavelength region of 400 to 750nm (i.e., visible light region) without using an integrating sphere attached thereto. Then, T is obtained from the measurement resultm. The results are shown in Table 1.
<U of protective filmmMeasurement of (2)>
The first release film was removed from the laminated film obtained above.
Next, the protective film-forming film provided with the second release film from which the first release film was removed was subjected to heat treatment at 145 ℃ for 2 hours in an air atmosphere, and thereby thermally cured to form a protective film.
Next, the second release film was removed from the protective film, and the amount of total light reflected light including specular reflected light (normal reflected light) and diffuse reflected light was measured at intervals of 1nm in a wavelength region of 1400 to 2600nm including a near infrared region and a mid infrared region using a UV-Vis SPECTROPHOTOMETER ("UV-Vis-NIR SPECTROPHOTOMETER UV-3600" manufactured by Shimadzu Corporation) for the protective film by an SCI method. Further, the light quantity of total ray reflected light was measured with respect to a reference plate made of barium sulfate by the same method. In any case, "large sample chamber MPC-3100" manufactured by Shimadzu Corporation was used as a sample holder, and "device with an integrating sphere ISR-3100" manufactured by Shimadzu Corporation was used as an integrating sphere, and an incident angle of incident light to the measurement object was set to 8 °. Then, a ratio of the measurement value of the protective film to the measurement value of the reference plate ([ measurement value of light amount of total light reflected light of protective film ]]/[ measurement value of light quantity of total ray reflected light on reference plate]X 100), i.e., the relative total light reflectance of the protective film, was used as the reflectance of light. Then, U is obtained from the measurement resultm. The results are shown in Table 1.
< measurement of the maximum temperature reached by the protective film during heating >
The first release film was removed from the laminated film obtained above, and the exposed surface of the film for forming a protective film thus produced was attached to a polished surface corresponding to the back surface of an 8-inch silicon wafer (thickness 350 μm) having no bumps (protruding electrodes). Then, the second release film is removed from the attached film for forming a protective film, and a laminated body (1) in which the film for forming a protective film and the silicon wafer are laminated is obtained (first lamination step).
Next, the laminate (1) was heat-treated at 145 ℃ for 2 hours using an oven manufactured by ESPEC corp, whereby the protective film-forming film was thermally cured to form a protective film (curing step).
Then, after the laminate (1) after the thermosetting is cooled slowly, a region of the exposed surface of the protective film (i.e., the surface opposite to the side on which the silicon wafer is provided) that is1 to 10mm from the peripheral portion of the protective film is brought into contact with a thermocouple and fixed.
Then, a dicing tape is attached to the exposed surface (the surface opposite to the side on which the silicon wafer is provided) of the protective film, thereby obtaining a laminate (2') in which the dicing tape (corresponding to the support sheet), the protective film, and the silicon wafer are laminated in this order in the thickness direction thereof (second lamination step). The dicing tape is a tape having a diameter larger than that of the laminate (1), and is disposed so as to be concentric with the protective film and the silicon wafer. In the laminated body (2'), the thermocouple is in a state of being clamped by the protective film and the cutting tape.
Then, the laminated body (2 ') with the thermocouple is fixed by attaching a region exposed along the peripheral portion of the dicing tape out of the surface on the protective film side of the dicing tape of the laminated body (2') in this state to an annular frame for fixing a silicon wafer.
Then, using a full-automatic division machine ("DDS 2300" manufactured by DISCO Corporation), the laminated body (2 ') was heated by irradiating the outer peripheral portion of the silicon wafer in the fixed laminated body (2') with light in all wavelength regions of 2000 to 3200nm at an angular velocity of 0.5 °/sec using a heat shrinking apparatus of the full-automatic division machine.
Next, the maximum reaching temperature of the protective film during the heating was measured using the thermocouple. The results are shown in Table 1.
Production of film for Forming protective film and evaluation of protective film
Examples 2 to 19 and reference examples 1 to 8
A protective film-forming film was produced in the same manner as in example 1 except that either or both of the kind and the blending amount of the blending components in the production of the protective film-forming composition (III-1) were changed to the kind and the content of the components contained in the protective film-forming composition (III-1) shown in tables 1 to 4, and the protective film was evaluated. The results are shown in tables 1 to 4.
[ Table 1]
Figure BDA0002710114310000761
[ Table 2]
Figure BDA0002710114310000771
[ Table 3]
Figure BDA0002710114310000781
[ Table 4]
Figure BDA0002710114310000791
From the above results, it is understood that in examples 1 to 19, the maximum reaching temperature of the protective film during heating was 165 ℃ or lower, and was suppressed to be low. This is due to Z of the protective film100Smaller, 0.23 or less. It was confirmed in advance that when the temperature of the protective film reached such a region, discoloration of the protective film was suppressed. That is, it was confirmed that, when the protective film-equipped chips having the protective films of examples 1 to 19 on the back surface and bumps on the circuit surface were used, unintended discoloration of the protective films could be suppressed when heat shrinkage such as dicing tape was performed.
In examples 1 to 19, the film for forming a protective film (composition (III-1)) contained 2 to 7 kinds of light absorbers (I).
In examples 1 to 19, the proportion of the content of the light absorber (I) to the total content of all the components except the solvent (i.e., the proportion of the content of the light absorber (I) in the film for forming a thermosetting protective film to the total mass of the film for forming a thermosetting protective film) in the composition (III-1) was 2 to 13.1 mass%.
In examples 1 to 19, TmThe content is 12% or less, the visible light transmittance is low, and the presence or absence of the protective film can be easily confirmed. Wherein, in examples 1 to 17 and 19, TmThe content is 6% or less, and the effect is particularly high.
In examples 1 to 19, U ismIs 11% or less, and has a low reflectance of near infrared rays or mid infrared rays. That is, the protective film forming films of examples 1 to 19 can form a protective film capable of suppressing the failure of the device using near infrared rays or middle infrared rays.
In reference examples 1 to 8, the maximum reaching temperature of the protective film during heating was 170 ℃ or higher, which is higher than that in the above examples. This is due to Z of the protective film100Larger, 0.3 or more. It was previously confirmed that when the temperature of the protective film reached such a region, discoloration of the protective film was not suppressed. That is, it was confirmed that, when the protective film-equipped chips having the protective films of reference examples 1 to 8 on the back surface and bumps on the circuit surface were used, unintended discoloration of the protective films could not be suppressed when heat shrinkage such as dicing tape was performed.
In reference examples 1 to 8, the film for forming a protective film (composition (III-1)) contained 2 to 4 kinds of light absorbers (I).
In reference examples 1 to 8, in the composition (III-1), the proportion of the content of the light absorber (I) to the total content of all the components except the solvent (i.e., the proportion of the content of the light absorber (I) in the film for forming a thermosetting protective film to the total mass of the film for forming a thermosetting protective film) was 3 to 5.8 mass%.
Production of composite sheet for Forming protective film
[ example 1]
Using the film for forming a protective film obtained in example 1, a composite sheet for forming a protective film was produced. More specifically, as described below.
In the present specification, the numbers of examples and reference examples in the production of a film for forming a protective film and in the evaluation of a protective film are used as they are as follows as the numbers of examples and reference examples in the production of a composite sheet for forming a protective film.
< preparation of adhesive composition (I-4) >
A non-energy ray-curable adhesive composition (I-4) was prepared, which contained 100 parts by mass of an acrylic resin and 10 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent ("TAKENATE D110N" manufactured by Mitsui Kogyo chemical corporation) and further contained methyl ethyl ketone as a solvent, wherein the total concentration of all components except the solvent was 25% by mass. The contents of the components other than methyl ethyl ketone shown here are all contents of the target product including no solvent.
The acrylic resin was obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass), and had a weight average molecular weight of 800000.
< production of supporting sheet >
The adhesive composition (I-4) obtained above was applied to a release-treated surface of a polyethylene terephthalate film using a release film (SP-PET 381031 manufactured by Lintec Corporation, "thickness 38 μm") whose one surface was subjected to release treatment by silicone treatment, and dried by heating at 100 ℃ for 2 minutes, thereby forming a non-energy ray-curable adhesive layer having a thickness of 5 μm.
Next, a polypropylene film (1) (having a thickness of 80 μm and no color) having a smooth surface on one side and an uneven surface on the other side was used as a substrate, and the exposed surface of the obtained non-energy ray-curable adhesive layer was bonded to the smooth surface of the substrate, thereby producing a laminate sheet in which the substrate, the adhesive layer, and the release film were laminated in this order in the thickness direction, that is, a support sheet with a release film.
< production of composite sheet for Forming protective film >
The release film was removed from the support sheet obtained above. Further, the first release film was removed from the laminated film obtained in example 1 (i.e., the film for forming a protective film including the first release film and the second release film). Then, the exposed surface of the adhesive layer formed by removing the release film and the exposed surface of the protective film forming film formed by removing the first release film are laminated to each other, thereby producing a protective film forming composite sheet in which a base material, an adhesive layer, a protective film forming film, and a second release film are laminated in this order in the thickness direction thereof. In the composite sheet for forming a protective film, the support sheet (base material and adhesive layer) is arranged so that the diameter thereof is larger than the diameter of the film for forming a protective film and the support sheet and the film for forming a protective film are concentric with each other.
Examples 2 to 19 and reference examples 1 to 8
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the laminated films obtained in examples 2 to 19 and reference examples 1 to 8 were used instead of the laminated film obtained in example 1.
Evaluation of protective film
<X of protective filmmin、S100、TmAnd UmAnd Z of the protective film100Is calculated by>
The same method as in example 5 was used to measure X of the protective film, except that the composite sheet for forming a protective film obtained in example 5 was used instead of the laminated film in example 5 abovemin、S100、TmAnd UmCalculating Z of the protective film100。
For example, in the determination of XminIn the case of forming the protective film, the second release film was removed from the composite sheet for forming the protective film, and the film for forming the protective film in the composite sheet for forming the protective film in this state was heat-treated at 145 ℃ for 2 hours, whereby the film was heat-cured to form the protective film. Then, the laminate (i.e., the support sheet) of the base material and the adhesive layer is removed from the protective film on the protective filmMeasuring the absorbance in a wavelength region of 1400 to 3200 nm. Measurement of S100、TmAnd UmIn this case, the formation of the protective film and the measurement of the above physical properties of the protective film were also performed in the same manner.
< measurement of the maximum temperature reached by the protective film during heating >
The second release film was removed from the composite sheet for forming a protective film obtained in example 5, and the exposed surface of the film for forming a protective film thus produced was attached to a polished surface corresponding to the back surface of an 8-inch silicon wafer (thickness 350 μm) having no bumps (projecting electrodes), thereby obtaining a laminate (3).
Then, a thermocouple is inserted between the support sheet and a region near the peripheral edge of the protective film forming film on the surface of the protective film forming composite sheet of the laminate (3) on the support sheet side of the protective film forming film, and the thermocouple is fixed between the support sheet and the region.
Then, in the laminated body (3) in this state, a region exposed along the peripheral portion of the support sheet on the surface on the protective film forming film side of the support sheet is attached to a ring frame for fixing a silicon wafer, whereby the laminated body (3) with a thermocouple is fixed.
Then, the laminate (3) with a thermocouple was subjected to a heat treatment at 145 ℃ for 2 hours using an oven manufactured by ESPEC corp, to thereby thermally cure the protective film-forming film and form a protective film (curing step). Thus, a multilayer body (3') with a thermocouple, which is configured by sequentially laminating a support sheet, a protective film, and a silicon wafer in the thickness direction thereof and further includes the thermocouple between the support sheet and the protective film, is obtained (laminating step).
Then, the laminated body (3 ') is heated by irradiating near-infrared rays and intermediate-infrared rays having wavelengths of 2000 to 3200nm with an angular velocity of 0.5 °/sec using a full-automatic division machine ("DDS 2300" manufactured by DISCO Corporation) using a heat shrinking apparatus of the full-automatic division machine, with the vicinity of the outer peripheral portion of the silicon wafer in the laminated body (3') being fixed.
Thereafter, the laminate (3 ') was heated in the same manner as in example 5, except that the laminate (3') with a thermocouple was used, and the maximum reaching temperature of the protective film during the heating was measured using the thermocouple.
As a result, the evaluation results of the protective film when the composite sheet for forming a protective film is used here are all the same as the evaluation results of the previous example 5 using the laminated film, or both are almost the same, that is, substantially the same, with only a negligible error.
Industrial applicability
The present invention is applicable to the manufacture of various substrate devices including semiconductor devices.

Claims (8)

1. A film for forming a protective film on a back surface of a chip,
using the minimum value X of the absorbance of the protective film at a wavelength of 2000 to 3200nmminAnd the specific heat S of the protective film at 100 DEG C100And Z is calculated by the following formula100Is less than 0.27, the wavelength is 2000-3200 nm, excluding 2701-2999 nm,
Z100＝Xmin/S100。
2. the protective film-forming film according to claim 1, wherein the protective film-forming film is thermosetting or energy ray-curable.
3. The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film contains two or more light absorbers capable of absorbing either or both of visible light and infrared light.
4. The protective film-forming film according to claim 1 or 2, wherein the protective film-forming film contains a carbon material.
5. The film for forming a protective film according to any one of claims 1 to 4, wherein the protective film has a transmittance for light having a wavelength of 400 to 750nmMinimum value TmIs 15% or less.
6. The film for forming a protective film according to any one of claims 1 to 5, wherein the protective film has a maximum value U of reflectance with respect to light having a wavelength of 2000 to 2600nmmIs 20% or less.
7. A composite sheet for forming a protective film, comprising a support sheet and a film for forming a protective film provided on one surface of the support sheet,
the film for forming a protective film according to any one of claims 1 to 6.
8. The composite sheet for forming a protective film according to claim 7, wherein the support sheet comprises a base material and an adhesive layer provided on one surface of the base material,
the adhesive layer is disposed between the base material and the protective film-forming film.
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