WO2016068042A1 - Film for forming protective coat and composite sheet for forming protective coat - Google Patents
Film for forming protective coat and composite sheet for forming protective coat Download PDFInfo
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- WO2016068042A1 WO2016068042A1 PCT/JP2015/079973 JP2015079973W WO2016068042A1 WO 2016068042 A1 WO2016068042 A1 WO 2016068042A1 JP 2015079973 W JP2015079973 W JP 2015079973W WO 2016068042 A1 WO2016068042 A1 WO 2016068042A1
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- protective film
- film
- forming
- sheet
- forming film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
Definitions
- the present invention relates to a protective film-forming film, a protective film-forming sheet, and a protective film-forming film capable of forming a protective film on a workpiece such as a semiconductor wafer or a workpiece (for example, a semiconductor chip) obtained by processing the workpiece. It relates to a composite sheet.
- semiconductor devices have been manufactured by a mounting method called a face-down method.
- a mounting method called a face-down method.
- the circuit surface side of the semiconductor chip is bonded to a chip mounting portion such as a lead frame. Therefore, the back surface side of the semiconductor chip on which no circuit is formed is exposed.
- a protective film made of a hard organic material is often formed on the back side of the semiconductor chip in order to protect the semiconductor chip.
- This protective film is formed using, for example, a film for semiconductor back surface or a dicing tape integrated wafer back surface protective film as disclosed in Patent Document 1 or 2.
- the protective film is generally formed of a thermosetting resin such as an epoxy resin.
- a thermosetting resin such as an epoxy resin.
- the curing temperature of the thermosetting resin exceeds 130 ° C. and the curing time requires about 2 hours, it has been an obstacle to improving the production efficiency. Therefore, a protective film having a curing mechanism that can shorten the processing time has been desired.
- Patent Document 3 discloses (A) a polymer component made of an acrylic copolymer having no double bond, (B) an energy ray-curable component, (C) a dye and / or a pigment, (D An energy ray curable chip protecting film having an energy ray curable protective film forming layer comprising an inorganic filler and (E) a photopolymerization initiator that absorbs light in a long wavelength region of 350 nm or longer is disclosed. Yes. Since such an energy ray-curable film for chip protection is cured mainly by ultraviolet irradiation in a short time, a protective film can be easily formed, which can contribute to an improvement in production efficiency.
- the component (C) used in the examples of Patent Document 3 is a black pigment, and a film for protecting a chip containing such a black pigment has a low ultraviolet transmittance. Therefore, when ultraviolet rays are irradiated to cure the chip protection film, the ultraviolet rays cannot sufficiently reach the inside of the film or the surface opposite to the ultraviolet irradiation surface, and the chip protection film is not cured. May be enough. Thus, when the film for chip protection is insufficiently cured, a problem occurs in the function as the protective film, such as the protective film obtained being easily peeled off by heat or the like.
- grinding marks are usually left by back grinding processing applied to the semiconductor wafer. From the viewpoint of the appearance of the semiconductor chip, it is desirable that such grinding marks are not visible with the naked eye, and are preferably hidden by the protective film.
- the present invention has been made in view of the actual situation as described above, and is capable of forming a protective film that is excellent in ultraviolet curability and that can form a protective film in which grinding marks present on a workpiece or a workpiece are not visible by visual inspection.
- An object is to provide a film, a protective film-forming sheet, and a protective film-forming composite sheet.
- the present invention comprises a protective film containing an ultraviolet curable component, having a light transmittance of 8% or more at a wavelength of 375 nm and a light transmittance of 12% or less at a wavelength of 550 nm.
- a formed film is provided (Invention 1).
- the protective film-forming film according to the above invention (Invention 1) is sufficiently cured by ultraviolet rays, and after ultraviolet curing, can form a protective film in which grinding marks present on the workpiece or workpiece are not visible.
- a colorant may be further contained (Invention 2).
- the colorant may be a red colorant (Invention 3).
- the colorant may be an organic colorant (Invention 4).
- the value W / T obtained by dividing the content W (% by mass) of the colorant in the protective film-forming film by the thickness T ( ⁇ m) of the protective film-forming film is 0.01 to 0.5 (Invention 5).
- the probe on the ultraviolet irradiation surface The ratio P2 / P1 of the probe tack peak value P2 on the surface opposite to the ultraviolet irradiation surface with respect to the tack peak value P1 may be 0.1 to 7 (Invention 6).
- the light transmittance at a wavelength of 1600 nm may be 25% or more (Invention 7).
- the present invention provides a protective film-forming sheet comprising the protective film-forming film (Inventions 1 to 7) and a release sheet laminated on one or both surfaces of the protective film-forming film (Invention). 8).
- sheet includes the concept of a tape.
- the present invention provides a composite sheet for forming a protective film comprising a support sheet and the protective film-forming film (Inventions 1 to 7) laminated on one surface side of the support sheet (Invention 9). .
- the said support sheet may consist of a base material and the adhesive layer laminated
- the protective film is sufficiently cured by ultraviolet rays, and the grinding traces present on the workpiece or workpiece are not visually observed. Can be formed.
- the protective film-forming film according to this embodiment is for forming a protective film on a workpiece or a workpiece obtained by processing the workpiece.
- the workpiece include a semiconductor wafer, and examples of a workpiece obtained by processing the workpiece include a semiconductor chip.
- the present invention is not limited to these.
- the protective film is formed on the back side of the semiconductor wafer (the side on which no electrodes such as bumps are formed).
- the protective film-forming film according to the present embodiment has a light transmittance of 8% or more at a wavelength of 375 nm and a light transmittance of 12% or less at a wavelength of 550 nm.
- the light transmittance in this specification is a value measured using an integrating sphere, and a spectrophotometer is used as a measuring instrument.
- the protective film-forming film according to the present embodiment contains an ultraviolet curable component.
- an ultraviolet curable component As described above, when the light transmittance at a wavelength of 375 nm is 8% or more, ultraviolet rays are easily transmitted through the protective film-forming film, and accordingly, the ultraviolet curable components in the protective film-forming film are easily cured. Therefore, even when the protective film forming film is irradiated with ultraviolet rays from one side, the entire protective film forming film is sufficiently cured, and there is insufficient curing on the inside of the protective film forming film or on the surface opposite to the ultraviolet irradiation surface. It can prevent effectively.
- the light transmittance at a wavelength of 375 nm of the protective film-forming film is preferably 10% or more, more preferably 13% or more, and 15% or more. Is more preferable, particularly 17% or more, and further preferably 20% or more.
- the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, but is naturally determined by setting the light transmittance at a wavelength of 550 nm to 12% or less.
- the light transmittance at a wavelength of 375 nm of the protective film-forming film is preferably 35% or less.
- grinding marks are usually left by back grinding applied to the semiconductor wafer.
- the protective film-forming film is difficult to transmit visible light. Therefore, the above-mentioned grinding mark is concealed by the protective film forming film (protective film) and hardly visible by visual inspection. Thereby, the external appearance of workpieces, such as a semiconductor chip, will be excellent.
- the light transmittance at a wavelength of 550 nm of the protective film-forming film is preferably 11% or less, particularly preferably 8% or less, and further preferably 5% or less. preferable.
- the lower limit of the light transmittance at a wavelength of 550 nm is not particularly limited, but is naturally determined by setting the light transmittance at a wavelength of 375 nm to 8% or more.
- the light transmittance at a wavelength of 375 nm of the protective film forming film is preferably 0% or more.
- the protective film-forming film according to this embodiment preferably has a light transmittance at a wavelength of 1600 nm of 25% or more, more preferably 40% or more, and particularly preferably 45% or more. Is preferably 50% or more.
- a crack or the like may occur due to stress generated during processing.
- infrared transmittance is improved, and infrared rays are obtained from the protective film forming film (or the protective film formed by the protective film forming film) side. Infrared inspection can be performed. Thereby, the crack etc. in workpieces, such as a semiconductor chip, can be discovered through a protective film formation film (protective film), and a product yield can be improved.
- the upper limit of the light transmittance of wavelength 1600nm is not specifically limited, By setting the light transmittance of wavelength 550nm to 12% or less, it will be decided naturally. Further, when using a workpiece (semiconductor chip or the like) on which a protective film is formed, the protective film-forming film has a light transmittance at a wavelength of 1600 nm of 90% or less, so that the workpiece easily affected by infrared rays from the outside can be obtained. Malfunction can be prevented.
- the protective film-forming film according to the present embodiment may be composed of a single layer or a plurality of layers.
- the protective film-forming film may be composed of a plurality of layers. It preferably consists of layers.
- the protective film-forming film is composed of a plurality of layers, it is preferable that the light transmittance is satisfied as a whole of the plurality of layers from the viewpoint of easy control of the light transmittance.
- the protective film forming film when the protective film forming film is irradiated with ultraviolet rays from one surface side, the side opposite to the ultraviolet irradiation surface with respect to the probe tack peak value P1 of the ultraviolet irradiation surface.
- the ratio P2 / P1 of the peak value P2 of the probe tack of the surface (hereinafter sometimes referred to as “ultraviolet irradiation opposite surface”) is preferably 0.1 to 7, and particularly preferably 0.5 to 4. Preferably, it is preferably 1 to 2.
- setting P2 / P1 to a value lower than 1 means, for example, that the protective film forming film is composed of a plurality of layers, and there are more layers than the layer forming the ultraviolet irradiation surface in the layer forming the ultraviolet irradiation opposite surface. It is possible by blending the ultraviolet curable component (A) described later.
- the probe tack measurement method is based on JIS Z1023 1999, and is specifically as shown in the test examples described later.
- the protective film forming film (protective film) is cured not only on the ultraviolet irradiation surface side but also on the ultraviolet irradiation opposite surface side, that is, the protective film forming film is in the thickness direction. It can be said that it is fully cured as a whole.
- the ratio E2 / E1 of the probe tack energy value E2 on the ultraviolet irradiation opposite surface to the probe tack energy value E1 on the ultraviolet irradiation surface is 0.1 to 10. In particular, it is preferably 0.5 to 5, and more preferably 1 to 2.5.
- setting E2 / E1 to a value lower than 1 means, for example, that the protective film-forming film is composed of a plurality of layers, and the number of layers forming the ultraviolet irradiation opposite surface is larger than the layer forming the ultraviolet irradiation surface. It is possible by blending the ultraviolet curable component (A) described later.
- the peak value P1 of the probe tack on the ultraviolet irradiation surface is preferably 0.05 to 1.5, particularly preferably 0.1 to 1, and more preferably 0.15 to 0.75. It is preferable that The energy value E1 of the probe tack on the ultraviolet irradiation surface is preferably 0.005 to 0.3, particularly preferably 0.008 to 0.15, and more preferably 0.01 to 0.00. 1 is preferable. That the peak value P1 and / or energy value E1 of the probe tack on the ultraviolet irradiation surface is in the above range, at least the ultraviolet irradiation surface side of the protective film forming film (protective film) is cured to a high degree. Can do.
- the protective film formation film which concerns on this embodiment contains an ultraviolet curable component (A).
- the ultraviolet curable component (A) is preferably an uncured ultraviolet curable component, and particularly preferably an uncured ultraviolet curable component having adhesiveness.
- Such a protective film-forming film is formed by stacking a protective film-forming film and a workpiece such as a semiconductor wafer and then curing the protective film-forming film by ultraviolet irradiation to form a durable protective film on a chip or the like. Can do. Since the said protective film formation film hardens
- the light transmittance of the protective film-forming film hardly changes even before or after curing. Therefore, if the light transmittance at a wavelength of 375 nm of the protective film forming film before curing is 8% or more and the light transmittance at a wavelength of 550 nm is 12% or less, the wavelength of the protective film forming film (protective film) after curing is 375 nm. The light transmittance is 13% or more, and the light transmittance at a wavelength of 550 nm is 12% or less.
- the protective film-forming film according to this embodiment preferably contains a colorant (B) in addition to the ultraviolet curable component (A).
- a colorant (B) in addition to the ultraviolet curable component (A).
- the protective film formation film which concerns on this embodiment contains a filler (C) together with a coloring agent (B).
- a coloring agent B
- the protective film formation film contains a filler, while being able to maintain the hardness of the protective film after hardening high, moisture resistance can be improved.
- the thermal expansion coefficient of the protective film after curing can be brought close to the thermal expansion coefficient of the semiconductor wafer, thereby reducing the warpage of the semiconductor wafer during processing.
- the protective film-forming film according to this embodiment preferably further contains a thermosetting component (D).
- a thermosetting component (D) By heating the protective film-forming film further containing the thermosetting component (D), the adhesive strength of the protective film-forming film to the work and the strength of the cured protective film can be improved.
- a protective film formation film contains an ultraviolet curable component (A) and a coloring agent (B)
- the sum total of the ratio of an ultraviolet curable component (A) and the ratio of a coloring agent (B) will be 100 mass%.
- the ratio of the ultraviolet curable component (A) and the ratio of the colorant (B) are set.
- the protective film-forming film contains an ultraviolet curable component (A), a colorant (B) and a filler (C)
- the proportion of the ultraviolet curable component (A), the proportion of the colorant (B) and the filler is set so that the total ratio of C) is 100% by mass.
- the protective film-forming film contains an ultraviolet curable component (A), a colorant (B), a filler (C), and a thermosetting component (D), the ratio of the ultraviolet curable component (A) and the colorant (B) UV curable component (A), colorant (B), filler (C), and thermosetting so that the total of the proportion of the filler, the proportion of filler (C) and the thermosetting component (D) is 100% by mass.
- the proportion of component (D) is set.
- the ultraviolet curable component (A) may be a polymer (A1) having an ultraviolet curable group introduced, or an ultraviolet curable compound (A3) excluding the polymer (A1) having an ultraviolet curable group introduced. ) May be contained.
- the ultraviolet curable component (A) in this embodiment contains an ultraviolet curable compound (A3), it is preferable to also contain a polymer such as a polymer (A2) that does not have ultraviolet curable properties.
- the term “polymer” includes the concept of “copolymer”.
- the polymer (A1) may be contained as it is in the protective film-forming film.
- at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent.
- Examples of the polymer (A1) introduced with an ultraviolet curable group include a functional group-containing acrylic polymer (A1-1) containing a functional group-containing monomer containing a functional group as a constituent, and the functional group Examples thereof include an acrylic polymer which is a reaction product of a reactive group and a curable group-containing compound (A1-2) having an ultraviolet curable carbon-carbon double bond.
- the functional group-containing acrylic polymer (A1-1) is a copolymerization reaction product of an acrylic monomer containing a functional group, an acrylic monomer not containing a functional group, and, if desired, a monomer other than the acrylic monomer. It is preferable. That is, the functional group-containing monomer is preferably an acrylic monomer containing a functional group.
- the term “polymer” or “resin” or the like used for a substance in which a monomer is polymerized is a “polymer” composed of structural units derived from the monomer (also referred to as repeating units) or It means “resin” or the like.
- the functional group of the acrylic monomer containing a functional group (functional group of the functional group-containing monomer), one that can react with the substituent of the curable group-containing compound (A1-2) is selected.
- a functional group include a hydroxy group, a carboxy group, an amino group, a substituted amino group, and an epoxy group, and among them, a hydroxy group is preferable.
- the ultraviolet curable component (A) in the present embodiment contains a crosslinking agent
- the functional group-containing acrylic polymer (A1-1) contains a functional group having a functional group that reacts with the crosslinking agent. It is preferable to contain a monomer as a constituent component, and the functional group-containing monomer may also serve as a functional group-containing monomer having a functional group capable of reacting with the substituent of the curable group-containing compound.
- acrylic monomer containing a hydroxy group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( And (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of reactivity with the curable group-containing compound (A1-2). These may be used alone or in combination of two or more.
- the acrylic monomer that does not contain a functional group preferably contains a (meth) acrylic acid alkyl ester monomer.
- (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid n- Pentyl, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, Examples include palmityl (meth) acrylate and stearyl (meth) acrylate.
- (meth) acrylic acid alkyl ester monomers those having 1 to 18 carbon atoms in the alkyl group are preferable, and those having 1 to 4 carbon atoms are particularly preferable. These may be used alone or in combination of two or more.
- acrylic monomers not containing functional groups include, for example, methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ( Non-crosslinkable acrylamides such as (meth) acrylic acid esters containing alkenyl groups such as ethoxyethyl (meth) acrylate and aromatic rings such as phenyl (meth) acrylate, acrylamide and methacrylamide (Meth) acrylic acid ester having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate may also be included.
- Non-crosslinkable acrylamides such as (meth) acrylic acid esters containing alkenyl groups such as ethoxyethyl (meth) acrylate and aromatic rings such as phenyl (meth) acryl
- monomers other than acrylic monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene.
- the proportion of the mass of the structural portion derived from the functional group-containing monomer in the total mass of the functional group-containing acrylic polymer (A1-1) is 0.1-50.
- the content is preferably 1% by mass, particularly preferably 1 to 40% by mass, and further preferably 3 to 30% by mass.
- the functional group-containing acrylic polymer (A1-1) can be obtained by copolymerizing the above monomers by a conventional method.
- the polymerization mode of the functional group-containing acrylic polymer (A1-1) may be a random copolymer or a block copolymer.
- the curable group-containing compound (A1-2) has a substituent that reacts with the functional group of the functional group-containing acrylic polymer (A1-1) and an ultraviolet curable carbon-carbon double bond.
- substituent that reacts with the functional group of the functional group-containing acrylic polymer (A1-1) include an isocyanate group, an epoxy group, and a carboxy group. Among them, an isocyanate group that is highly reactive with a hydroxy group. Is preferred.
- the curable group-containing compound (A1-2) preferably contains 1 to 5 ultraviolet curable carbon-carbon double bonds per molecule of the curable group-containing compound (A1-2), particularly 1 to It is preferable to include two.
- curable group-containing compound (A1-2) examples include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1-bis ( Acryloyloxymethyl) ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) acrylate And an acryloyl monoisocyanate compound obtained by the reaction.
- 2-methacryloyloxyethyl isocyanate is particularly preferable.
- the curable group-containing compound (A1-2) one kind can be used alone, or two or more kinds can be used in combination.
- the polymer (A1) into which the ultraviolet curable group has been introduced has a curable group derived from the curable group-containing compound (A1-2) as a functional group (curable group-containing compound (A1)). It is preferably contained in an amount of 20 to 120 mol%, particularly preferably 35 to 100 mol%, more preferably 50 to 100 mol%, based on the functional group reacting with the substituent of A1-2). Is preferred.
- the curable group-containing compound (A1-2) is monofunctional, the upper limit is 100 mol%, but when the curable group-containing compound (A1-2) is polyfunctional, it exceeds 100 mol%.
- the ratio of the curable group to the functional group is within the above range, the adhesive strength of the protective film after UV curing can be made extremely excellent.
- the weight average molecular weight (Mw) of the polymer (A1) having an ultraviolet curable group introduced is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.
- the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the ultraviolet curable component (A) in this embodiment contains a polymer (A2) that does not have ultraviolet curable properties
- the polymer (A2) may be contained as it is in the protective film-forming film, At least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent.
- the polymer (A2) include phenoxy resin, acrylic polymer (A2-1), urethane resin, polyester resin, rubber resin, acrylic urethane resin, and the like. Of these, the case of using the acrylic polymer (A2-1) will be described in detail.
- a conventionally known acrylic polymer can be used as the acrylic polymer (A2-1).
- the acrylic polymer (A2-1) may be a homopolymer formed from one type of acrylic monomer, or may be a copolymer formed from a plurality of types of acrylic monomers. It may be a copolymer formed from one or more types of acrylic monomers and monomers other than acrylic monomers.
- Specific types of the compound that becomes the acrylic monomer are not particularly limited, and specific examples include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, itaconic acid, and the like).
- (meth) acrylic acid esters include chain skeletons such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
- Cyclic skeletons such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and imide acrylate (Meth) acrylate having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate, N-methyl Having a reactive functional group other than hydroxy group, such as Minoechiru (meth) acrylate (meth) acrylate.
- monomers other than acrylic monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene.
- the acrylic monomer is an alkyl (meth) acrylate, the alkyl group preferably has 1 to 18 carbon atoms.
- the acrylic polymer (A2-1) preferably has a reactive functional group that reacts with the crosslinking agent.
- the type of the reactive functional group is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent.
- examples of the reactive functional group possessed by the acrylic polymer (A2-1) include a hydroxy group, a carboxy group, and an amino group. A highly functional hydroxy group is preferred.
- examples of the reactive functional group possessed by the acrylic polymer (A2-1) include a carboxy group, an amino group, an amide group, and the like. A highly functional carboxy group is preferred.
- the carboxy group is preferably 12 wt% or less based on the entire reactive functional group of the acrylic polymer (A2-1).
- the method for introducing the reactive functional group into the acrylic polymer (A2-1) is not particularly limited.
- the acrylic polymer (A2-1) is formed using a monomer having a reactive functional group, Examples thereof include a method in which a structural unit based on a monomer having a reactive functional group is contained in the polymer skeleton.
- the acrylic polymer (A2-1) may be formed using a monomer having a hydroxy group such as 2-hydroxyethyl acrylate.
- the reactive functional group occupies the total mass of the acrylic polymer (A2-1) from the viewpoint of making the degree of crosslinking in a favorable range.
- the proportion of the mass of the structural portion derived from the monomer having the above is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.
- the weight average molecular weight (Mw) of the acrylic polymer (A2-1) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000 from the viewpoint of film forming properties at the time of coating. .
- the ultraviolet curable component (A) may contain an ultraviolet curable compound (A3) excluding the polymer (A1) into which an ultraviolet curable group is introduced. It is preferable to contain the polymer (A2) that is not included. Moreover, it may replace with the polymer (A2) which does not have ultraviolet curing property, or may contain the polymer (A1) by which the ultraviolet curing group was introduce
- the ultraviolet curable compound (A3) is a compound having an ultraviolet curable group and polymerized when irradiated with ultraviolet rays.
- the ultraviolet curable group possessed by the ultraviolet curable compound (A3) is, for example, a group containing an ultraviolet curable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group and a vinyl group. Can do.
- an ultraviolet curable compound (A3) if it has said ultraviolet curable group, From a versatility viewpoint, it is a low molecular weight compound (monofunctional and polyfunctional monomer and oligomer). It is preferable.
- the low molecular weight ultraviolet curable compound (A3) include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, and 1,4 -Cyclic aliphatic skeleton-containing acrylates such as butylene glycol diacrylate, 1,6-hexanediol diacrylate, dicyclopentadiene dimethoxydiacrylate, isobornyl acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified Acrylate compounds such as acrylate, polyether acrylate, itaconic acid oligomers It is below.
- examples of the ultraviolet curable compound (A3) include an epoxy resin having an ultraviolet curable group and a phenol resin having an ultraviolet curable group.
- a resin for example, those described in JP 2013-194102 A can be used.
- Such a resin corresponds to a resin constituting the thermosetting component (C) described later, but also contributes to ultraviolet curing, and is therefore treated as an ultraviolet curable compound (A) in the present invention.
- the UV curable compound (A3) usually has a molecular weight of about 100 to 30,000, preferably about 300 to 10,000.
- the ultraviolet curable compound (A3) is used in a proportion of about 10 to 400 parts by weight, preferably about 30 to 350 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A1) and the polymer (A2). It is done.
- the protective film-forming film according to this embodiment preferably contains 5 to 89% by mass of the ultraviolet curable component (A), particularly preferably 10 to 80% by mass, based on the mass of the protective film-forming film. Further, it is preferable to contain 20 to 70% by mass. When the content of the ultraviolet curable component (A) is within the above range, it can be sufficiently cured by ultraviolet irradiation.
- the colorant (B) for example, known pigments such as inorganic pigments, organic pigments, and organic dyes can be used. From the viewpoint of improving the light transmittance, the colorant (B) is An organic colorant is preferred.
- the characteristics of the protective film-forming film according to this embodiment or the preferable characteristics of the protective film-forming film according to this embodiment are that the light transmittance at a wavelength of 375 nm is 8% or more and the light transmittance at a wavelength of 550 nm. The characteristic is that the light transmittance is lower in a certain wavelength region than in a lower wavelength region, such as a rate of 12% or less.
- the protective film-forming film according to this embodiment contains only an inorganic colorant, it is not always easy to impart the above properties to the protective film-forming film according to this embodiment.
- the protective film-forming film according to this embodiment contains an organic colorant, the protective film-forming film according to this embodiment can easily satisfy the above-described characteristics. .
- the colorant (B) is a pigment.
- the colorant (B) contained in the protective film-forming film according to the present embodiment is preferably composed of an organic pigment.
- the coloring agent (B) which the protective film formation film which concerns on this embodiment contains may be comprised from multiple types of material.
- organic pigments and organic dyes that are organic colorants include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, and naphthoquinone dyes.
- inorganic pigments include carbon black, cobalt dyes, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, ITO (indium) Tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
- the colorant (B) in the protective film-forming film according to the present embodiment may be composed of an organic colorant and an inorganic colorant.
- the protective film-forming film according to this embodiment contains a red colorant.
- the light transmittance at a wavelength of 375 nm and a wavelength of 550 nm (more preferably, a wavelength of 1600 nm) can be more easily controlled within the above-described range.
- the red colorant may be a pigment or a dye. Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. These can be used individually by 1 type or in mixture of 2 or more types.
- diketopyrrolopyrrole red colorants are preferred. According to such a red colorant, the light transmittance at a wavelength of 375 nm and a wavelength of 550 nm can be easily controlled within the above-described range.
- the content of the colorant (B) in the protective film-forming film is preferably determined according to the thickness of the protective film-forming film so that the light transmittance is in the range described above. Specifically, a value W / T obtained by dividing the content W (% by mass with respect to the total mass of the protective film forming film) of the colorant (B) in the protective film forming film by the thickness T ( ⁇ m) of the protective film forming film. However, it is preferably 0.01 to 0.5, particularly preferably 0.03 to 0.3, and more preferably 0.05 to 0.25.
- W / T When W / T is 0.5 or more, it is easy to control the light transmittance at a wavelength of 550 nm to 12% or less, and when W / T is 0.01 or less, the light transmittance at a wavelength of 375 nm is set to 13% or more. Easy to control.
- filler (C) examples include silica such as crystalline silica, fused silica and synthetic silica, and inorganic filler such as alumina and glass balloon. Among these, silica is preferable, synthetic silica is more preferable, and synthetic silica of the type in which ⁇ -ray sources that cause malfunction of the semiconductor device are removed as much as possible is optimal.
- shape of the filler (C) examples include a spherical shape, a needle shape, and an indefinite shape, but a spherical shape is preferable, and a true spherical shape is particularly preferable.
- the irregular shape means a shape having an irregular surface shape.
- the irregular surface may be multifaceted or a single curved surface.
- each surface may be a flat surface or a curved surface, or these may be mixed.
- the surface is multifaceted, the area of each face may be different.
- the surface shape may have a protruding shape or may have a concave shape.
- a functional filler may be blended in the protective film-forming film.
- a conductive filler in which gold, silver, copper, nickel, aluminum, stainless steel, carbon, ceramic, nickel, aluminum, or the like is coated with silver for the purpose of imparting conductivity after die bonding.
- metal materials such as gold, silver, copper, nickel, aluminum, magnesium, stainless steel, silicon, germanium and their alloys, oxides, nitrides, hydroxides, etc. Examples include thermally conductive fillers such as boron nitride.
- the average particle size of the filler (C) is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 3 ⁇ m, and particularly preferably 0.03 to 2 ⁇ m. Furthermore, it is preferably 0.05 to 1 ⁇ m.
- the average particle size of the filler (C) is 0.01 ⁇ m or more, it is easy to control the light transmittance at a wavelength of 550 nm to 13% or less so that grinding marks on a semiconductor chip or the like cannot be visually observed.
- the surface state of a protective film formation film can be favorably maintained as the average particle diameter of a filler (C) is 10 micrometers or less. Further, when the average particle diameter of the filler (C) is 3 ⁇ m or less, infrared reflection can be suppressed and infrared inspection can be performed satisfactorily.
- the average particle size of the filler (C) of less than 1 ⁇ m in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring device (Nikkiso Co., Ltd., Nanotrack Wave-UT151). .
- the average particle size of 1 ⁇ m or more of the filler (C) is a value measured by a laser diffraction / scattering method using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac MT3000II).
- the content of the filler (C) (particularly silica filler) in the protective film-forming film is preferably 10 to 80% by mass, particularly 20 to 70% by mass, based on the mass of the protective film-forming film. More preferably, the content is 30 to 65% by mass.
- the blending amount of the filler is 10% by mass or more, it is easy to control the light transmittance at a wavelength of 550 nm to 13% or less so that grinding marks on a semiconductor chip or the like cannot be visually observed.
- the blending amount of the filler (C) is 80% by mass or less, the protective film-forming film can be sufficiently cured by ultraviolet irradiation.
- thermosetting component (D) examples include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, benzoxazine resins, and mixtures thereof.
- an epoxy resin, a phenol resin, and a mixture thereof are preferably used.
- Epoxy resin has the property of forming a three-dimensional network and forming a strong film when heated.
- an epoxy resin conventionally known various epoxy resins are used, and those having a molecular weight of about 300 to 2000 are usually preferred, and those having a molecular weight of 300 to 500 are particularly preferred. Further, it is preferably used in a form in which a normal and liquid epoxy resin having a molecular weight of 330 to 400 is blended with a solid epoxy resin having a molecular weight of 400 to 2500, particularly 500 to 2000 at room temperature.
- the epoxy equivalent of the epoxy resin is preferably 50 to 5000 g / eq.
- epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; Glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; glycidyl type or alkyl glycidyl type epoxy resins in which active hydrogen bonded to nitrogen atom such as aniline isocyanurate is substituted with glycidyl group; vinylcyclohexane diepoxide; 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4 As such epoxy) cyclohexane
- bisphenol-based glycidyl type epoxy resins o-cresol novolac type epoxy resins and phenol novolac type epoxy resins are preferably used.
- These epoxy resins can be used alone or in combination of two or more.
- thermally activated latent epoxy resin curing agent is a type of curing agent that does not react with the epoxy resin at room temperature but is activated by heating at a certain temperature or more and reacts with the epoxy resin.
- the heat activated latent epoxy resin curing agent is activated by a method in which active species (anions and cations) are generated by a chemical reaction by heating; the epoxy resin is stably dispersed in the epoxy resin at around room temperature and is heated at a high temperature.
- thermally active latent epoxy resin curing agent examples include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, high melting point active hydrogen compounds such as imidazole compounds, and the like. These thermally activated latent epoxy resin curing agents can be used singly or in combination of two or more.
- the heat-activatable latent epoxy resin curing agent as described above is preferably 0.1 to 20 parts by weight, particularly preferably 0.2 to 10 parts by weight, and still more preferably 0.8 to 100 parts by weight of the epoxy resin. It is used at a ratio of 3 to 5 parts by weight.
- phenolic resin a condensate of phenols such as alkylphenol, polyhydric phenol, naphthol and aldehydes is used without any particular limitation.
- phenol novolak resin, o-cresol novolak resin, p-cresol novolak resin, t-butylphenol novolak resin, dicyclopentadiene cresol resin, polyparavinylphenol resin, bisphenol A type novolak resin, or modified products thereof Etc. are used.
- the phenolic hydroxyl group contained in these phenolic resins can easily undergo an addition reaction with the epoxy group of the above epoxy resin by heating to form a cured product having high impact resistance. For this reason, you may use together an epoxy resin and a phenol-type resin.
- the content of the thermosetting component (D) in the protective film-forming film is preferably 1 to 85% by weight, particularly preferably 2 to 75% by weight, based on the weight of the protective film-forming film. Further, it is preferably 5 to 70% by mass.
- the content of the thermosetting component (D) is within the above-mentioned range, so that the effect of adhering the protective film-forming film to the work by thermosetting and the strength of the cured protective film can be obtained without interfering with the ultraviolet curing property. Can be improved.
- the protective film formation film which concerns on this embodiment may contain a photoinitiator.
- a photopolymerization initiator By containing a photopolymerization initiator, the curing time and the amount of light irradiation of the ultraviolet curable component (A) can be reduced.
- the photopolymerization initiator is preferably 0.1 to 15% by mass with respect to the mass of the ultraviolet curable component (A).
- the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloranthraquinone, (2,4,6-trimethyl Benzyldiphenyl) phosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamate, oligo ⁇ 2-hydroxy-2-methyl- - [4-trimethyl
- the protective film-forming film according to this embodiment may contain a chain transfer agent.
- a chain transfer agent By containing the chain transfer agent, an effect that ultraviolet curing easily proceeds inside the protective film-forming film in the thickness direction is expected.
- the chain transfer agent for example, those described in JP2012-207179A can be used.
- the protective film-forming film according to this embodiment may contain a coupling agent.
- a coupling agent By containing the coupling agent, after curing of the protective film-forming film, the adhesiveness and adhesion between the protective film and the workpiece can be improved without impairing the heat resistance of the protective film, and water resistance ( (Moisture and heat resistance) can be improved.
- the coupling agent a silane coupling agent is preferable because of its versatility and cost merit.
- silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxy).
- the protective film-forming film according to this embodiment may contain a crosslinking agent such as an organic polyvalent isocyanate compound, an organic polyvalent imine compound, and an organometallic chelate compound in order to adjust the cohesive force before curing. Further, the protective film-forming film may contain an antistatic agent in order to suppress static electricity and improve the reliability of the chip. Furthermore, the protective film-forming film may contain a flame retardant such as a phosphoric acid compound, a bromine compound, or a phosphorus compound in order to enhance the flame retardance performance of the protective film and improve the reliability as a package.
- a crosslinking agent such as an organic polyvalent isocyanate compound, an organic polyvalent imine compound, and an organometallic chelate compound in order to adjust the cohesive force before curing.
- the protective film-forming film may contain an antistatic agent in order to suppress static electricity and improve the reliability of the chip.
- the protective film-forming film may contain a flame retardant such as a phosphoric acid compound, a bromine compound
- the thickness of the protective film-forming film is preferably 3 to 300 ⁇ m, particularly preferably 5 to 200 ⁇ m, more preferably 7 to 100 ⁇ m, in order to effectively exert the function as a protective film.
- the thickness of a protective film formation film is the value represented by the average which measured thickness with the contact-type thickness meter in arbitrary five places of a protective film formation film.
- FIG. 1 is a cross-sectional view of a protective film forming sheet according to an embodiment of the present invention.
- the protective film-forming sheet 2 according to this embodiment includes a protective film-forming film 1 and a release layer laminated on one surface (the lower surface in FIG. 1) of the protective film-forming film 1. And a sheet 21.
- the release sheet 21 is peeled off when the protective film forming sheet 2 is used.
- the release sheet 21 protects the protective film-forming film 1 until the protective film-forming sheet 2 is used, and is not necessarily required.
- the configuration of the release sheet 21 is arbitrary, and examples thereof include a plastic film in which the film itself is peelable from the protective film-forming film 1 and a film obtained by peeling the plastic film with a release agent or the like.
- Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
- the release agent silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable.
- the thickness of the release sheet 21 is not particularly limited, but is usually about 20 to 250 ⁇ m.
- the release sheet 21 as described above may also be laminated on the other surface (the upper surface in FIG. 1) of the protective film forming film 1. That is, the protective film forming film 1 may be sandwiched between the first release sheet 21 and the second release sheet 21. In this case, it is preferable that the release force of one release sheet 21 is increased to obtain a heavy release release sheet, and the release force of the other release sheet 21 is reduced to provide a light release release sheet.
- the release surface of the release sheet 21 (a surface having peelability; usually a surface subjected to a release treatment, but is not limited thereto).
- a protective film forming film 1 is formed. Specifically, a coating agent for a protective film-forming film containing a curable adhesive constituting the protective film-forming film 1 and, if desired, further a solvent is prepared, and a roll coater, a knife coater, a roll knife coater, an air knife
- the protective film-forming film 1 is formed by applying to the release surface of the release sheet 21 with a coating machine such as a coater, die coater, bar coater, gravure coater, curtain coater, and drying.
- the protective film forming film 1 of the protective film forming sheet 2 is attached to the back surface of the semiconductor wafer having a circuit formed on the front surface and subjected to back grinding. At this time, if desired, the protective film-forming film 1 may be heated to exhibit adhesiveness.
- the release sheet 21 is peeled from the protective film forming film 1.
- the protective film forming film 1 is irradiated with ultraviolet rays, the protective film forming film 1 is cured to form a protective film, and a semiconductor wafer with a protective film is obtained.
- the protective film-forming film 1 may be heated before or after the ultraviolet irradiation.
- the protective film-forming film 1 is excellent in ultraviolet curability when the light transmittance at a wavelength of 375 nm is 8% or more, the film is sufficiently cured as a whole by the above-described ultraviolet irradiation. Irradiation of the ultraviolet to the protection film forming film 1 is preferably 50 ⁇ 1000mJ / cm 2 in quantity, especially 100 ⁇ 500mJ / cm 2 preferably.
- the protective film is irradiated with laser light as desired to perform laser printing. In addition, you may perform this laser printing before hardening of the protective film formation film 1.
- the semiconductor wafer with a protective film is diced according to a conventional method to obtain a chip having a protective film (chip with a protective film). Thereafter, if necessary, the dicing sheet is expanded in the plane direction, and a chip with a protective film is picked up from the dicing sheet.
- the protective film forming film 1 (protective film) has a light transmittance of 12% or less at a wavelength of 550 nm, so that grinding marks due to back grinding are concealed by the protective film. Since it cannot be seen visually, it has an excellent appearance.
- the infrared light transmittance in the protective film forming film 1 is improved, and the chip with the protective film and the protective film are protected.
- the semiconductor wafer with a film can be subjected to infrared inspection through a protective film. Therefore, cracks and the like can be found by infrared inspection, and the product yield can be improved.
- the infrared inspection is an inspection performed using infrared rays, and by acquiring infrared rays from a workpiece such as a semiconductor wafer with a protective film or a workpiece such as a chip with a protective film through the protective film. It can be carried out.
- the wavelength of the infrared rays to be obtained is usually 800 to 2800 nm, preferably 1100 to 2100 nm.
- an infrared inspection apparatus a known apparatus such as an infrared camera or an infrared microscope can be used.
- FIG. 2 is a cross-sectional view of a protective film-forming composite sheet according to an embodiment of the present invention.
- the protective film-forming composite sheet 3 includes a support sheet 4 in which an adhesive layer 42 is laminated on one surface of a substrate 41, and an adhesive layer of the support sheet 4.
- the protective film forming film 1 laminated on the 42 side and the jig adhesive layer 5 laminated on the peripheral edge of the protective film forming film 1 opposite to the support sheet 4 are configured.
- the composite sheet 3 for forming the protective film includes the base material 41, the adhesive layer 42 on the base material 41, the protective film forming film 1 on the adhesive layer 42, and the jig on the protective film forming film 1.
- the jig pressure-sensitive adhesive layer 5 is located at the peripheral edge of the protective film-forming film 1 when viewed from the normal direction of the surface of the protective film-forming film 1.
- the jig pressure-sensitive adhesive layer 5 is a layer for bonding the protective film-forming composite sheet 3 to a jig such as a ring frame.
- the composite sheet 3 for forming a protective film according to the present embodiment is attached to the workpiece and holds the workpiece, and the protective film is formed on the workpiece or a workpiece obtained by processing the workpiece.
- This protective film is composed of a protective film-forming film 1, preferably a cured protective film-forming film 1.
- the composite sheet 3 for forming a protective film according to the present embodiment is used to hold a semiconductor wafer during dicing processing of a semiconductor wafer as a workpiece and to form a protective film on a semiconductor chip obtained by dicing.
- the present invention is not limited to this.
- the support sheet 4 of the protective film-forming composite sheet 3 is usually referred to as a dicing sheet.
- the support sheet 4 of the protective film-forming composite sheet 3 according to the present embodiment may include a base material 41 and an adhesive layer 42 laminated on one surface of the base material 41.
- the support sheet 4 is preferably composed only of the base material 41.
- the protective film-forming film 1 of the present embodiment is cured by ultraviolet irradiation, it becomes easy to pick up the chip with the protective film from the support sheet 4 in an example of a method for using the protective film-forming composite sheet described below.
- the support sheet 4 consists only of the base material 41, the primer layer, the antistatic layer, the heat-resistant layer, the stress relaxation layer, etc. may be provided in the base material 41.
- the base material 41 of the support sheet 4 is not particularly limited as long as the base material 41 is suitable for workpiece processing, for example, dicing and expanding of a semiconductor wafer.
- a resin-based material is the main material. It is comprised from a film (henceforth "resin film").
- resin films include polyethylene films such as low density polyethylene (LDPE) films, linear low density polyethylene (LLDPE) films, and high density polyethylene (HDPE) films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene films.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- Polyolefin films such as ethylene-norbornene copolymer film and norbornene resin film; ethylene-vinyl acetate copolymer film, ethylene- (meth) acrylic acid copolymer film, ethylene- (meth) acrylic acid ester copolymer
- Ethylene copolymer films such as films; Polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; Polyethylene terephthalate films, Polybutylene films Polyester film such as terephthalate film; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used.
- the substrate 41 may be a film made of one of these, or may be a laminated film in which two or more of these are combined.
- (meth) acrylic acid in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
- polyolefin films are preferable from the viewpoints of environmental safety, cost, and the like.
- the resin film may be subjected to a surface treatment such as an oxidation method or a concavo-convex method or a primer treatment on one or both sides as desired for the purpose of improving the adhesion with the pressure-sensitive adhesive layer 42 laminated on the surface.
- a surface treatment such as an oxidation method or a concavo-convex method or a primer treatment on one or both sides as desired for the purpose of improving the adhesion with the pressure-sensitive adhesive layer 42 laminated on the surface.
- a surface treatment such as an oxidation method or a concavo-convex method or a primer treatment on one or both sides as desired for the purpose of improving the adhesion with the pressure-sensitive adhesive layer 42 laminated on the surface.
- the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like.
- a thermal spraying method include a thermal spraying method.
- the base material 41 may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the resin film.
- the thickness of the base material 41 is not particularly limited as long as it can function properly in each process in which the protective film-forming composite sheet 3 is used.
- the range is preferably 20 to 450 ⁇ m, more preferably 25 to 400 ⁇ m, and particularly preferably 50 to 350 ⁇ m.
- the thickness of the base material 41 is a value represented by an average obtained by measuring the thickness of the base material 41 with a contact-type thickness meter at any five locations. *
- the elongation at break of the base material 41 of the support sheet 4 in this embodiment is preferably 100% or more as a value measured at 23 ° C. and a relative humidity of 50%, particularly preferably 200 to 1000%.
- the elongation at break is the elongation relative to the original length of the test piece at the time of breaking the test piece in a tensile test according to JIS K7161: 1994 (ISO 527-1 1993).
- the base material 41 having a breaking elongation of 100% or more is not easily broken during the expanding process, and the chips formed by cutting the workpiece can be easily separated.
- the tensile stress at 25% strain of the base material 41 of the support sheet 4 in this embodiment is preferably 5 to 15 N / 10 mm, and the maximum tensile stress is preferably 15 to 50 MPa.
- the tensile stress at 25% strain and the maximum tensile stress are measured by a test based on JIS K7161: 1994.
- the base material 2 is loosened when the workpiece is bonded to the dicing sheet 1 and then fixed to a frame such as a ring frame. Generation
- production is suppressed and it can prevent that a conveyance error arises.
- the dicing sheet 1 itself is prevented from peeling off from the ring frame during the expanding process.
- the elongation at break, the tensile stress at 25% strain, and the maximum tensile stress are values measured in the longitudinal direction of the original fabric in the base material 41.
- the pressure-sensitive adhesive layer 42 provided in the support sheet 4 of the protective film-forming composite sheet 3 according to the present embodiment is a type of pressure-sensitive adhesive that is not cured by ultraviolet rays (ultraviolet non-curable adhesive) or a type that is cured by ultraviolet rays. It is preferable to be comprised from the adhesive which hardened the adhesive previously.
- the adhesive In the case of a pressure-sensitive adhesive that is cured in advance with ultraviolet rays (ultraviolet-curable adhesive), when the protective film-forming film 1 is cured, when the protective film-forming composite sheet 3 is irradiated with ultraviolet rays, the adhesive
- the UV curable group that one or more of the components contained in the layer 42 usually has reacts with the UV curable group that the UV curable component (A) of the protective film forming film 1 reacts to form the pressure-sensitive adhesive layer 42 and the protective film. There is a concern that it may be difficult to peel both of them from the formed film 1.
- the ultraviolet non-curable pressure-sensitive adhesive those having desired adhesive strength and removability are preferable, for example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, A polyvinyl ether-based pressure-sensitive adhesive or the like can be used.
- acrylic pressure-sensitive adhesive that has high adhesiveness with the protective film-forming film 1 and can effectively prevent the workpiece or workpiece from falling off in a dicing process or the like is preferable.
- an uncured adhesive layer 42 is formed with a known UV-curable adhesive, and UV is applied at the time of manufacture. It is only necessary to cure the adhesive by irradiation.
- the thickness of the pressure-sensitive adhesive layer 42 is not particularly limited as long as it can function properly in each step in which the protective film-forming composite sheet 3 is used. Specifically, the thickness is preferably 1 to 50 ⁇ m, particularly preferably 2 to 30 ⁇ m, and further preferably 3 to 20 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer 42 is a value represented by an average obtained by measuring the thickness with a contact-type thickness meter at any five locations of the pressure-sensitive adhesive layer 42.
- the total thickness may be measured in the same manner as described above, and may be calculated by taking the difference from the thickness of another film that has been overlaid (measured by the same method as described above).
- tool what has desired adhesive force and removability is preferable, for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive Polyester-based pressure-sensitive adhesives, polyvinyl ether-based pressure-sensitive adhesives, and the like can be used.
- an acrylic pressure-sensitive adhesive that has high adhesion to a jig such as a ring frame and can effectively prevent the protective film-forming composite sheet 3 from being peeled off from the ring frame or the like in a dicing process or the like.
- the base material as a core material may intervene in the middle of the thickness direction of the adhesive layer 5 for jigs.
- the thickness of the pressure-sensitive adhesive layer 5 for jigs is preferably 5 to 200 ⁇ m, and particularly preferably 10 to 100 ⁇ m, from the viewpoint of adhesion to a jig such as a ring frame.
- the protective film-forming film is interposed via the support sheet 4. 1 may be irradiated with ultraviolet rays. Therefore, in such a case, it is preferable that the ultraviolet ray permeability of the support sheet 4 is high so that the curing of the protective film-forming film 1 can easily proceed.
- the protective film-forming composite sheet 3 is prepared separately from a first laminate including the protective film-forming film 1 and a second laminate including the support sheet 4. Then, it can be produced by laminating the protective film-forming film 1 and the support sheet 4 using the first laminated body and the second laminated body, but is not limited thereto.
- the protective film forming film 1 is formed on the release surface of the first release sheet.
- a coating agent for a protective film-forming film containing a curable adhesive constituting the protective film-forming film 1 and, if desired, further a solvent is prepared, and a roll coater, a knife coater, a roll knife coater, an air knife
- the protective film-forming film 1 is formed by applying to the release surface of the first release sheet with a coating machine such as a coater, die coater, bar coater, gravure coater, curtain coater, and drying.
- the protective film forming film 1 (and the second release sheet) may be formed in a desired shape, for example, a circle. In this case, what is necessary is just to remove suitably the protective film formation film 1 and the excess part of the 2nd peeling sheet which arose by the half cut.
- a coating agent for the pressure-sensitive adhesive layer further containing a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 42 and, if desired, a solvent, on the release surface of the third release sheet.
- the pressure-sensitive adhesive layer 42 is formed by applying and drying. Then, the base material 41 is crimped
- the pressure-sensitive adhesive is cured by irradiating with ultraviolet rays, preferably after obtaining the second laminate.
- the second release sheet in the first laminate is released and the third release sheet in the second laminate is released.
- the protective film forming film 1 exposed in the first laminate and the pressure-sensitive adhesive layer 42 of the support sheet 4 exposed in the second laminate are overlapped and pressure-bonded.
- the support sheet 4 may be half-cut if desired, and may have a desired shape, for example, a circle having a larger diameter than the protective film-forming film 1. At this time, an excess portion of the support sheet 4 generated by the half cut may be removed as appropriate. In this case, the protective film forming sheet 3 having the form shown in FIG. 3 is obtained.
- the support sheet 4 in which the pressure-sensitive adhesive layer 42 is laminated on the base material 41, the protective film-forming film 1 laminated on the pressure-sensitive adhesive layer 42 side of the support sheet 4, and the protective film-forming film 1 A protective sheet-forming composite sheet 3 comprising a first release sheet laminated on the side opposite to the support sheet 4 is obtained.
- a jig pressure-sensitive adhesive layer 5 is formed on the peripheral edge of the protective film forming film 1 opposite to the support sheet 4.
- the jig pressure-sensitive adhesive layer 5 can also be applied and formed in the same manner as the pressure-sensitive adhesive layer 42.
- the protective film forming film 1 is stuck to the semiconductor wafer 6 and the jig adhesive layer 5 is stuck to the ring frame 7.
- the protective film forming film 1 may be heated to exhibit adhesiveness if desired.
- the protective film forming film 1 is irradiated with ultraviolet rays via the support sheet 4 to cure the protective film forming film 1 to form a protective film, thereby obtaining a semiconductor wafer 6 with a protective film.
- the protective film-forming film 1 may be heated before or after the ultraviolet irradiation.
- hardening of the protective film formation film 1 may be performed after a dicing process, and may be performed after picking up the chip
- the protective film-forming film 1 is excellent in ultraviolet curability when the light transmittance at a wavelength of 375 nm is 8% or more, the film is sufficiently cured as a whole by the above-described ultraviolet irradiation. Irradiation of the ultraviolet to the protection film forming film 1 is preferably 50 ⁇ 1000mJ / cm 2 in quantity, especially 100 ⁇ 500mJ / cm 2 preferably.
- the semiconductor wafer 6 with a protective film is diced according to a conventional method to obtain a chip having a protective film (chip with a protective film). Thereafter, the support sheet 4 is expanded in a plane direction as desired, and a chip with a protective film is picked up from the support sheet 4.
- the protective film forming film 1 (protective film) has a light transmittance of 12% or less at a wavelength of 550 nm, so that grinding marks due to back grinding are concealed by the protective film. Since it cannot be seen visually, it has an excellent appearance.
- the infrared light transmittance in the protective film forming film 1 is improved, and the chip with the protective film and the protective film are protected.
- the semiconductor wafer with a film can be subjected to infrared inspection through a protective film. Therefore, cracks and the like can be found by infrared inspection, and the product yield can be improved.
- FIG. 3 is a cross-sectional view of a composite sheet for protective film formation according to another embodiment of the present invention.
- the protective sheet-forming composite sheet 3 ⁇ / b> A includes a support sheet 4 in which an adhesive layer 42 is laminated on one surface of a base material 41, and an adhesive layer of the support sheet 4. And a protective film forming film 1 laminated on the 42 side.
- the protective film forming film 1 in the embodiment is formed to be substantially the same as or slightly larger than the workpiece in the surface direction, and smaller than the support sheet 4 in the surface direction.
- the part of the pressure-sensitive adhesive layer 42 where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.
- each member of the protective film-forming composite sheet 3A according to this embodiment are the same as the material and thickness of each member of the protective film-forming composite sheet 3 described above.
- the jig adhesive layer 5 of the protective film-forming composite sheet 3 described above and the peripheral portion of the pressure-sensitive adhesive layer 42 of the support sheet 4 of the protective film-forming composite sheet 3A on the side opposite to the base 41 are provided.
- a similar adhesive layer for jigs may be provided separately.
- the protective sheet-forming composite sheet 3A includes the base material 41, the pressure-sensitive adhesive layer 42 on the base material 41, the protective film-forming film 1 on the pressure-sensitive adhesive layer 42, and the pressure-sensitive adhesive layer 42. You may have the adhesive layer 5 for jig
- FIG. In this case, the support sheet 4 may consist only of the base material 41.
- the protective film-forming composite sheet 3 ⁇ / b> A is on the base material 41, the protective film-forming film 1 on the base material 41, and the base material 41, and the adhesive for jigs located at the peripheral edge of the protective film-forming film 1. You may have the agent layer 5.
- a peeling force adjusting layer may be provided between the pressure-sensitive adhesive layer 42 and the protective film forming film 1.
- the protective sheet-forming composite sheet 3A includes the base material 41, the adhesive layer 42 on the base material 41, the peeling force adjustment layer on the adhesive layer 42, and the protective film forming film on the peeling force adjustment layer. 1 may be included.
- peeling between a peeling force adjustment layer and the protective film formation film 1 can be performed easily.
- the adhesive layer 42 that does not need to consider the influence on the process of picking up the chip with the protective film (protective film forming film) is given strong adhesiveness, and the support sheet 4 is fixed to the jig. Can be made easy.
- the peeling force adjusting layer can be formed from, for example, an adhesive having a lower adhesive strength than the adhesive used for the adhesive layer 42, and can also be formed from a resin film (including a peel-treated one).
- a release sheet may be laminated on the opposite side of the protective film-forming film 1 of the protective film-forming composite sheets 3 and 3A from the support sheet 4.
- Example 1 The following components were mixed at a blending ratio (mass ratio; solid content conversion) shown in Table 1, and diluted with methyl ethyl ketone so that the solid content concentration became 54% by mass to prepare a coating agent for a protective film forming film. .
- UV curable component 80 parts by mass of 2-hydroxyethyl acrylate-derived hydroxyl group of acrylic polymer obtained by copolymerizing 80 parts by mass of 2-ethylhexyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate
- Acrylic polymer obtained by reacting an amount of methacryloyloxyethyl isocyanate corresponding to a mole and having an ultraviolet curable group introduced in the side chain (weight average molecular weight: 400,000, glass transition temperature: ⁇ 10 ° C.)
- Red colorant diketopyrrolopyrrole red pigment (manufactured by Sanyo Pigment, Pigment Red 264)
- Black colorant Carbon black (Mitsubishi Chemical Corporation, # MA600B, average particle size 28 nm)
- Filler Silica filler (manufactured by Admatechs, SC2050MA, average particle size 0.5 ⁇ m)
- Thermosetting component bisphenol A type
- a first release sheet (manufactured by Lintec: SP-PET3811, thickness 38 ⁇ m) having a silicone release agent layer formed on one side of a polyethylene terephthalate (PET) film, and a silicone release agent on one side of the PET film
- a second release sheet (made by Lintec: SP-PET 381031, thickness 38 ⁇ m) formed with a layer was prepared.
- the above-mentioned coating agent for protective film-forming film was applied with a knife coater and then dried in an oven at 120 ° C. for 2 minutes to form a protective film-forming film.
- the thickness of the obtained protective film-forming film was 25 ⁇ m.
- the release surface of the second release sheet is laminated on the protective film-forming film and bonded together, and the first release sheet (release sheet 21 in FIG. 1) and the protective film-forming film (protective film-forming film in FIG. 1). 1) A protective film-forming sheet composed of (thickness: 25 ⁇ m) and a second release sheet was obtained.
- Examples 2 and 3 Comparative Examples 1 and 2
- a protective film-forming sheet was produced in the same manner as in Example 1 except that the types and blending amounts of the components constituting the protective film-forming film were changed as shown in Table 1.
- a value W / T obtained by dividing the content W (% by mass) of the colorant in each example by the thickness T ( ⁇ m) of the protective film-forming film was calculated and is shown in Table 1.
- the light transmittance at any wavelength is almost 0%.
- the light transmittance at a wavelength of 375 nm is 8% or more
- the light transmittance at a wavelength of 550 nm is 12% or less
- the light transmittance at a wavelength of 1600 nm is 25% or more.
- the protective film-forming film was irradiated with ultraviolet light (irradiation conditions: illuminance 215 mW / cm 2 , light amount 187 mJ / cm 2 three times). Irradiation, no nitrogen purge), the protective film-forming film was cured to form a protective film. Then, the 1st peeling sheet was peeled and the silicon wafer with a protective film was obtained.
- the laminate including the protective film was cut into a 1 cm square, and the second release sheet was peeled off.
- a polyethylene terephthalate film (thickness: 25 ⁇ m) as a base material was bonded to the exposed protective film at room temperature using a roller laminator under conditions of 70 ° C. and 1.2 m / min.
- the 1st peeling sheet by the side of an ultraviolet irradiation side was peeled, and this was made into the 1st sample (for ultraviolet irradiation surface measurement).
- the laminate including the protective film was cut into a 1 cm square, and the first release sheet was peeled off.
- a polyethylene terephthalate film (thickness: 25 ⁇ m) as a base material was bonded to the exposed protective film at room temperature using a roller laminator under conditions of 70 ° C. and 1.2 m / min.
- the second release sheet on the side opposite to the ultraviolet irradiation was peeled off, and this was used as a second sample (for measuring the surface opposite to the ultraviolet irradiation).
- Probe tack value (peak value P1, energy value E1) of the exposed surface (ultraviolet irradiation surface) of the protective film in the first sample using a tacking tester (manufactured by Reska, RHESCA PROBE TACK TESTER model RPT100), and The probe tack value (peak value P2, energy value E2) of the exposed surface (surface opposite to the ultraviolet irradiation) of the protective film in the second sample was measured.
- the measurement conditions are as follows. Further, from the measurement results, a ratio P2 / P1 of the peak value P2 to the peak value P1 and a ratio E2 / E1 of the energy value E2 to the energy value E1 were calculated. The results are shown in Table 1. ⁇ Measurement conditions of probe tack value> ⁇ Speed: 600mm / sec ⁇ Pressing load: 0.98N ⁇ Pressing time: 1 second
- the probe tack value of the ultraviolet irradiation surface and the probe tack value of the surface opposite to the ultraviolet irradiation surface in the protective film forming film (protective film) obtained in the examples are approximate. From this, it can be seen that the protective film of the example is cured in the whole thickness direction from the ultraviolet irradiation surface to the ultraviolet irradiation opposite surface. Moreover, the protective film of an Example is excellent also in grinding trace concealment property.
- the protective film-forming film, the protective film-forming sheet and the protective film-forming composite sheet according to the present invention are suitably used for manufacturing a chip having a protective film from a semiconductor wafer.
Abstract
Description
本願は、2014年10月29日に、日本に出願された特願2014-220295号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a protective film-forming film, a protective film-forming sheet, and a protective film-forming film capable of forming a protective film on a workpiece such as a semiconductor wafer or a workpiece (for example, a semiconductor chip) obtained by processing the workpiece. It relates to a composite sheet.
This application claims priority based on Japanese Patent Application No. 2014-220295 filed in Japan on October 29, 2014, the contents of which are incorporated herein by reference.
〔保護膜形成フィルム〕
本実施形態に係る保護膜形成フィルムは、ワークまたは当該ワークを加工して得られる加工物に保護膜を形成するためのものである。ワークとしては、例えば半導体ウエハ等が挙げられ、当該ワークを加工して得られる加工物としては、例えば半導体チップが挙げられるが、本発明はこれらに限定されるものではない。なお、ワークが半導体ウエハの場合、保護膜は、半導体ウエハの裏面側(バンプ等の電極が形成されていない側)に形成される。 Hereinafter, embodiments of the present invention will be described.
[Protective film forming film]
The protective film-forming film according to this embodiment is for forming a protective film on a workpiece or a workpiece obtained by processing the workpiece. Examples of the workpiece include a semiconductor wafer, and examples of a workpiece obtained by processing the workpiece include a semiconductor chip. However, the present invention is not limited to these. When the work is a semiconductor wafer, the protective film is formed on the back side of the semiconductor wafer (the side on which no electrodes such as bumps are formed).
本実施形態に係る保護膜形成フィルムは、波長375nmの光線透過率が8%以上であり、波長550nmの光線透過率が12%以下であるものである。なお、本明細書における光線透過率は、積分球を使用して測定した値とし、測定器具としては分光光度計を使用する。 1. Physical Properties The protective film-forming film according to the present embodiment has a light transmittance of 8% or more at a wavelength of 375 nm and a light transmittance of 12% or less at a wavelength of 550 nm. The light transmittance in this specification is a value measured using an integrating sphere, and a spectrophotometer is used as a measuring instrument.
本実施形態に係る保護膜形成フィルムは、紫外線硬化性成分(A)を含有する。紫外線硬化性成分(A)は、好ましくは未硬化の紫外線硬化性成分であり、特に好ましくは粘着性を有する未硬化の紫外線硬化性成分である。 2. Material The protective film formation film which concerns on this embodiment contains an ultraviolet curable component (A). The ultraviolet curable component (A) is preferably an uncured ultraviolet curable component, and particularly preferably an uncured ultraviolet curable component having adhesiveness.
なお、保護膜形成フィルムが紫外線硬化性成分(A)および着色剤(B)を含む場合、紫外線硬化性成分(A)の割合と着色剤(B)の割合の合計が、100質量%となるよう紫外線硬化性成分(A)の割合と着色剤(B)の割合を設定する。同様に、保護膜形成フィルムが紫外線硬化性成分(A)、着色剤(B)およびフィラー(C)を含む場合、紫外線硬化性成分(A)の割合と着色剤(B)の割合とフィラー(C)の割合の合計が、100質量%となるよう紫外線硬化性成分(A)、着色剤(B)およびフィラー(C)の割合を設定する。保護膜形成フィルムが紫外線硬化性成分(A)、着色剤(B)、フィラー(C)および熱硬化性成分(D)を含む場合、紫外線硬化性成分(A)の割合と着色剤(B)の割合とフィラー(C)の割合と熱硬化性成分(D)との合計が、100質量%となるよう紫外線硬化性成分(A)、着色剤(B)、フィラー(C)および熱硬化性成分(D)の割合を設定する。 The protective film-forming film according to this embodiment preferably further contains a thermosetting component (D). By heating the protective film-forming film further containing the thermosetting component (D), the adhesive strength of the protective film-forming film to the work and the strength of the cured protective film can be improved.
In addition, when a protective film formation film contains an ultraviolet curable component (A) and a coloring agent (B), the sum total of the ratio of an ultraviolet curable component (A) and the ratio of a coloring agent (B) will be 100 mass%. The ratio of the ultraviolet curable component (A) and the ratio of the colorant (B) are set. Similarly, when the protective film-forming film contains an ultraviolet curable component (A), a colorant (B) and a filler (C), the proportion of the ultraviolet curable component (A), the proportion of the colorant (B) and the filler ( The ratio of the ultraviolet curable component (A), the colorant (B) and the filler (C) is set so that the total ratio of C) is 100% by mass. When the protective film-forming film contains an ultraviolet curable component (A), a colorant (B), a filler (C), and a thermosetting component (D), the ratio of the ultraviolet curable component (A) and the colorant (B) UV curable component (A), colorant (B), filler (C), and thermosetting so that the total of the proportion of the filler, the proportion of filler (C) and the thermosetting component (D) is 100% by mass. The proportion of component (D) is set.
紫外線硬化性成分(A)は、紫外線硬化性基が導入された重合体(A1)であってもよいし、紫外線硬化性基が導入された重合体(A1)を除く紫外線硬化性化合物(A3)を含有するものであってもよい。本実施形態における紫外線硬化性成分(A)が紫外線硬化性化合物(A3)を含有する場合には、紫外線硬化性を有しない重合体(A2)等の重合体をも含有することが好ましい。なお、本明細書における「重合体」には「共重合体」の概念も含まれるものとする。 (1) UV curable component (A)
The ultraviolet curable component (A) may be a polymer (A1) having an ultraviolet curable group introduced, or an ultraviolet curable compound (A3) excluding the polymer (A1) having an ultraviolet curable group introduced. ) May be contained. When the ultraviolet curable component (A) in this embodiment contains an ultraviolet curable compound (A3), it is preferable to also contain a polymer such as a polymer (A2) that does not have ultraviolet curable properties. In the present specification, the term “polymer” includes the concept of “copolymer”.
本実施形態における紫外線硬化性成分(A)が紫外線硬化性基が導入された重合体(A1)を含有する場合、かかる重合体(A1)は、保護膜形成フィルムにそのまま含有されていてもよく、また少なくともその一部が架橋剤と架橋反応を行って架橋物として含有されていてもよい。 (1-1) Polymer having ultraviolet curable group introduced (A1)
When the ultraviolet curable component (A) in this embodiment contains the polymer (A1) having an ultraviolet curable group introduced, the polymer (A1) may be contained as it is in the protective film-forming film. In addition, at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent.
本明細書において、モノマーが重合された物質に対して使用される、用語「重合体」又は「樹脂」等は、前記モノマーから導かれる構成単位(繰り返し単位ともいう)からなる「重合体」又は「樹脂」等を意味する。 The functional group-containing acrylic polymer (A1-1) is a copolymerization reaction product of an acrylic monomer containing a functional group, an acrylic monomer not containing a functional group, and, if desired, a monomer other than the acrylic monomer. It is preferable. That is, the functional group-containing monomer is preferably an acrylic monomer containing a functional group.
In the present specification, the term “polymer” or “resin” or the like used for a substance in which a monomer is polymerized is a “polymer” composed of structural units derived from the monomer (also referred to as repeating units) or It means “resin” or the like.
本実施形態における紫外線硬化性成分(A)が紫外線硬化性を有しない重合体(A2)を含有する場合、当該重合体(A2)は、保護膜形成フィルムにそのまま含有されていてもよく、また少なくともその一部が架橋剤と架橋反応を行って架橋物として含有されていてもよい。重合体(A2)としては、フェノキシ樹脂、アクリル系重合体(A2-1)、ウレタン樹脂、ポリエステル樹脂、ゴム系樹脂、アクリルウレタン樹脂等が挙げられる。これらのうち、アクリル系重合体(A2-1)を用いる場合について詳しく説明する。 (1-2) Polymer having no ultraviolet curing property (A2)
When the ultraviolet curable component (A) in this embodiment contains a polymer (A2) that does not have ultraviolet curable properties, the polymer (A2) may be contained as it is in the protective film-forming film, At least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent. Examples of the polymer (A2) include phenoxy resin, acrylic polymer (A2-1), urethane resin, polyester resin, rubber resin, acrylic urethane resin, and the like. Of these, the case of using the acrylic polymer (A2-1) will be described in detail.
紫外線硬化性成分(A)は、紫外線硬化性基が導入された重合体(A1)を除く紫外線硬化性化合物(A3)を含有するものであってもよく、この場合、上述した紫外線硬化性を有しない重合体(A2)を合わせて含有することが好ましい。また、紫外線硬化性を有しない重合体(A2)に代えて、またはこれと共に紫外線硬化性基が導入された重合体(A1)を含有していてもよい。紫外線硬化性化合物(A3)は、紫外線硬化性基を有し、紫外線の照射を受けると重合する化合物である。 (1-3) UV curable compound (A3)
The ultraviolet curable component (A) may contain an ultraviolet curable compound (A3) excluding the polymer (A1) into which an ultraviolet curable group is introduced. It is preferable to contain the polymer (A2) that is not included. Moreover, it may replace with the polymer (A2) which does not have ultraviolet curing property, or may contain the polymer (A1) by which the ultraviolet curing group was introduce | transduced with this. The ultraviolet curable compound (A3) is a compound having an ultraviolet curable group and polymerized when irradiated with ultraviolet rays.
着色剤(B)としては、例えば、無機系顔料、有機系顔料、有機系染料など公知のものを使用することができるが、光線透過率の制御性を高める観点から、着色剤(B)は有機系の着色剤であることが好ましい。上述したように、本実施形態に係る保護膜形成フィルムが備える特性または本実施形態に係る保護膜形成フィルムについて好ましい特性は、波長375nmの光線透過率が8%以上であり、波長550nmの光線透過率が12%以下である等、ある波長領域において、それよりも低い波長領域におけるよりも、低い光線透過率を示すという特性である。ここで、無機系の着色剤のみを用いた場合には、光線の波長が増加するにつれて、光線透過率が一次関数的に上昇していく傾向がある(後述する試験例1の結果・図5参照)。したがって、本実施形態に係る保護膜形成フィルムが無機系の着色剤のみを含有する場合には、本実施形態に係る保護膜形成フィルムに上記のような特性を付与することは必ずしも容易でない。一方、本実施形態に係る保護膜形成フィルムが有機系の着色剤を含有する場合には、本実施形態に係る保護膜形成フィルムを、上記のような特性を満たすものとすることが容易となる。また、着色剤の化学的安定性(具体的には、溶出しにくさ、色移りの生じにくさ、経時変化の少なさが例示される。)を高める観点から、着色剤(B)は顔料からなることが好ましい。したがって、本実施形態に係る保護膜形成フィルムが含有する着色剤(B)は、有機系顔料からなることが好ましい。なお、本実施形態に係る保護膜形成フィルムが含有する着色剤(B)は、複数種類の材料から構成されていてもよい。 (2) Colorant (B)
As the colorant (B), for example, known pigments such as inorganic pigments, organic pigments, and organic dyes can be used. From the viewpoint of improving the light transmittance, the colorant (B) is An organic colorant is preferred. As described above, the characteristics of the protective film-forming film according to this embodiment or the preferable characteristics of the protective film-forming film according to this embodiment are that the light transmittance at a wavelength of 375 nm is 8% or more and the light transmittance at a wavelength of 550 nm. The characteristic is that the light transmittance is lower in a certain wavelength region than in a lower wavelength region, such as a rate of 12% or less. Here, when only the inorganic colorant is used, the light transmittance tends to increase linearly as the wavelength of the light increases (results of Test Example 1 described later, FIG. 5). reference). Therefore, when the protective film-forming film according to this embodiment contains only an inorganic colorant, it is not always easy to impart the above properties to the protective film-forming film according to this embodiment. On the other hand, when the protective film-forming film according to this embodiment contains an organic colorant, the protective film-forming film according to this embodiment can easily satisfy the above-described characteristics. . Further, from the viewpoint of enhancing the chemical stability of the colorant (specifically, the elution is difficult, the color transfer is difficult to occur, and the change over time is exemplified), the colorant (B) is a pigment. Preferably it consists of. Therefore, the colorant (B) contained in the protective film-forming film according to the present embodiment is preferably composed of an organic pigment. In addition, the coloring agent (B) which the protective film formation film which concerns on this embodiment contains may be comprised from multiple types of material.
フィラー(C)としては、結晶シリカ、溶融シリカ、合成シリカ等のシリカや、アルミナ、ガラスバルーン等の無機フィラーが挙げられる。中でもシリカが好ましく、合成シリカがより好ましく、特に半導体装置の誤作動の要因となるα線の線源を極力除去したタイプの合成シリカが最適である。フィラー(C)の形状としては、球形、針状、不定形等が挙げられるが、球形であることが好ましく、特に真球形であることが好ましい。フィラーが球形または真球形であると、光線の乱反射が生じ難く、前述した赤外線検査を良好に行うことができる。ここで不定形とは、表面形状が不規則な形状を意味する。不定形の表面は、多面であってもよいし、一つの曲面であってもよい。表面が多面である場合、それぞれの面は、平面でも曲面でもよく、これらが混在していてもよい。また表面が多面である場合、それぞれの面の面積は、異なっていてよい。表面形状は突形状を有していてもよいし、凹形状を有していてもよい。 (3) Filler (C)
Examples of the filler (C) include silica such as crystalline silica, fused silica and synthetic silica, and inorganic filler such as alumina and glass balloon. Among these, silica is preferable, synthetic silica is more preferable, and synthetic silica of the type in which α-ray sources that cause malfunction of the semiconductor device are removed as much as possible is optimal. Examples of the shape of the filler (C) include a spherical shape, a needle shape, and an indefinite shape, but a spherical shape is preferable, and a true spherical shape is particularly preferable. When the filler is spherical or true spherical, irregular reflection of light hardly occurs, and the above-described infrared inspection can be performed satisfactorily. Here, the irregular shape means a shape having an irregular surface shape. The irregular surface may be multifaceted or a single curved surface. When the surface is polyhedral, each surface may be a flat surface or a curved surface, or these may be mixed. When the surface is multifaceted, the area of each face may be different. The surface shape may have a protruding shape or may have a concave shape.
熱硬化性成分(D)としては、例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ポリイミド樹脂、ベンゾオキサジン樹脂等およびこれらの混合物が挙げられる。これらの中でも、エポキシ樹脂、フェノール樹脂およびこれらの混合物が好ましく用いられる。 (4) Thermosetting component (D)
Examples of the thermosetting component (D) include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, benzoxazine resins, and mixtures thereof. Among these, an epoxy resin, a phenol resin, and a mixture thereof are preferably used.
本実施形態に係る保護膜形成フィルムは、光重合開始剤を含有してもよい。光重合開始剤を含有することにより、紫外線硬化性成分(A)の硬化時間および光線照射量を少なくすることができる。光重合開始剤は、紫外線硬化性成分(A)の質量に対し、0.1~15質量%であることが好ましい。 (5) Other components The protective film formation film which concerns on this embodiment may contain a photoinitiator. By containing a photopolymerization initiator, the curing time and the amount of light irradiation of the ultraviolet curable component (A) can be reduced. The photopolymerization initiator is preferably 0.1 to 15% by mass with respect to the mass of the ultraviolet curable component (A).
保護膜形成フィルムの厚さは、保護膜としての機能を効果的に発揮させるために、3~300μmであることが好ましく、特に5~200μmであることが好ましく、さらには7~100μmであることが好ましい。ここで、保護膜形成フィルムの厚さは、保護膜形成フィルムの任意の5箇所で、接触式厚み計で厚さを測定した平均で表される値である。なお保護膜形成フィルムの厚さを測定する際、直接に接触式厚み計を適用することが困難であるときは、基材フィルムや、後述する剥離材など、他のフィルムが重ね合わされた状態で、上記と同様に全体の厚さを測定し、重ね合わせられていた他のフィルムの厚さ(上記と同様の方法で測定したもの)との差分を取ることで算出してもよい。 3. Thickness The thickness of the protective film-forming film is preferably 3 to 300 μm, particularly preferably 5 to 200 μm, more preferably 7 to 100 μm, in order to effectively exert the function as a protective film. Preferably there is. Here, the thickness of a protective film formation film is the value represented by the average which measured thickness with the contact-type thickness meter in arbitrary five places of a protective film formation film. When measuring the thickness of the protective film-forming film, it is difficult to directly apply a contact-type thickness meter. In the state where other films such as a base film and a release material to be described later are overlaid. The total thickness may be measured in the same manner as described above, and may be calculated by taking the difference from the thickness of another film that has been overlaid (measured by the same method as described above).
図1は、本発明の一実施形態に係る保護膜形成用シートの断面図である。図1に示すように、本実施形態に係る保護膜形成用シート2は、保護膜形成フィルム1と、保護膜形成フィルム1の一方の面(図1では下側の面)に積層された剥離シート21とを備えて構成される。ただし、剥離シート21は、保護膜形成用シート2の使用時に剥離されるものである。 [Protective film forming sheet]
FIG. 1 is a cross-sectional view of a protective film forming sheet according to an embodiment of the present invention. As shown in FIG. 1, the protective film-forming sheet 2 according to this embodiment includes a protective film-forming
図2は、本発明の一実施形態に係る保護膜形成用複合シートの断面図である。図2に示すように、本実施形態に係る保護膜形成用複合シート3は、基材41の一方の面に粘着剤層42が積層されてなる支持シート4と、支持シート4の粘着剤層42側に積層された保護膜形成フィルム1と、保護膜形成フィルム1における支持シート4とは反対側の周縁部に積層された治具用粘着剤層5とを備えて構成される。言い換えれば、保護膜形成用複合シート3は、基材41と、基材41上の粘着剤層42と、粘着剤層42上の保護膜形成フィルム1と、保護膜形成フィルム1上の治具用粘着剤層5とを有する。治具用粘着剤層5は、保護膜形成フィルム1の表面の法線方向から見た場合における保護膜形成フィルム1の周縁部に位置する。治具用粘着剤層5は、保護膜形成用複合シート3をリングフレーム等の治具に接着するための層である。 [Composite sheet for protective film formation]
FIG. 2 is a cross-sectional view of a protective film-forming composite sheet according to an embodiment of the present invention. As shown in FIG. 2, the protective film-forming composite sheet 3 according to this embodiment includes a
本実施形態に係る保護膜形成用複合シート3の支持シート4は、基材41と、基材41の一方の面に積層された粘着剤層42とを備えて構成されてもよいが、支持シート4は、基材41のみからなるものであることが好ましい。この場合、本実施形態の保護膜形成フィルム1が紫外線照射により硬化すると、後述する保護膜形成用複合シートの使用方法の一例において、保護膜付きチップを支持シート4からピックアップすることが容易となるという利点がある。なお、支持シート4が基材41のみからなるものである場合、基材41にはプライマー層や帯電防止層、耐熱層、応力緩和層等が設けられていてもよい。 1. Support Sheet The
支持シート4の基材41は、ワークの加工、例えば半導体ウエハのダイシングおよびエキスパンディングに適するものであれば、その構成材料は特に限定されず、通常は樹脂系の材料を主材とするフィルム(以下「樹脂フィルム」という。)から構成される。 1-1. The
本実施形態に係る保護膜形成用複合シート3の支持シート4が備える粘着剤層42は、紫外線で硬化しないタイプの粘着剤(紫外線非硬化性粘着剤)または紫外線で硬化するタイプの粘着剤を予め硬化させた粘着剤から構成されることが好ましい。予め硬化されていない紫外線で硬化するタイプの粘着剤(紫外線硬化性粘着剤)の場合、保護膜形成フィルム1を硬化させる際に、保護膜形成用複合シート3に紫外線を照射すると、当該粘着剤層42が含有する成分の一つ以上が通常有する紫外線硬化性基と、保護膜形成フィルム1の紫外線硬化性成分(A)が有する紫外線硬化性基とが反応し、粘着剤層42と保護膜形成フィルム1との間で両者を剥離することが困難となる懸念がある。 1-2. The pressure-sensitive adhesive layer The pressure-
保護膜形成用複合シート3は、好ましくは、保護膜形成フィルム1を含む第1の積層体と、支持シート4を含む第2の積層体とを別々に作製した後、第1の積層体および第2の積層体を使用して、保護膜形成フィルム1と支持シート4とを積層することにより製造することができるが、これに限定されるものではない。 2. Method for Producing Protective Film-Forming Composite Sheet Preferably, the protective film-forming composite sheet 3 is prepared separately from a first laminate including the protective film-forming
本実施形態に係る保護膜形成用複合シート3を用いて、一例としてワークとしての半導体ウエハから保護膜付きチップを製造する方法を以下に説明する。 3. Method for Using Protective Film Forming Composite Sheet A method for producing a chip with a protective film from a semiconductor wafer as a workpiece by using the protective film forming composite sheet 3 according to this embodiment will be described below.
図3は、本発明の他の実施形態に係る保護膜形成用複合シートの断面図である。図3に示すように、本実施形態に係る保護膜形成用複合シート3Aは、基材41の一方の面に粘着剤層42が積層されてなる支持シート4と、支持シート4の粘着剤層42側に積層された保護膜形成フィルム1とを備えて構成される。実施形態における保護膜形成フィルム1は、面方向にてワークとほぼ同じか、ワークよりも少し大きく形成されており、かつ支持シート4よりも面方向に小さく形成されている。保護膜形成フィルム1が積層されていない部分の粘着剤層42は、リングフレーム等の治具に貼付することが可能となっている。 4). Other Embodiment of Composite Sheet for Protective Film Formation FIG. 3 is a cross-sectional view of a composite sheet for protective film formation according to another embodiment of the present invention. As shown in FIG. 3, the protective sheet-forming composite sheet 3 </ b> A according to this embodiment includes a
次の各成分を表1に示す配合比(質量比;固形分換算)で混合し、固形分濃度が54質量%となるようにメチルエチルケトンで希釈して、保護膜形成フィルム用塗布剤を調製した。
(a)紫外線硬化性成分:2-エチルヘキシルアクリレート80質量部および2-ヒドロキシエチルアクリレート20質量部を共重合してなるアクリル系重合体の2-ヒドロキシエチルアクリレート由来の水酸基100モルに対して、80モルに相当する量のメタクリロイルオキシエチルイソシアネートを反応させて得られた、側鎖に紫外線硬化性基が導入されたアクリル系重合体(重量平均分子量:40万,ガラス転移温度:-10℃)
(b1)赤色着色剤:ジケトピロロピロール系赤色色素(山陽色素社製,Pigment Red264)
(b2)黒色着色剤:カーボンブラック(三菱化学社製,#MA600B,平均粒径28nm)
(c)フィラー:シリカフィラー(アドマテックス社製,SC2050MA,平均粒径0.5μm)
(d)熱硬化性成分:ビスフェノールA型エポキシ樹脂(三菱化学社製,JER828,エポキシ当量183~194g/eq)
(e)光重合開始剤:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製, イルガキュア184) [Example 1]
The following components were mixed at a blending ratio (mass ratio; solid content conversion) shown in Table 1, and diluted with methyl ethyl ketone so that the solid content concentration became 54% by mass to prepare a coating agent for a protective film forming film. .
(A) UV curable component: 80 parts by mass of 2-hydroxyethyl acrylate-derived hydroxyl group of acrylic polymer obtained by copolymerizing 80 parts by mass of 2-ethylhexyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate Acrylic polymer obtained by reacting an amount of methacryloyloxyethyl isocyanate corresponding to a mole and having an ultraviolet curable group introduced in the side chain (weight average molecular weight: 400,000, glass transition temperature: −10 ° C.)
(B1) Red colorant: diketopyrrolopyrrole red pigment (manufactured by Sanyo Pigment, Pigment Red 264)
(B2) Black colorant: Carbon black (Mitsubishi Chemical Corporation, # MA600B, average particle size 28 nm)
(C) Filler: Silica filler (manufactured by Admatechs, SC2050MA, average particle size 0.5 μm)
(D) Thermosetting component: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828, epoxy equivalent 183 to 194 g / eq)
(E) Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, Irgacure 184)
保護膜形成フィルムを構成する各成分の種類および配合量を表1に示すように変更する以外、実施例1と同様にして保護膜形成用シートを製造した。
なお、各例における着色剤の含有量W(質量%)を、保護膜形成フィルムの厚さT(μm)で除した値W/Tを算出し、これを表1に示した。 [Examples 2 and 3, Comparative Examples 1 and 2]
A protective film-forming sheet was produced in the same manner as in Example 1 except that the types and blending amounts of the components constituting the protective film-forming film were changed as shown in Table 1.
A value W / T obtained by dividing the content W (% by mass) of the colorant in each example by the thickness T (μm) of the protective film-forming film was calculated and is shown in Table 1.
実施例および比較例で得られた保護膜形成用シートから第2の剥離シートを剥離し、70℃、1.2m/minの条件で、ローラー式ラミネーターでガラス板にラミネートした。その後、第1の剥離シートを剥離して、これを測定用サンプルとした。 [Test Example 1] <Measurement of light transmittance>
The second release sheet was peeled from the protective film-forming sheets obtained in Examples and Comparative Examples, and laminated on a glass plate with a roller laminator under the conditions of 70 ° C. and 1.2 m / min. Then, the 1st peeling sheet was peeled and this was made into the sample for a measurement.
実施例および比較例で得られた保護膜形成用シートから第2の剥離シートを剥離し、保護膜形成フィルムを露出させた。#2000研磨したシリコンウエハ(直径200mm,厚さ350μm)の研磨面に、上記保護膜形成フィルムを、テープマウンター(リンテック社製 Adwill RAD-3600 F/12)を用いて70℃に加熱しながら貼付した。 [Test Example 2] <Evaluation of grinding mark concealment>
The second release sheet was peeled from the protective film-forming sheets obtained in the examples and comparative examples to expose the protective film-forming film. The above protective film-forming film is applied to a polished surface of a # 2000 polished silicon wafer (diameter 200 mm, thickness 350 μm) while heating to 70 ° C. using a tape mounter (Adwill RAD-3600 F / 12, manufactured by Lintec). did.
紫外光照射機(リンテック社製,ADWILL RAD-2000)を用いて、実施例および比較例で得られた保護膜形成用シートの第1の剥離シート側から、当該保護膜形成用シートに対して紫外線を照射し(照射条件:照度215mW/cm2、光量187mJ/cm2で3回照射,窒素パージなし)、保護膜形成フィルムを硬化させて保護膜とした。 [Test Example 3] <Measurement of probe tack>
From the first release sheet side of the protective film forming sheets obtained in Examples and Comparative Examples, using an ultraviolet light irradiation machine (manufactured by Lintec, ADWILL RAD-2000), the protective film forming sheet Ultraviolet rays were irradiated (irradiation conditions: illuminance 215 mW / cm 2 , irradiation with light intensity 187 mJ / cm 2 three times, no nitrogen purge), and the protective film forming film was cured to form a protective film.
<プローブタック値の測定条件>
・スピード:600mm/sec
・押し付け荷重:0.98N
・押し付け時間:1秒 Probe tack value (peak value P1, energy value E1) of the exposed surface (ultraviolet irradiation surface) of the protective film in the first sample using a tacking tester (manufactured by Reska, RHESCA PROBE TACK TESTER model RPT100), and The probe tack value (peak value P2, energy value E2) of the exposed surface (surface opposite to the ultraviolet irradiation) of the protective film in the second sample was measured. The measurement conditions are as follows. Further, from the measurement results, a ratio P2 / P1 of the peak value P2 to the peak value P1 and a ratio E2 / E1 of the energy value E2 to the energy value E1 were calculated. The results are shown in Table 1.
<Measurement conditions of probe tack value>
・ Speed: 600mm / sec
・ Pressing load: 0.98N
・ Pressing time: 1 second
2…保護膜形成用シート
21…剥離シート
3,3A…保護膜形成用複合シート
4…支持シート
41…基材
42…粘着剤層
5…治具用粘着剤層
6…半導体ウエハ
7…リングフレーム DESCRIPTION OF
Claims (10)
- 紫外線硬化性成分を含有し、
波長375nmの光線透過率が8%以上であり、
波長550nmの光線透過率が12%以下である保護膜形成フィルム。 Contains UV curable ingredients,
The light transmittance at a wavelength of 375 nm is 8% or more,
A protective film-forming film having a light transmittance of 12% or less at a wavelength of 550 nm. - 着色剤をさらに含有する請求項1に記載の保護膜形成フィルム。 The protective film-forming film according to claim 1, further comprising a colorant.
- 前記着色剤が、赤色着色剤である請求項2に記載の保護膜形成フィルム。 The protective film-forming film according to claim 2, wherein the colorant is a red colorant.
- 前記着色剤が、有機系の着色剤である請求項2または3に記載の保護膜形成フィルム。 The protective film-forming film according to claim 2 or 3, wherein the colorant is an organic colorant.
- 前記保護膜形成フィルムにおける前記着色剤の含有量W(質量%)を、前記保護膜形成フィルムの厚さT(μm)で除した値W/Tが、0.01~0.5である請求項2~4のいずれか一項に記載の保護膜形成フィルム。 A value W / T obtained by dividing the content W (% by mass) of the colorant in the protective film-forming film by the thickness T (μm) of the protective film-forming film is 0.01 to 0.5. Item 5. The protective film-forming film according to any one of Items 2 to 4.
- 前記保護膜形成フィルムに対し一方の面側から、照度215mW/cm2、光量187mJ/cm2の紫外線を3回照射した場合に、紫外線照射面のプローブタックのピーク値P1に対する前記紫外線照射面とは反対側の面のプローブタックのピーク値P2の比P2/P1が、0.1~7となる請求項1~5のいずれか一項に記載の保護膜形成フィルム。 When the ultraviolet ray having an illuminance of 215 mW / cm 2 and a light amount of 187 mJ / cm 2 is irradiated from the one surface side to the protective film forming film three times, the ultraviolet irradiation surface with respect to the peak value P1 of the probe tack on the ultraviolet irradiation surface; 6. The protective film-forming film according to claim 1, wherein the ratio P2 / P1 of the probe tack peak value P2 on the opposite side surface is 0.1 to 7.
- 波長1600nmの光線透過率が25%以上である請求項1~6のいずれか一項に記載の保護膜形成フィルム。 The protective film-forming film according to any one of claims 1 to 6, wherein the light transmittance at a wavelength of 1600 nm is 25% or more.
- 請求項1~7のいずれか一項に記載の保護膜形成フィルムと、
前記保護膜形成フィルムの一方の面または両面に積層された剥離シートとを備える保護膜形成用シート。 A protective film-forming film according to any one of claims 1 to 7;
A protective film-forming sheet comprising a release sheet laminated on one or both surfaces of the protective film-forming film. - 支持シートと、
前記支持シートの一方の面側に積層された請求項1~7のいずれか一項に記載の保護膜形成フィルムと
を備える保護膜形成用複合シート。 A support sheet;
A composite sheet for forming a protective film, comprising the protective film-forming film according to any one of claims 1 to 7 laminated on one surface side of the support sheet. - 前記支持シートは、基材と前記基材の前記保護膜形成フィルム側に積層された粘着剤層とからなるか、基材からなる請求項9に記載の保護膜形成用複合シート。 The composite sheet for forming a protective film according to claim 9, wherein the support sheet includes a base material and an adhesive layer laminated on the protective film forming film side of the base material or a base material.
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Also Published As
Publication number | Publication date |
---|---|
JP6585068B2 (en) | 2019-10-02 |
JPWO2016068042A1 (en) | 2017-08-10 |
KR102467143B1 (en) | 2022-11-14 |
TWI671338B (en) | 2019-09-11 |
TW201620963A (en) | 2016-06-16 |
CN113980535A (en) | 2022-01-28 |
SG11201703250YA (en) | 2017-05-30 |
CN107112219A (en) | 2017-08-29 |
KR20170078630A (en) | 2017-07-07 |
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