WO2014092200A1 - Film constituant une membrane de retenue - Google Patents

Film constituant une membrane de retenue Download PDF

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Publication number
WO2014092200A1
WO2014092200A1 PCT/JP2013/083628 JP2013083628W WO2014092200A1 WO 2014092200 A1 WO2014092200 A1 WO 2014092200A1 JP 2013083628 W JP2013083628 W JP 2013083628W WO 2014092200 A1 WO2014092200 A1 WO 2014092200A1
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Prior art keywords
protective film
film
forming
curing
mass
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PCT/JP2013/083628
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English (en)
Japanese (ja)
Inventor
尚哉 佐伯
山本　大輔
高野　健
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2014552108A priority Critical patent/JP6270736B2/ja
Priority to KR1020157014737A priority patent/KR102152605B1/ko
Priority to CN201380064452.XA priority patent/CN104837942B/zh
Publication of WO2014092200A1 publication Critical patent/WO2014092200A1/fr

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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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a protective film-forming film capable of forming a protective film on a semiconductor wafer or a semiconductor chip and improving the manufacturing efficiency of the semiconductor chip.
  • the present invention relates to a protective film forming film used for manufacturing a semiconductor chip to be mounted by a so-called face-down method.
  • chip a semiconductor chip having electrodes such as bumps on a circuit surface
  • the electrodes are bonded to a substrate.
  • the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.
  • the exposed chip back surface may be protected by an organic film.
  • a chip having a protective film made of an organic film is obtained by applying a liquid resin to the back surface of a wafer by spin coating, drying and curing, and cutting the protective film together with the wafer.
  • the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.
  • Patent Document 1 an energy ray curable chip protecting film formed on a release sheet is disclosed.
  • the chip protective film with a smooth surface after curing is obtained by temporarily fixing a support with a smooth surface to the exposed surface of the chip protective film affixed to the wafer or chip, and peeling the support after curing. can get. That is, by curing the chip protection film in a state where the chip protection film is temporarily fixed to a support having a smooth surface, deformation on the surface of the chip protection film due to the curing reaction can be suppressed. If the film for chip protection after curing is peeled off from the support, the smoothness of the support is transferred to the film for chip protection after curing, and the same surface shape as the chip back surface without using the conventional film for chip protection Can be imparted to the chip protection film after curing. As a result, the visibility of characters and the like laser-printed on the cured chip protection film is improved.
  • An object of the present invention is to provide a protective film-forming film that is easy to peel off from a support after curing the protective film-forming film temporarily fixed to the support and has excellent adhesive strength with a chip. .
  • the present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above-mentioned problems can be solved by giving a difference in the adhesive force on each surface of the protective film-forming film after curing, and have completed the present invention.
  • the gist of the present invention is as follows. [1] A curable protective film-forming film having a first surface and a second surface, A film for forming a protective film, wherein the adhesive force of the first surface after curing to the silicon wafer is higher than the adhesive force of the second surface to the silicon wafer after curing.
  • the resin layer including at least the second surface contains a release agent, and the content of the release agent in the resin layer including the second surface is greater than the content of the release agent in the resin layer including the first surface [ 7]
  • the content of the release agent in the resin layer including the first surface is 0 to 0.001 with respect to 100 parts by mass of the solid content excluding the release agent out of the total solids constituting the resin layer including the first surface.
  • Mass part The content of the release agent in the resin layer including the second surface is 0.001 to 20 parts by mass with respect to 100 parts by mass of the solid content excluding the release agent out of the total solids constituting the resin layer including the second surface.
  • the protective film-forming film is cured with the support temporarily fixed, it is easy to peel off from the support, and the cured protective film-forming film peels off from the wafer or chip. There is nothing. Therefore, desired smoothness can be imparted to the surface of the protective film-forming film after curing. As a result, the visibility of characters and the like laser-printed on the cured protective film-forming film is improved.
  • Sectional drawing of the film for protective film formation concerning this invention is shown.
  • the 1st aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown.
  • the 2nd aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown.
  • 3rd aspect of the composite sheet for protective film formation formed using the film for protective film formation which concerns on this invention is shown.
  • 4th aspect of the composite sheet for protective film formation formed using the film for protective film formation which concerns on this invention is shown.
  • the schematic of the evaluation method of the removability in the 2nd surface of the film for protective film formation concerning this invention is shown.
  • the schematic of the evaluation method of the adhesive force of the film for protective film formation concerning this invention is shown.
  • the protective film-forming film 10 has a first surface a and a second surface b, and the adhesive force of the first surface a after curing to the silicon wafer is the second surface b after curing. It is higher than the adhesive strength to silicon wafers.
  • the protective film-forming film is cured with its first surface attached to an adherend such as a semiconductor wafer or semiconductor chip. For this reason, it may be difficult to maintain the smoothness of the exposed second surface due to deformation due to the curing reaction.
  • the smoothness of the second surface of the cured film for forming a protective film decreases, the visibility of characters laser-printed on the second surface of the protective film decreases in the subsequent laser printing step. There was a thing.
  • the protective film forming film 10 is cured, if a silicon wafer or the like is temporarily fixed as a support for imparting smoothness to the second surface, for example, the surface of the silicon wafer is provided on the second surface b. The shape is transferred. For this reason, the surface shape comparable as a chip
  • tip back surface can be provided to the 2nd surface b of a protective film.
  • a silicon wafer or the like may be attached to the first surface a of the protective film forming film 10 as an adherend for forming the protective film, for example, and the second of the protective film forming film as described above.
  • the silicon wafer or the like temporarily fixed to the second surface b of the cured protective film forming film can be easily peeled off. There is a need.
  • the first surface a has a higher adhesive force to the silicon wafer from the first surface a after curing than the second surface b to the silicon wafer after curing.
  • an adherend such as a silicon wafer is affixed to the second surface b, and a protective film forming film is cured by temporarily fixing a support such as a silicon wafer to the second surface b, the deformation caused by the curing reaction on the second surface b Is suppressed, and it becomes easy to peel the support from the second surface b.
  • the smoothness of the support surface can be transferred to the second surface b, so that the smoothness of the second surface b after curing is improved and laser printing is performed.
  • a protective film excellent in the visibility of the written characters can be formed on the adherend.
  • the ratio of the adhesive force of the first surface to the silicon wafer after curing and the adhesive force of the second surface to the silicon wafer after curing is Preferably, it is 1.2 to 100, more preferably 1.3 to 50, still more preferably 1.5 to 30, and particularly preferably 3 to 20.
  • the ratio of the adhesive forces is smaller than 1.2, since the difference in adhesive strength between the first surface and the second surface after curing is small, when peeling the support from the second surface b, the first surface a The adherend may also peel off.
  • the ratio of the adhesive strength is larger than 100, the adhesive strength to the support is insufficient, and the protective film-forming film may be peeled off from the support during the curing of the protective film-forming film.
  • the adhesive strength of the second surface to the silicon wafer after curing is preferably 0.01 to 100N, more preferably 0.05 to 20N, still more preferably 0.1 to 5N, and particularly preferably 0.4 to 5N. It is.
  • adhesive force is the adhesive force of the chip
  • the probe tack value on the second surface of the protective film-forming film is preferably 0.01 to 3 N / 5 mm ⁇ , more preferably 0.1 to 1.5 N / 5 mm ⁇ , and still more preferably 0.3 to 1. .5N / 5mm ⁇ .
  • the probe tack value on the second surface is the probe tack value of the protective film-forming film before curing measured with a 70 ° C. probe, and is specifically measured by the measurement method in the examples described later.
  • a method for producing a protective film-forming film having the above physical properties two or more resin layers having different compositions are obtained by changing the composition of each component constituting the protective film-forming film, and the resin layers are laminated.
  • a method of inclining the composition in the thickness direction (providing a concentration gradient) in a single-layer protective film forming film; heating and / or energy irradiation of only the second surface in advance to make it a semi-cured state And a method of reducing the adhesive force on the second surface to obtain a protective film-forming film.
  • the film for protective film formation of this invention is the structure which laminates
  • the adhesive layer is not particularly limited as long as it does not impair the object of the present invention.
  • At least the functions required for the protective film-forming film are (1) sheet shape maintenance, (2) initial adhesiveness, and (3) curability.
  • the protective film-forming film can be provided with (1) sheet shape maintainability and (3) curability by adding a binder component.
  • the binder component the polymer component (A) and the curable component (B ) Containing the first binder component or the second binder component containing the curable polymer component (AB) having the properties of the component (A) and the component (B).
  • it is a function for temporarily attaching the protective film-forming film to the adherend until it is cured.
  • the initial adhesiveness may be pressure-sensitive adhesiveness, and is softened and bonded by heat. It may be a property to do.
  • the initial adhesiveness is usually controlled by adjusting various properties of the binder component and adjusting the blending amount of the inorganic filler (C) described later.
  • a 1st binder component provides a sheet
  • the 1st binder component does not contain a curable polymer component (AB) for the convenience of distinguishing from a 2nd binder component.
  • the polymer component (A) is added to the protective film-forming film mainly for the purpose of imparting sheet shape maintenance to the protective film-forming film.
  • the weight average molecular weight (Mw) of the polymer component (A) is usually 20,000 or more, preferably 20,000 to 3,000,000.
  • the value of the weight average molecular weight (Mw) is a value when measured by a gel permeation chromatography method (GPC) method (polystyrene standard).
  • the measurement by such a method is carried out, for example, by using a high-speed GPC apparatus “HLC-8120GPC” manufactured by Tosoh Corporation and a high-speed column “TSK gold column H XL- H”, “TSK Gel GMH XL ”, “TSK Gel G2000 H XL ”. (The above, all manufactured by Tosoh Corporation) are connected in this order, and the detector is used as a differential refractometer at a column temperature of 40 ° C. and a liquid feed rate of 1.0 mL / min.
  • the polymer component (A) does not have a curing functional functional group described later.
  • an acrylic polymer obtained by reacting a urethane prepolymer having an isocyanate group at a molecular terminal with an acrylic polyol which is an acrylic polymer having a hydroxyl group, which is a combination of two or more of these. May be. Furthermore, two or more of these may be used in combination, including a polymer in which two or more are bonded.
  • acrylic polymer (A1) As the acrylic polymer polymer component (A), acrylic polymer (A1) is preferably used.
  • the glass transition temperature (Tg) of the acrylic polymer (A1) is preferably in the range of ⁇ 60 to 50 ° C., more preferably ⁇ 50 to 40 ° C., and further preferably ⁇ 40 to 30 ° C. When the glass transition temperature of the acrylic polymer (A1) is high, the probe tack value of the protective film-forming film tends to decrease, and the adhesiveness after curing tends to decrease.
  • the glass transition temperature (Tg) of the acrylic polymer (A1) used for the resin layer containing the 2nd surface b ) Is particularly preferably in the range of ⁇ 40 to ⁇ 5 ° C.
  • the weight average molecular weight of the acrylic polymer (A1) is preferably 100,000 to 1,500,000.
  • the weight average molecular weight of the acrylic polymer (A1) is high, the probe tack value of the protective film-forming film tends to decrease, and the adhesiveness after curing tends to decrease. Since there exists such a tendency, when forming the film for protective film formation from two or more resin layers, the weight average molecular weight of the acrylic polymer (A1) used for the resin layer containing the 2nd surface b is 600. More preferably, it is from 1,000 to 1,200,000.
  • the acrylic polymer (A1) contains (meth) acrylic acid ester in at least a constituent monomer.
  • (meth) acrylic acid esters include alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms, specifically methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, etc .; (meth) acrylate having a cyclic skeleton, specifically cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ( Examples include meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate. Moreover, what is (meth
  • (meth) acryl may be used in the meaning including both acryl and methacryl.
  • a monomer having a hydroxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • a monomer having a hydroxyl group may be used.
  • the monomer having a hydroxyl group include (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxylethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-methylol (meth) acrylamide and the like.
  • a monomer having a carboxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • a carboxyl group is introduced into the acrylic polymer (A1), and the protective film-forming film contains an energy ray-curable component (B2) separately, and this is acrylic. Compatibility with the system polymer (A1) is improved.
  • the monomer having a carboxyl group include (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid.
  • an epoxy-based thermosetting component as the curable component (B) described below, the carboxyl group and the epoxy group in the epoxy-based thermosetting component react with each other. The amount used is preferably small.
  • a monomer having an amino group may be used as a monomer constituting the acrylic polymer (A1).
  • a monomer having an amino group examples include (meth) acrylic acid esters having an amino group such as monoethylamino (meth) acrylate.
  • the monomer constituting the acrylic polymer (A1) vinyl acetate, styrene, ethylene, ⁇ -olefin and the like may be used.
  • the acrylic polymer (A1) may be cross-linked.
  • Crosslinking is performed by adding a crosslinking agent to the composition for forming a protective film-forming film, in which the acrylic polymer (A1) before being crosslinked has a crosslinkable functional group such as a hydroxyl group. This is performed by reacting the crosslinkable functional group with the functional group of the crosslinker.
  • the cohesive force of the protective film-forming film can be adjusted.
  • crosslinking agent examples include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
  • organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds.
  • examples thereof include terminal isocyanate urethane prepolymers obtained by reacting with a polyol compound.
  • organic polyvalent isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-.
  • organic polyvalent imine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylol. Mention may be made of methane-tri- ⁇ -aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine.
  • the crosslinking agent is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer (A1) before crosslinking. Used in ratio.
  • the polymer component (A) when the content of the component constituting the protective film-forming film is determined based on the content of the polymer component (A), the polymer component (A) is a crosslinked acrylic polymer. In some cases, the reference content is the content of the acrylic polymer before being crosslinked.
  • Non-acrylic resin In addition, as the polymer component (A), polyester, phenoxy resin (for the purpose of distinguishing from the curable polymer (AB) described later, limited to those having no epoxy group), polycarbonate, poly One type of non-acrylic resin (A2) selected from ethers, polyurethanes, polysiloxanes, rubber polymers, or a combination of two or more of these may be used, or a combination of two or more types. Such a resin preferably has a weight average molecular weight of 20,000 to 100,000, more preferably 20,000 to 80,000.
  • the glass transition temperature of the non-acrylic resin (A2) is preferably in the range of ⁇ 30 to 150 ° C., more preferably in the range of ⁇ 20 to 120 ° C.
  • the protective film-forming film is transferred to the adherend using the protective film-forming composite sheet described later.
  • delamination between the support sheet and the protective film-forming film can be easily performed, and furthermore, the protective film-forming film follows the transfer surface, and generation of voids can be suppressed.
  • the content of the non-acrylic resin (A2) is such that the non-acrylic resin (A2) and the acrylic polymer (
  • the mass ratio (A2: A1) to A1) is usually in the range of 1:99 to 60:40, preferably 1:99 to 30:70.
  • the content of the non-acrylic resin (A2) is in this range, the above effect can be obtained.
  • the curable component (B) is added to the protective film-forming film mainly for the purpose of imparting curability to the protective film-forming film.
  • a thermosetting component (B1) or an energy beam curable component (B2) can be used. Moreover, you may use combining these.
  • the thermosetting component (B1) contains at least a compound having a functional group that reacts by heating.
  • the energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by irradiation with energy rays, and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams.
  • Curing is realized by the functional groups of these curable components reacting to form a three-dimensional network structure. Since the curable component (B) is used in combination with the polymer component (A), the viscosity of the coating composition for forming the protective film-forming film is suppressed, and the handleability is improved. Usually, its weight average molecular weight (Mw) is 10,000 or less, preferably 100 to 10,000.
  • thermosetting component for example, an epoxy thermosetting component is preferable.
  • the epoxy thermosetting component preferably contains a compound (B11) having an epoxy group and a combination of a compound (B11) having an epoxy group and a thermosetting agent (B12).
  • epoxy compound (B11) Compound having an epoxy group
  • a conventionally known compound can be used. Specifically, polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as epoxy resins and phenylene skeleton type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.
  • the protective film-forming film preferably contains 1 to 1500 parts by mass of the epoxy compound (B11) with respect to 100 parts by mass of the polymer component (A).
  • the content is preferably 3 to 1200 parts by mass.
  • the resin layer containing the second surface b is a solid at room temperature as an epoxy compound (B11).
  • an epoxy compound (B11) it is particularly preferable that 70 to 150 parts by mass of the epoxy compound (B11) is contained with respect to 100 parts by mass of the polymer component (A).
  • thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11).
  • a preferable thermosetting agent includes a compound having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.
  • phenolic curing agent examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zylock type phenolic resins, and aralkylphenolic resins.
  • amine curing agent is DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the thermosetting agent (B12) is preferably 0.1 to 500 parts by mass and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy compound (B11). When there is little content of a thermosetting agent, there exists a tendency for the adhesiveness after hardening to fall.
  • Curing accelerator A curing accelerator (B13) may be used to adjust the rate of thermal curing of the protective film-forming film.
  • the curing accelerator (B13) is particularly preferably used when an epoxy thermosetting component is used as the thermosetting component (B1).
  • Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. These can be used individually by 1 type or in mixture of 2 or more types.
  • the curing accelerator (B13) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). Included in the amount of.
  • the curing accelerator (B13) By containing the curing accelerator (B13) in an amount within the above range, it has excellent adhesiveness even when exposed to high temperatures and high humidity, and has high reliability even when exposed to severe reflow conditions. Can be achieved.
  • the adhesiveness after curing of the protective film-forming film can be improved. Such an action becomes stronger as the content of the curing accelerator (B13) increases.
  • the film for forming the protective film includes an energy beam curable component, so that the film for forming the protective film is cured without performing a heat curing step that requires a large amount of energy and a long time. Can do. Thereby, the manufacturing cost can be reduced.
  • the energy ray-curable component the compound (B21) having a functional group that reacts by irradiation with energy rays may be used alone, but the compound (B21) having a functional group that reacts by irradiation with energy rays and a photopolymerization initiator ( It is preferable to use a combination of B22).
  • (B21) Compound having a functional group that reacts upon irradiation with energy rays
  • Compound (B21) having a functional group that reacts upon irradiation with energy rays (hereinafter sometimes referred to as “energy ray-reactive compound (B21)”)
  • energy ray-reactive compound (B21) trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate
  • Examples include acrylate compounds such as acrylates, oligoester acrylates, urethane acrylate oligomers, epoxy acrylates, polyether acrylates, and esters.
  • the energy ray reactive compound (B21) is preferably 1 to 1500 parts by mass with respect to 100 parts by mass of the polymer component (A) in the protective film-forming film. Contained, more preferably 3 to 1200 parts by mass.
  • photopolymerization initiator (B22) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal.
  • a photoinitiator (B22) can be used individually by 1 type or in combination of 2 or more types.
  • the blending ratio of the photopolymerization initiator (B22) is preferably 0.1 to 10 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy ray reactive compound (B21). . If the blending ratio of the photopolymerization initiator (B22) is less than 0.1 parts by mass, sufficient curability may not be obtained due to insufficient photopolymerization, and if it exceeds 10 parts by mass, the residue does not contribute to photopolymerization. May cause a malfunction.
  • a 2nd binder component provides sheet shape maintenance property and curability to the film for protective film formation by containing a curable polymer component (AB).
  • the curable polymer component is a polymer having a functional functional group.
  • the curing functional group is a functional group that can react with each other to form a three-dimensional network structure, and examples thereof include a functional group that reacts by heating and a functional group that reacts by energy rays.
  • the functional functional group may be added to the unit of a continuous structure that becomes the skeleton of the curable polymer (AB) or may be added to the terminal. When the functional functional group is added in the unit of the continuous structure that becomes the skeleton of the curable polymer component (AB), the functional functional group may be added to the side chain or directly to the main chain. You may do it.
  • the weight average molecular weight (Mw) of the curable polymer component (AB) is usually 20,000 or more from the viewpoint of achieving the purpose of imparting sheet shape maintainability to the protective film-forming film.
  • an example of a functional group that reacts by heating is an epoxy group.
  • the curable polymer component (AB) having an epoxy group include a high molecular weight epoxy group-containing compound and a phenoxy resin having an epoxy group.
  • it is a polymer similar to the above-mentioned acrylic polymer (A1), which is polymerized using a monomer having an epoxy group as a monomer (epoxy group-containing acrylic polymer). Also good.
  • monomers include (meth) acrylic acid esters having a glycidyl group such as glycidyl (meth) acrylate.
  • the preferred embodiment is the same as that of the acrylic polymer (A1).
  • thermosetting agent (B12) or the curing accelerator (B13) is used as in the case of using an epoxy thermosetting component as the curable component (B). ) May be used in combination.
  • Examples of the functional group that reacts with energy rays include a (meth) acryloyl group.
  • the curable polymer component (AB) having a functional group that reacts with energy rays an acrylate compound having a polymer structure such as polyether acrylate, and the like having a high molecular weight can be used.
  • a polymer prepared by reacting a low molecular compound having a functional group that reacts with the above may be used.
  • the preferred mode of the raw material polymer is the same as that of the acrylic polymer (A1).
  • the photopolymerization initiator (B22) may be used in the same manner as when the energy ray curable component (B2) is used. .
  • the second binder component may contain the above-described polymer component (A) and curable component (B) in combination with the curable polymer component (AB).
  • the polymer component (A), the curable component (B) and the curable polymer component (AB) constituting the binder component By changing the type (characteristic) and content ratio, the adhesive force on the first surface and the adhesive force on the second surface of the protective film-forming film can be adjusted.
  • the adhesive force in the 1st surface of the film for protective film formation and the adhesive force in the 2nd surface can be adjusted by changing content of a thermosetting agent (B12) or a hardening accelerator (B13).
  • the type (characteristic) and content ratio of (AB) or the content of the thermosetting agent (B12) or the curing accelerator (B13) hereinafter also referred to as “binder component main composition”
  • the first of the protective film-forming film is a type (characteristic) and content ratio of (AB) or the content of the thermosetting agent (B12) or the curing accelerator (B13) (hereinafter also referred to as “binder component main composition”).
  • a protective film can be formed by blending inorganic filler (C), coupling agent (E), release agent (F), etc., which will be described later You may make it produce a difference in the adhesive force in the 1st surface of a forming film, and the adhesive force in a 2nd surface.
  • the binder component main composition of the resin layer including the second surface b is adjusted, and by adding the release agent (F), the adhesive force and the probe tack value on the second surface of the protective film-forming film are set to a predetermined value. Control to range.
  • the binder component main composition of the resin layer including the first surface a is approximated to the binder component main composition of the resin layer including the second surface b, and the release agent is applied to the resin layer including the first surface a.
  • (F) is not added, or is added in an amount smaller than that added to the resin layer including the second surface b.
  • the adhesive force on the second surface of the protective film-forming film and the adhesive force on the first surface of the protective film-forming film do not substantially differ depending on the main composition of the binder component.
  • the adhesive force on the second surface of the protective film-forming film is increased. It can control so that it may become lower than the adhesive force in the 1st surface of the film for protective film formation.
  • the first surface a is included in the case where a substantial difference is not caused between the adhesive force on the first surface and the adhesive force on the second surface of the protective film-forming film.
  • the following can be said about the resin layer.
  • the acrylic polymer (A1) is used for the resin layer including the first surface a
  • the glass transition temperature (Tg) of the acrylic polymer (A1) in the resin layer including the second surface b is similar to the glass transition temperature.
  • the temperature (Tg) is preferably in the range of ⁇ 40 to ⁇ 5 ° C.
  • the weight average molecular weight is 600, similar to the weight average molecular weight of the acrylic polymer (A1) in the resin layer including the second surface b. , 1,000 to 1,200,000 is preferable.
  • the resin layer including the first surface a when only the epoxy compound (B11) that is solid at room temperature is used, similarly to the content of the epoxy compound (B11) in the resin layer including the second surface b, It is preferable that 70 to 150 parts by mass of the epoxy compound (B11) is contained with respect to 100 parts by mass of the polymer component (A).
  • the binder component main component of the resin layer including the first surface a When the composition and the binder component main composition of the resin layer including the second surface b are approximate, the difference in volume shrinkage during curing of both layers tends to be small. For this reason, the effect that the curvature of the film for protective film formation at the time of hardening is suppressed may be acquired.
  • the protective film-forming film may contain the following components in addition to the binder component.
  • the film for forming an inorganic filler protective film may contain an inorganic filler (C).
  • an inorganic filler (C) By blending the inorganic filler (C) in the protective film-forming film, it is possible to adjust the thermal expansion coefficient in the cured protective film, and the thermal expansion coefficient of the protective film after curing with respect to the adherend. By optimizing, the reliability of the semiconductor device can be improved. It is also possible to reduce the hygroscopicity of the protective film after curing.
  • the inorganic filler (C) is exposed in the portion scraped off by the laser light, and the reflected light diffuses to exhibit a color close to white. Thereby, when the film for protective film formation contains the coloring agent (D) mentioned later, there is an effect that a contrast difference is obtained between the laser marking portion and other portions, and the printing becomes clear.
  • the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like, beads formed by spheroidizing these, single crystal fibers, and glass fibers.
  • silica filler and alumina filler are preferable.
  • the said inorganic filler (C) can be used individually or in mixture of 2 or more types.
  • the content of the inorganic filler (C) is preferably a proportion of the total solid content constituting the resin layer including the first surface a, It is 0 to 70% by mass, more preferably 30 to 60% by mass, and the ratio of the total solid content constituting the resin layer including the second surface b is preferably 40 to 80% by mass, more preferably 50% by mass. Is 75% by mass.
  • the adhesive force on the first surface and the adhesive force on the second surface of the protective film-forming film can be adjusted.
  • the adhesive force on the first surface of the film for protective film formation and the second surface may be adjusted.
  • the concentration of the inorganic filler (C) is lower on the first surface side of the protective film-forming film than on the second surface side, the wettability is excellent for adherends such as semiconductor wafers and chips. And exhibits adhesion.
  • concentration of an inorganic filler (C) is high compared with the 1st surface side, the 2nd surface side improves the visibility of laser printing.
  • the content of the inorganic filler (C) further occupies 50 to 80% by mass of the total solid content constituting the protective film-forming film, such an effect tends to become remarkable. Therefore, it is preferably 60 to 80% by mass.
  • the method for forming the concentration gradient of the inorganic filler (C) in the thickness direction is not particularly limited, but the following methods may be mentioned. First, the protective film-forming composition containing the inorganic filler (C) is applied onto the release sheet, and left for a certain period of time, whereby the inorganic filler (C) is precipitated in the protective film-forming film. Then, the film for protective film formation in which the density
  • Colorant (D) can be mix
  • the colorant By blending the colorant, malfunction of the semiconductor device due to infrared rays or the like generated from surrounding devices when the semiconductor device is incorporated into equipment can be prevented.
  • the protective film is engraved by means such as laser marking, there is an effect that marks such as characters and symbols can be easily recognized. That is, in a semiconductor device or semiconductor chip on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off and printed).
  • a laser marking method a method in which the surface of the protective film is scraped off and printed.
  • colorant organic or inorganic pigments and dyes are used.
  • black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties.
  • the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor device.
  • a coloring agent (D) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the colorant (D) is preferably 0.1 to 35 parts by weight, more preferably 0.5 to 25 parts by weight, particularly 100 parts by weight of the total solid content constituting the protective film-forming film.
  • the amount is preferably 1 to 15 parts by mass.
  • Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.
  • the functional group that reacts with the organic functional group is a group that reacts with the functional group of the polymer component (A), the curable component (B), the curable polymer component (AB), and the like.
  • Some silane coupling agents are preferably used.
  • Such silane coupling agents include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxy).
  • the silane coupling agent is usually 0.1 to 20 parts by weight, preferably 0.8 parts per 100 parts by weight in total of the polymer component (A), the curable component (B) and the curable polymer component (AB). 2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass. If the content of the silane coupling agent is less than 0.1 parts by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, it may cause outgassing.
  • the content of the coupling agent (E) is preferably a proportion of the total solid content constituting the resin layer including the first surface a. Is 0.03 to 2% by mass, more preferably 0.05 to 1% by mass, and the proportion of the total solid content constituting the resin layer including the second surface b is preferably 0 to 1.5%. % By mass, more preferably 0.01 to 1% by mass.
  • the adhesive force on the first surface of the film for protective film formation and the second surface You may adjust the adhesive force in.
  • the first surface side of the protective film-forming film has a higher concentration of the coupling agent (E) than the second surface side, it exhibits excellent adhesion to adherends such as semiconductor wafers and chips.
  • the content of the coupling agent (E) is preferably 0.01 to 2% by mass, more preferably 0.05% of the total solid content constituting the protective film-forming film. To 1% by mass.
  • the method for forming the concentration gradient of the coupling agent (E) in the thickness direction is not particularly limited, and is the same as the method for forming the concentration gradient of the inorganic filler (C) described above. .
  • a release agent may be added.
  • the release agent include silicone compounds such as polydimethylsiloxane, polyphenylmethylsiloxane, and polydiphenylsiloxane, and fluorine compounds.
  • silicone compounds such as polydimethylsiloxane, polyphenylmethylsiloxane, and polydiphenylsiloxane, and fluorine compounds.
  • a silicone compound is preferable, and an organopolysiloxane having an aromatic ring-containing group as a side chain and a kinematic viscosity at 25 ° C. of 50 to 100,000 mm 2 / s is more preferable.
  • Polysiloxane is a compound in which a plurality of unit structures represented by —Si (X) 2 —O— (X represents a side chain) is connected, and the number of unit structures is not particularly limited, but usually 3 or more It is.
  • the kinematic viscosity value can be controlled by increasing or decreasing the number of unit structures.
  • the silicone compound lowers the adhesion with the support by the siloxane portion of the organopolysiloxane and has a high lipid solubility by having the above aromatic ring-containing group in the side chain, and other components in the composition for forming a protective film High compatibility with.
  • the curing component (B) in the composition for forming a protective film often has an aromatic ring as a constituent component, and in such a case, the compatibility of the silicone compound with the aromatic ring-containing group further increases.
  • the aromatic ring-containing group include a phenyl group and an aralkyl group.
  • the aralkyl group here means that the alkyl part is linear or branched, the alkyl part preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and the aryl part preferably has carbon atoms.
  • Preferable examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylisopropyl group.
  • the aromatic ring-containing group is preferably an aralkyl group.
  • the resin layer containing at least the second surface b contains a release agent, and the content of the release agent (F) in the resin layer containing the second surface b
  • the content of the release agent (F) in the resin layer including the first surface a is larger.
  • the adhesive force in the 1st surface of the film for protective film formation and the adhesive force in the 2nd surface can be adjusted.
  • the content of the release agent (F) is preferably 0 to 0. 0 with respect to 100 parts by mass of the solid content excluding the release agent among the total solids constituting the resin layer including the first surface a.
  • the adhesive force on the first surface and the adhesive force on the second surface of the protective film-forming film can be adjusted.
  • the resin layer including the second surface b by setting the content of the release agent (F) in the above range, the re-peeling performance to the support and the adhesive strength with the support are excellent, and the protective film-forming film It can prevent that the film for protective film formation peels from a support body during hardening of this.
  • additives may be added to the general-purpose additive protective film-forming film as necessary.
  • additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, and the like.
  • the protective film-forming film has initial adhesiveness and curability, and is easily adhered by pressing against a semiconductor wafer, a chip or the like in an uncured state. Moreover, you may heat the film for protective film formation, when pressing. Then, after curing, a protective film having high impact resistance can be provided, the adhesive strength is excellent, and a sufficient protective function can be maintained even under severe high temperature and high humidity conditions.
  • the protective film-forming film may have a single layer structure or a multilayer structure.
  • the film for forming a protective film is obtained, for example, using a composition (composition for forming a protective film) obtained by mixing the above components at an appropriate ratio.
  • the composition for forming a protective film may be diluted with a solvent in advance, or may be added to the solvent during mixing. Moreover, you may dilute with a solvent at the time of use of the composition for protective film formation. Examples of such a solvent include ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, cyclohexane, toluene, heptane and the like.
  • the thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, and particularly preferably 7 to 200 ⁇ m.
  • the maximum transmittance at a wavelength of 300 to 1200 nm which is a measure showing the transmittance of visible light and / or infrared rays and ultraviolet rays in the protective film-forming film, is preferably 20% or less, more preferably 0 to 15%. Preferably, it is more than 0% and not more than 10%, particularly preferably 0.001 to 8%.
  • the maximum transmittance of the protective film-forming film at a wavelength of 300 to 1200 nm can be adjusted by the colorant (D).
  • the maximum transmittance of the protective film-forming film was determined by using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation), and the entire thickness of the protective film-forming film (thickness 25 ⁇ m) after curing at 300 to 1200 nm. The light transmittance is measured and set to the highest value (maximum transmittance).
  • the protective film-forming film of the present invention is used as a protective film for a semiconductor wafer or chip made of silicon, gallium arsenide, or the like as an adherend.
  • a protective film-forming film can be formed on the process film.
  • Film formation is performed by applying a composition for forming a protective film-forming film on the process film according to a generally known method such as a roll knife coater, gravure coater, die coater, reverse coater, and drying.
  • the process film can be used as it is as a support sheet or cover film which will be described later.
  • the process film may be either the support sheet or the cover film, and the material to be transferred may be the other one of the support sheet or the cover film.
  • a protective film-forming film is produced by laminating two or more resin layers having different compositions, first, a resin layer is formed on the process film by the same method as described above. Next, a resin layer having a different composition is formed on another process film. Then, the film for protective film formation can be manufactured by bonding the obtained resin layers together.
  • the composite sheet for forming a protective film is obtained by forming a support sheet on the second surface side of the film for forming a protective film so as to be peelable.
  • the shape of the composite sheet for forming a protective film is not limited to a single sheet, and may be a long strip or roll it up. Examples of the support sheet include a release sheet, and an adhesive sheet described later can be used.
  • the composite sheet for forming a protective film is affixed to various adherends, and in some cases, the adherend is subjected to necessary processing such as dicing on the composite sheet for forming a protective film. Thereafter, the support film is peeled off by allowing the protective film-forming film to remain adhered to the adherend. That is, it is used in a process including a step of transferring a protective film-forming film from a support sheet to an adherend.
  • the protective film-forming film can have the same shape as the support sheet.
  • the protective film-forming composite sheet is prepared by making the protective film-forming film substantially the same shape as the wafer or including the shape of the wafer, and having a larger size than the protective film-forming film. A so-called pre-molded configuration laminated on the supporting sheet may be adopted.
  • release sheets include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene-terephthalate film, polyurethane film. , Ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film Etc. are used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.
  • the surface tension of the surface of the release sheet in contact with the protective film-forming film is preferably 40 mN / m or less, more preferably 37 mN / m or less, and particularly preferably 35 mN / m or less.
  • the lower limit is usually about 25 mN / m.
  • Such a release sheet having a relatively low surface tension can be obtained by appropriately selecting the material, and can also be obtained by applying a release agent to the surface of the release sheet and performing a release treatment. .
  • alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like are used as the release agent used for the release treatment.
  • alkyd, silicone, and fluorine release agents are heat resistant. This is preferable.
  • the release agent can be used without any solvent, or can be diluted or emulsified in a solvent to obtain a gravure coater, Mayer bar coater, air knife coater.
  • the release sheet coated with a release coater may be applied at room temperature or under heating, or may be cured with an electron beam to form a release agent layer.
  • the surface tension of the release sheet may be adjusted by laminating films by wet lamination, dry lamination, hot melt lamination, melt extrusion lamination, coextrusion processing, or the like. That is, a film in which the surface tension of at least one surface is within a preferable range as the surface in contact with the protective film-forming film of the release sheet described above is such that the surface is in contact with the protective film-forming film.
  • a laminate laminated with another film may be manufactured and used as a release sheet.
  • an adhesive sheet having an adhesive layer formed on a substrate is preferably used as the support sheet.
  • the protective film-forming film is laminated on the pressure-sensitive adhesive layer provided on the support sheet.
  • the pressure-sensitive adhesive layer may be a weakly-adhesive layer having an adhesive strength that can peel off the protective film-forming film, or an energy-ray-curing layer that decreases in adhesive strength when irradiated with energy rays. May be.
  • the pressure-sensitive adhesive layer includes various conventionally known pressure-sensitive adhesives (for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives, energy ray-curable pressure-sensitive adhesives, A thermal expansion component-containing pressure-sensitive adhesive or the like).
  • various conventionally known pressure-sensitive adhesives for example, rubber-based, acrylic-based, silicone-based, urethane-based, vinyl ether-based general-purpose pressure-sensitive adhesives, pressure-sensitive adhesives, energy ray-curable pressure-sensitive adhesives, A thermal expansion component-containing pressure-sensitive adhesive or the like.
  • the protective film-forming composite sheet functions as a dicing sheet for supporting the adherend in the dicing process, there is no need to dice by dicing a separate dicing sheet to the wafer with the protective film-forming film in the dicing process.
  • the manufacturing process of the semiconductor device can be simplified.
  • the protective film-forming composite sheet When the protective film-forming composite sheet has a pre-formed configuration, the protective film-forming composite sheet may have the following first, second, or third configuration.
  • first, second, or third configuration Hereinafter, each configuration of the protective film-forming composite sheet 100 will be described with reference to FIGS.
  • the first configuration is a configuration in which a pressure-sensitive adhesive sheet 3 having a pressure-sensitive adhesive layer 2 formed on a substrate 1 is formed on the second surface side of a protective film-forming film 10 so as to be peelable.
  • the pressure-sensitive adhesive layer is energy ray curable, and the region where the protective film-forming film is laminated is preliminarily irradiated with energy rays to reduce the adhesiveness, while other regions are irradiated with energy rays.
  • This is a configuration in which the adhesive strength is kept high without performing.
  • an energy beam shielding layer may be provided by printing or the like in a region corresponding to the other region of the support sheet, and the energy beam irradiation may be performed from the support sheet side.
  • the second configuration is a configuration in which a jig adhesive layer 4 is separately provided on the pressure-sensitive adhesive layer 2 of the protective film-forming composite sheet 100 in a region that does not overlap with the protective film-forming film 10. is there.
  • tool adhesion layer the layer which consists of a double-sided adhesive sheet which has a core material, and the single layer of an adhesive can be employ
  • the third configuration includes an interfacial adhesion adjusting layer 5 having a shape that can completely include the shape of the protective film-forming film between the protective film-forming film 10 and the pressure-sensitive adhesive layer 2.
  • the interface adhesion adjusting layer may be a predetermined film or an interface adhesion adjusting pressure-sensitive adhesive layer.
  • the interfacial adhesion-adjusting pressure-sensitive adhesive layer is preferably a layer obtained by previously irradiating an energy ray-curable pressure-sensitive adhesive and curing it.
  • the protective film-forming composite sheet By forming the protective film-forming composite sheet in these first to third configurations, the protective film is formed in the region surrounding the protective film-forming film due to sufficient adhesiveness of the pressure-sensitive adhesive layer or the jig adhesive layer.
  • the forming composite sheet can be adhered to a jig.
  • the adhesiveness at the interface between the protective film-forming film and the pressure-sensitive adhesive layer or the interfacial adhesion adjusting layer can be controlled to facilitate the pickup of the protective film-forming film or the chip to which the protective film is fixed.
  • the protective film-forming composite sheet does not have a pre-molded configuration, that is, as shown in FIG. 5, the protective film-forming film 10 and the support sheet (in FIG. 5, the adhesive layer 2 is formed on the substrate 1.
  • the jig adhesive layer 4 may be provided on the outer peripheral portion of the surface (first surface) of the protective film-forming film 10. As the jig adhesive layer, the same one as described above can be used.
  • the thickness of the support sheet is usually 10 to 500 ⁇ m, preferably 15 to 300 ⁇ m, particularly preferably 20 to 250 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is 3 to 50 ⁇ m in the support sheet.
  • a cover film may be temporarily attached to the first surface of the protective film-forming film.
  • the cover film may cover the pressure-sensitive adhesive layer when the support sheet is a pressure-sensitive adhesive sheet or the jig adhesive layer.
  • the same cover film as the above-described release sheet can be used.
  • the film thickness of the cover film is usually about 5 to 300 ⁇ m, preferably about 10 to 200 ⁇ m, particularly preferably about 20 to 150 ⁇ m.
  • Such a protective film-forming film of the protective film-forming composite sheet can be used as a protective film of an adherend.
  • the protective film-forming film is affixed to the back surface of the face-down chip semiconductor wafer or semiconductor chip, and is cured by an appropriate means to have a function of protecting the semiconductor wafer or semiconductor chip as an alternative to the sealing resin.
  • the protective film When pasted on a semiconductor wafer, the protective film has a function of reinforcing the wafer, so that damage to the wafer can be prevented.
  • the method for manufacturing a semiconductor device preferably includes a step of attaching a protective film-forming film of the protective film-forming composite sheet to a semiconductor wafer to obtain a semiconductor chip having the protective film. Specifically, a protective film-forming film of the protective film-forming composite sheet is attached to the back surface of a semiconductor wafer having a circuit formed on the front surface, and then a semiconductor chip having a protective film on the back surface is obtained.
  • the protective film is preferably a protective film for a semiconductor wafer or a semiconductor chip.
  • the method for manufacturing a semiconductor device according to the present invention preferably further includes the following steps (1) to (5), wherein steps (1) to (4) are performed in this order, and step (5) is arbitrarily performed. It is characterized by performing in order.
  • Step (1) peeling off the protective film-forming film and the support sheet
  • Step (2) placing the protective film-forming film on the support
  • Step (3) The protective film-forming film is cured to obtain a protective film.
  • the method for manufacturing a semiconductor device according to the present invention may further include the following step (6).
  • the step (6) can also be performed.
  • the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Formation of a circuit on the wafer surface can be performed by various methods including conventionally used methods such as an etching method and a lift-off method. Next, the opposite surface (back surface) of the circuit surface of the semiconductor wafer is ground.
  • the grinding method is not particularly limited, and grinding may be performed by a known means using a grinder or the like. At the time of back surface grinding, an adhesive sheet called a surface protection sheet is attached to the circuit surface in order to protect the circuit on the surface.
  • the circuit surface side (that is, the surface protection sheet side) of the wafer is fixed by a chuck table or the like, and the back surface side on which no circuit is formed is ground by a grinder.
  • the thickness of the wafer after grinding is not particularly limited, but is usually about 50 to 500 ⁇ m.
  • the crushed layer generated during back grinding is removed.
  • the crushed layer is removed by chemical etching, plasma etching, or the like.
  • step (5) is performed in an arbitrary order. As an example, the case where it carries out in order of process (5), (1), (2), (3), (4) is demonstrated.
  • the protective film-forming film (first surface) of the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer having a circuit formed on the front surface.
  • an adhesive sheet may be used as a support sheet for the protective film-forming composite sheet.
  • the pressure-sensitive adhesive sheet can serve as a dicing sheet that supports the semiconductor wafer via the protective film-forming film.
  • a semiconductor wafer is affixed to the inner peripheral portion of the protective film forming composite sheet via a protective film forming film, and the outer peripheral portion of the protective film forming composite sheet is bonded to another jig such as a ring frame.
  • the composite sheet for forming a protective film affixed to the semiconductor wafer is fixed to the apparatus, and dicing is performed. Dicing of the semiconductor wafer on the composite sheet for forming a protective film is performed in the same manner as a conventional method using a known dicing sheet.
  • the support sheet is peeled off from the second surface of the protective film-forming film by picking up the diced chip (chip with protective film-forming film) by general means such as a collet.
  • the support is temporarily fixed to the protective film-forming film (second surface) to obtain a laminate in which the chip, the protective film-forming film, and the support are laminated in this order.
  • the support is not particularly limited as long as the surface thereof is a smooth material, and examples thereof include a plate made of an organic resin such as a silicon wafer, a glass plate, and a polymethyl methacrylate plate.
  • the surface roughness (Ra) of these supports is preferably 200 nm or less, more preferably 0.01 to 100 nm.
  • the surface roughness (arithmetic mean roughness Ra) in the present invention is a surface roughness meter (Mittoyo Corporation) with a measurement length of 10 mm, a scanning speed of 0.1 mm / second, and a data sampling pitch of 80 ⁇ m based on JIS B0601; This is a value measured by SV-3000S4).
  • the support preferably has heat resistance. Examples of the support having heat resistance include a silicon wafer and a glass plate.
  • the protective film-forming film is thermally cured or energy ray cured to form a protective film on the back surface of the chip.
  • the protective film-forming film is blended with a thermosetting component (B1) or a thermosetting curable polymerizable component (AB), and an energy ray curable component (B2) or an energy ray curable curable weight.
  • a thermosetting component (B1) or a thermosetting curable polymerizable component (AB) an energy ray curable component (B2) or an energy ray curable curable weight.
  • the coalescence component (AB) is blended, curing by heating and energy beam irradiation may be performed simultaneously or sequentially.
  • the energy rays to be irradiated include ultraviolet rays (UV) and electron beams (EB), and preferably ultraviolet rays are used.
  • a protective film made of a cured resin is formed on the back surface of the chip, and the strength is improved as compared with the case of the chip alone, so that damage during handling of the thinned chip can be reduced.
  • the thickness uniformity of the protective film is excellent as compared with a coating method in which a coating solution for a resin film is directly applied to the back surface of the chip.
  • the support is peeled from the protective film to obtain a chip with a protective film.
  • a protective film having high thickness uniformity can be easily formed on the back surface of the chip, and cracks after the dicing process and packaging are less likely to occur.
  • the support is temporarily fixed to the protective film-forming film (second surface) and then cured, deformation due to the curing reaction is suppressed on the second surface, and the smoothness of the support surface is made to the second surface. Can be transferred. As a result, the smoothness of the second surface after curing is improved, and the visibility of the characters laser-printed on the second surface of the protective film is improved in the laser printing step described later.
  • the protective film (second surface).
  • Laser printing is performed by a laser marking method, and the surface of the protective film is scraped off by laser light irradiation to mark a product number or the like on the protective film.
  • the second surface of the protective film has the same level of smoothness as the support because the smoothness of the support is transferred. Therefore, the visibility of the product number printed on the second surface of the protective film is excellent.
  • a semiconductor device can be manufactured by mounting a chip with a protective film on a predetermined base in a face-down manner. Further, a semiconductor device can be manufactured by adhering a semiconductor chip having a protective film on the back surface to another member (on the chip mounting portion) such as a die pad portion or another semiconductor chip.
  • the protective film-forming film of the present invention and the protective film-forming composite sheet using the film can be used for the protection of semiconductor compounds, glass, ceramics, metals, etc., in addition to the above usage methods.
  • ⁇ removability on the second surface> ⁇ adhesive force between the first surface and the second surface>, ⁇ probe tack value>, and ⁇ laser marking suitability> are as follows: Measured and evaluated.
  • the first surface of the protective film-forming film is stuck to a polished surface (No. 2000 finish) of a silicon wafer polished to a thickness of 350 ⁇ m at a table temperature of 60 ° C.
  • a laminate of the silicon wafer and the protective film forming film was obtained.
  • a dicing tape (D-676H manufactured by Lintec Co., Ltd.) is applied to the protective film forming film side (second surface) of the laminate, and the laminate is diced to 2 mm ⁇ 2 mm and protected by picking up. A chip with a film-forming film was obtained.
  • the second surface of the film for forming a protective film of the chip was stuck on the polished surface (No. 2000 finish) of the support 7 (500 ⁇ m thick silicon wafer) at 100 ° C., 300 g, for 10 seconds. .
  • the protective film-forming film was thermally cured at 130 ° C. for 2 hours to obtain a laminate of the support 7, the protective film 11, and the chip 8.
  • the support 7 of the laminate is fixed, and the protective film is measured at a measurement speed of 200 ⁇ m / second and a measurement temperature of 23 ° C.
  • the attached chip 20 was peeled from the support body 7 by applying a load from the side surface.
  • the case where peeling was possible at the interface between the protective film 11 and the support 7 was evaluated as “good”, and the protective film 11 was partially peeled off at the interface between the protective film 11 and the chip 8, and the chip 8 was exposed.
  • the case where the protective film 11 remained on the support 7 was evaluated as “bad”.
  • the above evaluation was performed on 10 laminated bodies of the support 7, the protective film 11, and the chip 8, and the number of evaluations “good” was counted.
  • a dicing tape (D-676H manufactured by Lintec Co., Ltd.) is applied to the protective film forming film side (second surface) of the laminate, and the laminate is diced to 2 mm ⁇ 2 mm and protected by picking up. A chip having a film forming film was obtained.
  • the protective film-forming film was thermally cured at 130 ° C. for 2 hours to obtain a chip with a protective film.
  • the protective film (second surface) of the chip with protective film was fixed to the metal plate with an adhesive.
  • the metal plate 9 was fixed using a shear strength measuring tool 6 of a shear strength measuring machine (bond tester Dage series 4000 manufactured by Dage), and the measurement speed was 200 ⁇ m / second and the measurement temperature was 23 ° C. Then, a load was applied to the chip 8 from the side surface of the chip 20 with the protective film, and the adhesive force between the first surface of the protective film 11 and the chip 8 (adhesive force of the first surface to the silicon wafer after curing) was measured. . The adhesive force was the maximum value of the load when the chip 8 was peeled from the protective film 11 (at the time of breakage).
  • the adhesion between the second surface of the protective film and the chip is performed in the same manner as described above except that the second surface of the protective film-forming film is attached to the silicon wafer and the dicing tape is attached to the first surface side.
  • the force adheresion force of the second surface to the silicon wafer after curing was measured.
  • the ratio (adhesive force of the first surface to the silicon wafer / adhesive force of the second surface to the silicon wafer) was calculated from the adhesive force obtained above.
  • the probe tack value was measured on the second surface of the protective film-forming film prepared in Examples or Comparative Examples using PROBETACKTESTER manufactured by Rigaku Industry Co., Ltd. according to JIS Z0237: 1991 Reference 5. Specifically, the film for forming a protective film before thermosetting is cut into a 25 mm ⁇ 25 mm test piece, and in a 23 ° C. environment, the second surface of the test piece is made of stainless steel having a diameter of 5 mm heated to 70 ° C. After contacting the probe for 10 seconds with a contact load of 0.98 N / cm 2 , the probe was separated from the test piece at a speed of 10 mm / second, and the stress at that time was measured.
  • the protective film-forming film was thermally cured at 130 ° C. for 2 hours without temporarily fixing the chip with the protective film-forming film obtained in the evaluation of removability on the second surface to the support, and the support and the protective film A chip laminate was obtained and used as a sample. Moreover, in the evaluation of the removability on the second surface, a sample having a “good” evaluation among the laminates of the protective film and the chip obtained by thermosetting on the support was used as a sample.
  • Contrast value by CCD camera is less than 30%
  • composition ( ⁇ ) Each component which comprises the composition for protective film formation ((alpha)), and its compounding quantity are shown below.
  • the compounding quantity of each component shows the mass part of solid content conversion, and solid content means all components other than a solvent in this invention.
  • composition for forming protective film ( ⁇ ) The amount of component (F) is the same as that of the protective film-forming composition ( ⁇ ) except that the amount of component (A) to (F) is 0.5 parts by mass with respect to 100 parts by mass in total.
  • the amount of component (F) is the same as that for the protective film-forming composition ( ⁇ ) except that the amount of component (F) is 1.5 parts by mass with respect to 100 parts by mass in total of (A) to (F).
  • the amount of component (F) is the same as that for the protective film-forming composition ( ⁇ ) except that the amount of component (F) is 3.0 parts by mass with respect to 100 parts by mass in total of (A) to (F).
  • composition ( ⁇ ) It is the same as the composition ( ⁇ ) for forming a protective film except that the following polymer component (A ′) is used instead of the polymer component (A).
  • a ′ Polymer component: acrylic polymer (weight average) obtained by copolymerizing 15 parts by mass of n-butyl acrylate, 50 parts by mass of methyl methacrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (Molecular weight: 900,000, glass transition temperature: -1 ° C)
  • composition for forming protective film ( ⁇ ) The component (F) is the same as the protective film-forming composition ( ⁇ ) except that the amount of component (F) is 0 part by mass with respect to 100 parts by mass in total of (A) to (F).
  • Example 1 As a release sheet, a polyethylene terephthalate film (SP-P502010 manufactured by Lintec Corporation, thickness 50 ⁇ m) having a release treatment on one side was prepared. A methyl ethyl ketone solution (solid content concentration: 61% by weight) of the composition for forming a protective film ( ⁇ ) was applied on the release-treated surface of the release sheet so that the thickness after drying was 25 ⁇ m, and dried (drying conditions: oven At 120 ° C. for 3 minutes to form a resin layer ( ⁇ ) on the release sheet.
  • SP-P502010 polyethylene terephthalate film manufactured by Lintec Corporation, thickness 50 ⁇ m
  • a polyethylene terephthalate film (SP-P502010, Lintec Corporation, thickness 50 ⁇ m) having a release treatment on one side was prepared.
  • a methyl ethyl ketone solution (solid content concentration: 61% by weight) of the composition for forming a protective film ( ⁇ ) was applied onto the release-treated surface of the release sheet so that the thickness after drying was 25 ⁇ m and dried (drying conditions: A resin layer ( ⁇ ) was formed on the release sheet by heating in an oven at 120 ° C. for 3 minutes.
  • Example 2 A protective film-forming film was obtained in the same manner as in Example 1 except that the protective film-forming composition ( ⁇ ) was used instead of the protective film-forming composition ( ⁇ ). Each evaluation result is shown in Table 1.
  • Example 3 A protective film-forming film was obtained in the same manner as in Example 1, except that the protective film-forming composition ( ⁇ ) was used instead of the protective film-forming composition ( ⁇ ). Each evaluation result is shown in Table 1.
  • Example 4 A protective film-forming film was obtained in the same manner as in Example 1, except that the protective film-forming composition ( ⁇ ) was used instead of the protective film-forming composition ( ⁇ ). Each evaluation result is shown in Table 1.
  • Example 5 A protective film-forming film was obtained in the same manner as in Example 1 except that the protective film-forming composition ( ⁇ ) was used instead of the protective film-forming composition ( ⁇ ). Each evaluation result is shown in Table 1.
  • Example 1 A protective film-forming film was obtained in the same manner as in Example 1 except that the protective film-forming composition ( ⁇ ) was used instead of the protective film-forming composition ( ⁇ ). Each evaluation result is shown in Table 1.
  • SYMBOLS 10 Film for protective film formation a: 1st surface b: 2nd surface 100: Composite sheet for protective film formation 1: Base material 2: Adhesive layer 3: Adhesive sheet 4: Jig adhesion layer 5: Interface adhesion adjustment layer 6: Tool for measuring shear strength 7: Support 8: Tip 9: Metal plate 11: Protective film 20: Tip with protective film

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne la réalisation d'un film constituant une membrane de retenue qui, après polymérisation alors qu'elle est fixée de façon temporaire à un corps support, se détache facilement du corps support et présente une excellente force d'adhésion à un microcircuit. À cet effet, le film polymérisable constituant la membrane de retenue comporte une première surface et une seconde surface, la force d'adhésion de la première surface à une plaquette de silicium après polymérisation étant supérieure à la force d'adhésion de la seconde surface à une plaquette de silicium après polymérisation.
PCT/JP2013/083628 2012-12-14 2013-12-16 Film constituant une membrane de retenue WO2014092200A1 (fr)

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JP2014552108A JP6270736B2 (ja) 2012-12-14 2013-12-16 保護膜形成用フィルム
KR1020157014737A KR102152605B1 (ko) 2012-12-14 2013-12-16 보호막 형성용 필름
CN201380064452.XA CN104837942B (zh) 2012-12-14 2013-12-16 保护膜形成用膜

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JP2016032018A (ja) * 2014-07-29 2016-03-07 日立化成株式会社 仮固定用樹脂組成物、仮固定用樹脂フィルム及び仮固定用樹脂フィルムシート
JPWO2016113998A1 (ja) * 2015-01-14 2017-10-19 リンテック株式会社 樹脂膜形成用シート、樹脂膜形成用複合シート、及びシリコンウエハの再生方法
CN107428963A (zh) * 2015-03-12 2017-12-01 琳得科株式会社 保护膜形成用膜
CN107428963B (zh) * 2015-03-12 2021-02-09 琳得科株式会社 保护膜形成用膜
JP2016105456A (ja) * 2015-09-17 2016-06-09 リンテック株式会社 保護膜形成用フィルム
WO2017191815A1 (fr) * 2016-05-02 2017-11-09 日立化成株式会社 Film de résine pour fixation temporaire
JPWO2017191815A1 (ja) * 2016-05-02 2018-11-08 日立化成株式会社 仮固定用樹脂フィルム
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KR20170126796A (ko) 2016-05-10 2017-11-20 닛토덴코 가부시키가이샤 시트, 테이프, 및 반도체 장치의 제조 방법
WO2019082963A1 (fr) * 2017-10-27 2019-05-02 リンテック株式会社 Film de formation de film protecteur, feuille composite de formation de film protecteur, et procédé de fabrication de puce en semiconducteur
KR20200112941A (ko) 2018-01-30 2020-10-05 닛토덴코 가부시키가이샤 반도체 배면 밀착 필름 및 다이싱 테이프 일체형 반도체 배면 밀착 필름
KR20200115205A (ko) 2019-03-25 2020-10-07 닛토덴코 가부시키가이샤 다이싱 테이프 일체형 반도체 배면 밀착 필름
WO2022210241A1 (fr) * 2021-03-31 2022-10-06 日産化学株式会社 Stratifié, composition d'agent antiadhésif, et procédé de fabrication d'un substrat en semi-conducteur usiné

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KR102152605B1 (ko) 2020-09-07
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JP6270736B2 (ja) 2018-01-31
CN104837942A (zh) 2015-08-12

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