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WO2014148642A1 - Protective film-forming film and protective film-forming composite sheet - Google Patents

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

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Publication number
WO2014148642A1
WO2014148642A1 PCT/JP2014/058038 JP2014058038W WO2014148642A1 WO 2014148642 A1 WO2014148642 A1 WO 2014148642A1 JP 2014058038 W JP2014058038 W JP 2014058038W WO 2014148642 A1 WO2014148642 A1 WO 2014148642A1
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WO
WIPO (PCT)
Prior art keywords
protective film
film
forming
thermosetting
wafer
Prior art date
Application number
PCT/JP2014/058038
Other languages
French (fr)
Japanese (ja)
Inventor
尚哉 佐伯
山本　大輔
高野　健
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2014530843A priority Critical patent/JP5615471B1/en
Priority to KR1020217018040A priority patent/KR102377100B1/en
Priority to KR1020217018041A priority patent/KR102541666B1/en
Priority to SG11201507775XA priority patent/SG11201507775XA/en
Priority to CN201480004970.7A priority patent/CN104937712B/en
Priority to KR1020157026015A priority patent/KR20150135284A/en
Priority to KR1020227007805A priority patent/KR20220035981A/en
Publication of WO2014148642A1 publication Critical patent/WO2014148642A1/en
Priority to PH12015502208A priority patent/PH12015502208A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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 a protective film forming sheet for chips having a curable protective film forming layer containing a heat or energy ray curable component is disclosed.
  • the wafer itself when the wafer itself is sufficiently thick, the wafer itself has not warped.
  • the shrinkage ratio between the wafer surface on which the circuit is formed and the back surface of the wafer on which the circuit is not formed There is a problem that warpage occurs in the thinned wafer due to the difference in the above.
  • a wafer having a large warp may cause a conveyance failure during the subsequent chip manufacturing process.
  • the wafer may be difficult to dice due to the warpage of the wafer.
  • the protective film-forming film attached to the back surface of the wafer is required to have a capability of correcting the warpage of the wafer.
  • the following flip chip type semiconductor back film is used to suppress or prevent warping of semiconductor elements such as semiconductor wafers and semiconductor chips.
  • patent document 3 using the film for flip chip type semiconductor back surfaces whose shrinkage
  • An object of the present invention is to provide a film for forming a protective film that can suppress warping of a wafer and can form a highly reliable protective film on a chip.
  • the gist of the present invention is as follows. [1] It has thermosetting properties, The glass transition temperature after thermosetting is 150 to 300 ° C., A protective film-forming film having a tensile elastic modulus at 23 ° C. of 0.5 to 10 GPa after thermosetting.
  • thermosetting polymer component is contained, and 135 parts by mass of the thermosetting component with respect to a total of 100 parts by mass of the polymer component and the thermosetting polymer component.
  • the protective film-forming film according to [2] which is contained in a part or less.
  • the protective film-forming film contains an inorganic filler, The protective film-forming film according to any one of [1] to [3], wherein the content of the inorganic filler is 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film.
  • the protective film-forming film contains a thermosetting polymer component, The film for forming a protective film according to any one of [1] to [5], wherein the thermosetting polymer component is an acrylic polymer containing an epoxy group-containing monomer as a constituent monomer.
  • a composite sheet for forming a protective film wherein a support sheet is detachably formed on one side of the film for forming a protective film according to any one of [1] to [6].
  • the protective film-forming film can be cured and contracted by applying a protective film-forming film to the back surface of the wafer and thermally curing the wafer due to shrinkage caused by circuit formation on the wafer front side.
  • the warpage of the wafer can be corrected by the resulting stress, and a highly reliable chip with a protective film can be obtained.
  • 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. It is drawing explaining the "warpage amount" evaluated in the Example.
  • the protective film-forming film of the present invention has thermosetting properties, and has a glass transition temperature (Tg) after thermosetting of 150 to 300 ° C, preferably 170 to 280 ° C, more preferably 220 to 270 ° C.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) after thermosetting of the protective film-forming film is ⁇ 50 to in the dynamic viscoelasticity measurement of the protective film-forming film (protective film) after thermosetting measured at a frequency of 11 Hz. It indicates the temperature at which the loss tangent tan ⁇ exhibits a maximum value in a low temperature region of 30 ° C.
  • the Tg after thermosetting of the protective film-forming film is less than 150 ° C., the fluidity of the protective film-forming film is increased in the thermosetting process of the protective film-forming film usually performed at about 120 to 150 ° C., Stress due to curing shrinkage of the protective film-forming film is relieved and reduced. As a result, the correction of the warpage of the wafer is insufficient.
  • the Tg of the protective film-forming film after thermosetting exceeds 300 ° C., the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. As a result, the reliability of the chip with protective film decreases.
  • the protective film-forming film has a predetermined rigidity in the thermosetting process of the film, so that stress due to curing shrinkage of the film is relieved. Instead, the warpage of the wafer or chips obtained by dividing the wafer into pieces can be corrected.
  • the protective film-forming film has a tensile elastic modulus at 23 ° C. after thermosetting of 0.5 to 10 GPa, preferably 1 to 10 GPa, more preferably more than 5 GPa and 8 GPa or less. If the tensile elastic modulus at 23 ° C. after thermal curing of the protective film-forming film is less than 0.5 GPa, stress due to curing shrinkage of the protective film-forming film cannot be maintained, and the stress is relieved. The correction of the warpage of the wafer becomes insufficient. On the other hand, if the tensile elastic modulus at 23 ° C.
  • the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. There is.
  • the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film within the above range, it is possible to correct the warpage of the wafer and the chip and improve the reliability of the chip with the protective film.
  • the thermal shrinkage rate of the protective film-forming film when heated at 130 ° C. for 2 hours is preferably 0.1 to 10%, more preferably 0.5 to 5%.
  • the thermal shrinkage rate when the protective film-forming film is heated at 130 ° C. for 2 hours within the above range, the effect of correcting the warpage of the wafer (warpage correction performance) is improved.
  • the thermal contraction rate of the protective film-forming film when heated at 130 ° C. for 2 hours is obtained from the area of the protective film-forming film before and after the protective film-forming film is put in an environment at 130 ° C. by the following formula. .
  • Heat shrinkage rate (%) ⁇ (area of protective film forming film before loading) ⁇ (area of protective film forming film after loading) ⁇ / area of protective film forming film before loading ⁇ 100
  • the functions required for the protective film-forming film are (1) sheet shape maintenance, (2) initial adhesiveness, and (3) curability.
  • the film for protective film formation of this invention has thermosetting as above-mentioned, you may have the property hardened
  • 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 thermosetting component ( The first binder component containing B) or the second binder component containing the thermosetting polymer component (AB) having the properties of the component (A) and the component (B) can be used.
  • 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
  • a 1st binder component does not contain a thermosetting polymer component (AB) for convenience which distinguishes 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.
  • polymer component (A) examples include acrylic polymers, polyesters, phenoxy resins (for the purpose of distinguishing from thermosetting polymer components (AB) described later, those having no epoxy group), polycarbonates, and polyethers.
  • Polyurethane, polysiloxane, rubber polymer, etc. can be used.
  • it is an acrylic urethane resin 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.
  • 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. If the glass transition temperature of the acrylic polymer (A1) is high, the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend. In addition, when the glass transition temperature of the acrylic polymer (A1) is low, the peeling force between the protective film-forming film and a support sheet described later may increase, and transfer failure of the protective film-forming film may occur.
  • the Tg of the acrylic polymer is a value determined from the FOX equation.
  • the weight average molecular weight (Mw) of the acrylic polymer (A1) is preferably 100,000 to 1,500,000.
  • Mw weight average molecular weight of the acrylic polymer (A1)
  • the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend.
  • the weight average molecular weight of the acrylic polymer (A1) is low, the adhesion between the protective film-forming film and the support sheet is increased, which may cause transfer failure of the protective film-forming film.
  • 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, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (Meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, etc .; (meth) acrylate
  • a (meth) acrylic acid ester having a hydroxyl group a (meth) acrylic acid ester having a carboxyl group, or a (meth) acrylic acid having an amino group
  • a (meth) acrylic acid ester having a hydroxyl group a (meth) acrylic acid ester having a carboxyl group
  • a (meth) acrylic acid having an amino group By using the ester, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film within a predetermined range.
  • (meth) acryl may be used to include both acrylic and methacrylic.
  • a monomer having a hydroxyl group may be used as a monomer constituting the acrylic polymer (A1).
  • monomers having a hydroxyl group include hydroxyl groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate (meth).
  • a monomer having a carboxyl group may be used as the monomer constituting the acrylic polymer (A1).
  • the monomer having a carboxyl group include (meth) acrylic acid esters having a carboxyl group such as 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxypropyl phthalate; Maleic acid, fumaric acid, itaconic acid and the like can be mentioned.
  • an epoxy thermosetting component as the thermosetting component (B) described later, the carboxyl group and the epoxy group in the epoxy thermosetting component react with each other, so that the monomer having a carboxyl group The amount used is preferably small.
  • a monomer having an amino group may be used as the monomer constituting the acrylic polymer (A1).
  • the monomer monomer having an amino group include (meth) acrylic acid esters having an amino group such as monomethylamino (meth) acrylate, monoethylamino (meth) acrylate, and diethylamino (meth) acrylate.
  • vinyl acetate, styrene, ethylene, ⁇ -olefin and the like may be used as the monomer constituting the acrylic polymer (A1).
  • 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.
  • the crosslink density of the acrylic polymer (A1) the glass transition temperature of the protective film-forming film after thermosetting and the tensile elastic modulus at 23 ° C. after thermosetting can be controlled.
  • the crosslinking density can be controlled by the addition amount of a crosslinking agent described later.
  • 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.
  • thermosetting component (B) Thermosetting component
  • the thermosetting component (B) is added to the protective film-forming film mainly for the purpose of imparting thermosetting properties to the protective film-forming film.
  • the thermosetting component (B) contains at least a compound having a functional group that reacts by heating. Curing is realized by the functional groups of the thermosetting component (B) reacting to form a three-dimensional network structure. Since the thermosetting 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. Therefore, the weight average molecular weight (Mw) is usually 10,000 or less, preferably 100 to 10,000.
  • thermosetting component (B) for example, an epoxy thermosetting component is preferable.
  • the epoxy thermosetting component contains a compound (B11) having an epoxy group (hereinafter sometimes referred to as “epoxy compound (B11)”), a compound (B11) having an epoxy group, and a thermosetting agent (B12). ) are preferably used, and more preferably a combination of a curing accelerator (B13).
  • (B11) As a compound epoxy compound (B11) having an epoxy group , conventionally known compounds can be used. Specifically, polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenols Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as F-type epoxy resins and phenylene skeleton-type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.
  • 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.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride.
  • phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, phenolic hydroxyl groups and amino groups are more preferable, and amine-based curing agents having amino groups are particularly preferable.
  • thermosetting agent other than an amine curing agent, such as a phenol curing agent
  • the glass transition temperature after thermal curing of the protective film-forming film is the range described above unless more thermosetting agent is blended. It is difficult to adjust.
  • thermosetting agent (B12) content of the whole thermosetting component (B) must be increased, and there exists a possibility that content of a thermosetting component (B) may become excessive.
  • phenolic curing agent examples include polyfunctional phenolic resin, biphenol, novolac type phenolic resin, dicyclopentadiene type phenolic resin, zylock type phenolic resin, and aralkylphenolic resin.
  • 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 ignition curing agent (B12) is usually about 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).
  • the glass transition temperature after the thermosetting of the film for protective film formation can be controlled by adjusting content of an epoxy compound (B11), a thermosetting agent (B12), and a hardening accelerator (B13).
  • the amount of epoxy groups possessed by the epoxy compound (B11) and the amount of active hydrogen possessed by the amine curing agent are in a molar ratio (active hydrogen / Epoxy group), preferably 0.4 to 1.5, more preferably 0.5 to 1.3, particularly preferably 0.6 to 1.1, when the protective film-forming film is thermally cured. It becomes easy to control the later glass transition temperature within the above range.
  • the amine-based curing agent is a film for forming a protective film.
  • the content is preferably 5 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).
  • 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 (B).
  • 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 contained in an amount of preferably 1 to 10 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). It is. 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. By adding the curing accelerator (B13), 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.
  • a 2nd binder component provides sheet shape maintenance property and thermosetting to the film for protective film formation by containing a thermosetting polymer component (AB).
  • thermosetting 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 includes a functional group that reacts by heating.
  • the functional functional group may be added to the unit of the continuous structure that becomes the skeleton of the thermosetting polymer component (AB) or may be added to the terminal.
  • the curing functional group may be added to the side chain or directly to the main chain. It may be added.
  • the weight average molecular weight (Mw) of the thermosetting 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.
  • thermosetting polymer component (AB) having an epoxy group examples include a phenoxy resin having an epoxy group.
  • thermosetting polymer component (AB) having an epoxy group examples include 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 epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers.
  • epoxy group-containing (meth) acrylic acid esters examples include glycidyl (meth) Non-acrylic epoxy group-containing monomers such as acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-epoxycyclo-2-hydroxypropyl (meth) acrylate, etc. Examples thereof include glycidyl crotonate and allyl glycidyl ether.
  • the epoxy group-containing monomer an epoxy group-containing (meth) acrylic acid ester is preferable, and glycidyl (meth) acrylate is particularly preferable.
  • the preferred embodiment is the same as that of the acrylic polymer (A1).
  • the thermosetting agent described later as being contained in the second binder component is an amine-based curing agent
  • the epoxy group reacts with active hydrogen possessed by the amine-based curing agent. By doing so, it contributes to the glass transition temperature after thermosetting of the protective film-forming film, and it becomes easy to control the glass transition temperature within the above range. In addition, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film.
  • thermosetting polymer component (AB) having an epoxy group when used, the thermosetting agent (B12) or the curing accelerator is used as in the case of using the epoxy thermosetting component as the thermosetting component (B). It is preferable to use (B13) in combination.
  • the second binder component may contain the above-described polymer component (A) and thermosetting component (B) in combination with the thermosetting polymer component (AB).
  • the protective film-forming film contains one or both of the thermosetting component (B) and the thermosetting polymer component (AB), the protective film-forming film has thermosetting properties. .
  • the protective film-forming film contains at least the thermosetting component (B). It is preferable. However, when the protective film-forming film contains only the thermosetting component (B), the sheet shape maintainability of the protective film-forming film may be inferior. Then, it is preferable that the film for protective film formation contains a thermosetting component (B) and any one or both of a polymer component (A) and a thermosetting polymer component (AB).
  • the thermosetting component (B) is preferably 70 with respect to a total of 100 parts by mass of the polymer component (A) and the thermosetting polymer component (AB). More than mass parts are contained, more preferably more than 85 parts by mass.
  • the content of the thermosetting component (B) is in such a range with respect to the lower limit, the glass transition temperature after thermosetting of the protective film-forming film and the tensile elastic modulus at 23 ° C. after thermosetting are described above. Easy to adjust.
  • the reference content is the content of the epoxy group-containing acrylic polymer before being crosslinked.
  • the thermosetting component (B) is preferably contained in an amount of 135 parts by mass or less with respect to 100 parts by mass in total of the polymer component (A) and the thermosetting polymer component (AB). It is.
  • the content of the thermosetting component (B) is in such a range with respect to the upper limit, the sheet shape maintainability and flexibility of the protective film-forming film tend to be kept good.
  • the protective film-forming film contains an inorganic filler (C) described later, if the content of the inorganic filler (C) is large, the sheet shape maintainability and flexibility of the protective film-forming film are reduced. In addition, resistance to bending and handleability may be reduced. Therefore, it is particularly preferable that the content of the thermosetting component (B) is in such a range with respect to the upper limit.
  • the protective film-forming film contains a total of 100 masses of the polymer component (A) and the thermosetting polymer component (AB).
  • the epoxy compound (B11) is preferably contained in an amount of 70 parts by mass or more, more preferably 85 to 130 parts by mass, and still more preferably 85 to 120 parts by mass with respect to parts.
  • the film for forming a protective film may contain the following components.
  • the inorganic filler protective film-forming film preferably contains an inorganic filler (C).
  • blending an inorganic filler (C) with the film for protective film formation it becomes easy to adjust the tensile elasticity modulus in 23 degreeC after thermosetting in the above-mentioned range.
  • 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.
  • 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.
  • Preferred inorganic fillers 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, glass fibers, and the like.
  • 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 range of the content of the inorganic filler (C) for obtaining the above-mentioned effect more reliably is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film, More preferred is 40 to 70 parts by mass, and particularly preferred is 55 to 65 parts by mass.
  • the average particle size of the inorganic filler (C) is preferably 0.02 to 5 ⁇ m, more preferably 0.05 to 4.5 ⁇ m, and particularly preferably 0.1 to 4 ⁇ m. By setting the average particle diameter of the inorganic filler (C) within the above range, the warp correction function is improved.
  • the average particle diameter of the inorganic filler (C) is the number average particle diameter calculated as the arithmetic average value of 20 major axis diameters of 20 inorganic fillers (C) randomly selected with an electron microscope.
  • 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.
  • silane coupling agent a functional group that reacts with the organic functional group reacts with a functional group that the polymer component (A), the thermosetting component (B), the thermosetting polymer component (AB), or the like has.
  • a silane coupling agent which is a group is 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 mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the polymer component (A), the thermosetting component (B) and the thermosetting polymer component (AB). It is contained in a proportion of 0.2 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.
  • additives may be blended in the film for forming a general-purpose additive protective film as necessary.
  • additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, and the like.
  • the protective film-forming film has an initial adhesive property and a thermosetting property, and adheres easily by being pressed 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. Finally, a protective film having high impact resistance can be provided through thermosetting, excellent in adhesive strength, and can maintain a sufficient protective function 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 was measured and set to the highest value (maximum transmittance).
  • the film for forming a protective 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.
  • the composite sheet for forming a protective film is obtained by forming the support sheet so as to be peelable on one side of the film for forming a protective film.
  • 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 pre-molded configuration may be taken that is laminated on the support sheet.
  • 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 1st structure is the structure by which the adhesive sheet 3 in which the adhesive layer 2 was formed on the base material 1 was formed so that peeling was possible on the single side
  • the pressure-sensitive adhesive layer is composed of an energy ray-curable pressure-sensitive adhesive, and the region where the protective film-forming film is laminated is irradiated with energy rays in advance to reduce the adhesiveness. On the other hand, other regions may be maintained with high adhesive strength without being irradiated with energy rays.
  • 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. 4, the protective film-forming film 10 and the support sheet (in FIG. 4, the pressure-sensitive adhesive layer 2 is formed on the substrate 1).
  • a jig adhesive layer 4 may be provided on the outer peripheral portion of the 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 heel 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 surface opposite to the surface to be attached to the support sheet 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.
  • 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 preferably further includes the following steps (1) to (3), and in order to exert the function of correcting the warpage of the wafer included in the protective film-forming film, Step (2) is performed prior to 3).
  • the process (3) is performed from the viewpoint of simplifying the manufacturing process of the semiconductor device.
  • Step (1) peeling off the protective film-forming film or protective film and the support sheet
  • Step (2) The protective film-forming film is cured to obtain a protective film.
  • the method for manufacturing a semiconductor device in the present invention may further include the following step (4) in addition to the above steps (1) to (3).
  • 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 is removed by chemical etching, plasma etching, or the like.
  • a protective film-forming film of the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer.
  • the steps (1) to (3) are performed in the order of the steps (1), (2), (3), the steps (2), (1), (3) or the steps (2), (3), It is performed in any order of the order of (1). Details of this process are described in detail in JP-A-2002-280329. As an example, the case where it performs in order of process (1), (2), (3) is demonstrated.
  • the protective film-forming film 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.
  • the support sheet is peeled from the protective film-forming film to obtain a laminate of the semiconductor wafer and the protective film-forming film.
  • the protective film-forming film is cured, and a protective film is formed on the entire surface of the wafer.
  • the protective film-forming film is cured by thermosetting.
  • a protective film made of a cured resin is formed on the back surface of the wafer, and the strength is improved as compared with the case of the wafer alone, so that damage during handling of the thinned wafer can be reduced.
  • the thickness of the protective film is excellent compared to a coating method in which a coating liquid for the protective film is directly applied to the back surface of the wafer or chip.
  • the laminated body of the semiconductor wafer and the protective film is diced for each circuit formed on the wafer surface. Dicing is performed so as to cut both the wafer and the protective film.
  • the wafer is diced by a conventional method using a dicing sheet. As a result, a group of semiconductor chips that are separated on the dicing sheet and have a protective film on the back surface is obtained.
  • 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.
  • a semiconductor chip having a protective film on the back surface is picked up by a general-purpose means such as a collet to obtain a chip with a protective film. Then, the semiconductor device can be manufactured by mounting the chip with protective film on a predetermined base by the face-down method. 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. According to the present invention as described above, 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 step (3) is performed before the step (1) (steps (2), (3),
  • the composite sheet for forming a protective film can serve as a dicing sheet. That is, it can be used as a sheet for supporting the semiconductor wafer during the dicing process.
  • the semiconductor wafer is bonded to the inner peripheral portion of the protective film forming composite sheet via the protective film forming film, and the outer peripheral portion of the protective film forming composite sheet is joined to another jig such as a ring frame.
  • the composite sheet for forming a protective film attached to the semiconductor wafer is fixed to the apparatus, and dicing is performed.
  • 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.
  • ⁇ Glass transition temperature after thermosetting> Four protective film-forming films with a thickness of 45 ⁇ m are laminated and thermally cured (at 130 ° C. for 2 hours) in an oven to form a strip with a width of 4.5 mm, a length of 20.0 mm, and a thickness of 0.18 mm.
  • the test piece was produced by cutting. Using a viscoelasticity measuring apparatus (DMA instruments made by TA instruments, DMA Q800), in a tensile mode, the tan ⁇ (ratio of loss elastic modulus to storage elastic modulus) of the test piece was set to a frequency of 11 Hz, a heating rate of 3 ° C./min, The measurement was performed at 0 to 300 ° C. in an air atmosphere. The temperature at which tan ⁇ exhibited the maximum value in this temperature range was read and used as the glass transition temperature (Tg) after thermosetting of the protective film-forming film.
  • Tg glass transition temperature
  • thermosetting> The storage elastic modulus at 23 ° C. of the measurement data obtained by the above measurement of ⁇ glass transition temperature after thermosetting> was read, and the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film was obtained.
  • a test piece (size: 100 mm ⁇ 100 mm) in which a film for forming a protective film having a thickness of 45 ⁇ m was attached to a copper foil having a thickness of 30 ⁇ m was thermally cured (at 130 ° C. for 2 hours) in an atmosphere in an oven. Then, due to the shrinkage accompanying thermal curing of the protective film-forming film, the distance between the points is the maximum value in the rounded shape of the copper foil that is rounded with the surface on which the protective film-forming film is attached inside. The following two points were taken and the distance was measured. It means that the copper foil is greatly warped as the distance is smaller, and the stress due to thermal shrinkage of the protective film-forming film is larger, so that it can be judged that the warp correction ability is high.
  • ⁇ Reliability evaluation> 1 Production of chip with protective film # 2000 Polished protective film-forming film of composite sheet for protective film formation on a polished silicon wafer (200 mm diameter, 350 ⁇ m thickness) tape mounter (Adwill RAD-3600 F / 12) was applied while heating to 70 ° C., and then the support sheet was peeled off. Thereafter, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to obtain a laminate of a silicon wafer and a protective film.
  • the protective film side of the laminate obtained above is affixed to a dicing tape (Adwill D-686H manufactured by Lintec Corporation), and is diced to a size of 3 mm ⁇ 3 mm using a dicing apparatus (DFD651 manufactured by Disco Corporation). A chip with a protective film for property evaluation was obtained.
  • ⁇ Wafer warpage evaluation> An 8-inch wafer with a circuit having a thickness of 200 ⁇ m and having a concave warpage (warpage amount: 10 mm) on the circuit surface side (surface side) was prepared (see FIG. 5). Next, a protective film-forming film was attached to the back surface of the wafer, and heat cured at 130 ° C. for 2 hours. Then, the case where the amount of warpage of the obtained wafer was 2 mm or less was evaluated as “good”, and the case where the amount of warpage of the wafer exceeded 2 mm was evaluated as “bad”. If the amount of warpage of the wafer is 2 mm or less, it can be transferred by a general wafer mounter.
  • composition for forming protective film Each component which comprises the composition for protective film formation is shown below.
  • A1-1) Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 15 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight) (Average molecular weight: 900,000, glass transition temperature: -28 ° C)
  • A1-2 Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 35 parts by mass of methyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 900,000, Glass transition temperature: -31 ° C)
  • B11-1) Bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent of 184 to 194 g / eq)
  • B11-2) Bis
  • Examples and Comparative Examples The said component was mix
  • the compounding quantity of each component in Table 1 shows the mass part of solid content conversion, and solid content means all components other than a solvent in this invention.
  • the protective film-forming composition having the composition shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration was 61% by mass, and the release-treated surface of the support sheet (SP-PET3811 manufactured by Lintec, thickness 38 ⁇ m) Coating and drying (drying conditions: 120 ° C.
  • Base material 2 Adhesive layer 3: Adhesive sheet (support sheet) 4: Jig adhesion layer 5: Interfacial adhesion adjustment layer 10: Film for protective film formation 100: Composite sheet for protective film formation

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Abstract

[Problem] To provide a protective film-forming film that minimizes warping of a wafer, and is capable of forming a highly-reliable protective film on a chip. [Solution] This protective film-forming film is thermally curable, has a glass transition temperature after being thermally cured of 150 to 300°C, and has a modulus of elasticity at a temperature of 23°C after being thermally cured of 0.5 to 10 GPa.

Description

保護膜形成用フィルムおよび保護膜形成用複合シートProtective film forming film and protective film forming composite sheet
　本発明は、半導体ウエハや半導体チップに保護膜を形成でき、かつ、半導体チップの製造効率の向上が可能な保護膜形成用フィルムに関する。特にいわゆるフェースダウン（face down）方式で実装される半導体チップの製造に用いられる保護膜形成用フィルムに関する。 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. In particular, 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.
　近年、いわゆるフェースダウン（face down）方式と呼ばれる実装法を用いた半導体装置の製造が行われている。フェースダウン方式においては、回路面上にバンプなどの電極を有する半導体チップ（以下、単に「チップ」ともいう。）が用いられ、該電極が基板と接合される。このため、チップの回路面とは反対側の面（チップ裏面）は剥き出しとなることがある。 In recent years, semiconductor devices have been manufactured using a so-called “face-down” mounting method. In the face-down method, a semiconductor chip (hereinafter simply referred to as “chip”) having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.
　この剥き出しとなったチップ裏面は、有機膜により保護されることがある。従来、この有機膜からなる保護膜を有するチップは、液状の樹脂をスピンコート法によりウエハ裏面に塗布し、乾燥し、硬化してウエハとともに保護膜を切断して得られる。しかしながら、このようにして形成される保護膜の厚み精度は充分でないため、製品の歩留まりが低下することがあった。 The exposed chip back surface may be protected by an organic film. Conventionally, 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. However, since the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.
　上記問題を解決するため、熱またはエネルギー線硬化性成分を含む硬化性保護膜形成層を有するチップ用保護膜形成用シートが開示されている（特許文献１）。 In order to solve the above problem, a protective film forming sheet for chips having a curable protective film forming layer containing a heat or energy ray curable component is disclosed (Patent Document 1).
　従来、ウエハ自体が充分に厚い場合には、ウエハ自体が反ることはなかったが、ウエハが薄くなるに伴い、回路が形成されたウエハ表面と回路が形成されていないウエハ裏面との収縮率の差などによって薄化したウエハに反りが生じるという問題が発生している。
　反りの大きなウエハは、その後のチップ製造工程中に搬送不良を引き起こすおそれがある。また、ウエハの反りに起因してウエハのダイシングが困難になるおそれがある。
　このようなウエハの反りによる問題を解消するために、ウエハ裏面に貼付される保護膜形成用フィルムにはウエハの反りを矯正する性能が求められている。 Conventionally, when the wafer itself is sufficiently thick, the wafer itself has not warped. However, as the wafer becomes thinner, the shrinkage ratio between the wafer surface on which the circuit is formed and the back surface of the wafer on which the circuit is not formed. There is a problem that warpage occurs in the thinned wafer due to the difference in the above.
A wafer having a large warp may cause a conveyance failure during the subsequent chip manufacturing process. Further, the wafer may be difficult to dice due to the warpage of the wafer.
In order to solve the problem caused by the warpage of the wafer, the protective film-forming film attached to the back surface of the wafer is required to have a capability of correcting the warpage of the wafer.
　特許文献２では、熱硬化させる際の２３℃から１６５℃までの範囲内における体積収縮率が１００ｐｐｍ／℃以上４００ｐｐｍ／℃以下であり、熱硬化後の２３℃における引張貯蔵弾性率が１ＧＰａ以上５ＧＰａ以下であるフリップチップ型半導体裏面用フィルムを用いて、半導体ウエハや半導体チップ等の半導体素子に反りが発生することを抑制または防止している。
　また、特許文献３では、熱硬化前の全体積に対する熱硬化による収縮量が２体積％以上３０体積％以下であるフリップチップ型半導体裏面用フィルムを用いて、半導体素子に反りが発生することを抑制または防止している。 In Patent Document 2, the volume shrinkage in the range from 23 ° C. to 165 ° C. when thermosetting is 100 ppm / ° C. or more and 400 ppm / ° C. or less, and the tensile storage modulus at 23 ° C. after thermosetting is 1 GPa or more and 5 GPa. The following flip chip type semiconductor back film is used to suppress or prevent warping of semiconductor elements such as semiconductor wafers and semiconductor chips.
Moreover, in patent document 3, using the film for flip chip type semiconductor back surfaces whose shrinkage | contraction by thermosetting with respect to the whole volume before thermosetting is 2 volume% or more and 30 volume% or less, that a semiconductor element warps generate | occur | produces. Suppressed or prevented.
特開２００４－２１４２８８号公報JP 2004-214288 A 特開２０１２－３３５５４号公報JP 2012-33554 A 特開２０１１－２２８４９９号公報JP 2011-228499 A
　近年、ウエハ表面に形成される回路パターンが多種多様化し、回路形成に起因した反りが大きなウエハが増えてきている。そのため、さらに著しいウエハの反りを矯正しうる保護膜形成用フィルムが求められているが、特許文献２や特許文献３のフリップチップ型半導体裏面用フィルムでは、ウエハやチップの反りを充分に解消できないことがあった。また、本発明者らが反りの矯正機能のさらなる向上を鋭意試みたところ、得られる保護膜付チップにおいて保護膜とチップとの接合部における剥離や保護膜におけるクラックが発生することがあり、その信頼性が充分なものでないことがあった。 In recent years, circuit patterns formed on the wafer surface have been diversified, and an increasing number of wafers have a large amount of warpage due to circuit formation. Therefore, a film for forming a protective film that can correct a more significant warpage of the wafer is demanded. However, the films for flip-chip type semiconductor back surfaces of Patent Document 2 and Patent Document 3 cannot sufficiently eliminate the warpage of the wafer or chip. There was a thing. Moreover, when the present inventors diligently tried to further improve the correction function of the warp, in the obtained chip with protective film, peeling at the joint between the protective film and the chip or cracks in the protective film may occur, In some cases, the reliability was not sufficient.
　本発明の課題は、ウエハの反りを抑制すると共に、チップに信頼性の高い保護膜を形成できる保護膜形成用フィルムを提供することである。 An object of the present invention is to provide a film for forming a protective film that can suppress warping of a wafer and can form a highly reliable protective film on a chip.
　本発明の要旨は以下の通りである。
〔１〕熱硬化性を有し、
　熱硬化後のガラス転移温度が１５０～３００℃であり、
　熱硬化後の２３℃における引張弾性率が０．５～１０ＧＰａである保護膜形成用フィルム。 The gist of the present invention is as follows.
[1] It has thermosetting properties,
The glass transition temperature after thermosetting is 150 to 300 ° C.,
A protective film-forming film having a tensile elastic modulus at 23 ° C. of 0.5 to 10 GPa after thermosetting.
〔２〕エポキシ化合物およびアミン系硬化剤を含有してなる熱硬化性成分が含まれる〔１〕に記載の保護膜形成用フィルム。 [2] The film for forming a protective film according to [1], comprising a thermosetting component containing an epoxy compound and an amine curing agent.
〔３〕さらに重合体成分および熱硬化性重合体成分のいずれか単独または両方を含有し、重合体成分および熱硬化性重合体成分の合計１００質量部に対して、熱硬化性成分を１３５質量部以下含む〔２〕に記載の保護膜形成用フィルム。 [3] Further, either or both of the polymer component and the thermosetting polymer component are contained, and 135 parts by mass of the thermosetting component with respect to a total of 100 parts by mass of the polymer component and the thermosetting polymer component. [2] The protective film-forming film according to [2], which is contained in a part or less.
〔４〕保護膜形成用フィルムには無機フィラーが含まれ、
　無機フィラーの含有量が、保護膜形成用フィルムを構成する全固形分１００質量部に対して１０～７０質量部である〔１〕～〔３〕のいずれかに記載の保護膜形成用フィルム。 [4] The protective film-forming film contains an inorganic filler,
The protective film-forming film according to any one of [1] to [3], wherein the content of the inorganic filler is 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film.
〔５〕無機フィラーの平均粒径が０．０２～５μｍである〔４〕に記載の保護膜形成用フィルム。 [5] The film for forming a protective film according to [4], wherein the inorganic filler has an average particle size of 0.02 to 5 μm.
〔６〕保護膜形成用フィルムには熱硬化性重合体成分が含まれ、
　熱硬化性重合体成分は、構成する単量体としてエポキシ基含有単量体を含むアクリル系重合体である〔１〕～〔５〕のいずれかに記載の保護膜形成用フィルム。 [6] The protective film-forming film contains a thermosetting polymer component,
The film for forming a protective film according to any one of [1] to [5], wherein the thermosetting polymer component is an acrylic polymer containing an epoxy group-containing monomer as a constituent monomer.
〔７〕上記〔１〕～〔６〕のいずれかに記載の保護膜形成用フィルムの片面に支持シートを剥離可能に形成してなる保護膜形成用複合シート。 [7] A composite sheet for forming a protective film, wherein a support sheet is detachably formed on one side of the film for forming a protective film according to any one of [1] to [6].
　本発明によれば、ウエハ表面側の回路形成に起因した収縮によるウエハの反りに対して、ウエハ裏面に保護膜形成用フィルムを貼付し熱硬化することで、保護膜形成用フィルムの硬化収縮に起因した応力により、ウエハの反りを矯正でき、かつ、信頼性の高い保護膜付チップを得ることができる。 According to the present invention, the protective film-forming film can be cured and contracted by applying a protective film-forming film to the back surface of the wafer and thermally curing the wafer due to shrinkage caused by circuit formation on the wafer front side. The warpage of the wafer can be corrected by the resulting stress, and a highly reliable chip with a protective film can be obtained.
本発明に係る保護膜形成用フィルムを用いて形成される保護膜形成用複合シートの第１の態様を示す。The 1st aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown. 本発明に係る保護膜形成用フィルムを用いて形成される保護膜形成用複合シートの第２の態様を示す。The 2nd aspect of the composite sheet for protective film formation formed using the film for protective film formation concerning this invention is shown. 本発明に係る保護膜形成用フィルムを用いて形成される保護膜形成用複合シートの第３の態様を示す。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. 本発明に係る保護膜形成用フィルムを用いて形成される保護膜形成用複合シートの第４の態様を示す。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. 実施例において評価した「反り量」を説明する図面である。It is drawing explaining the "warpage amount" evaluated in the Example.
　以下、本発明の保護膜形成用フィルムの詳細を説明する。 Hereinafter, the details of the protective film-forming film of the present invention will be described.
［保護膜形成用フィルム］
　本発明の保護膜形成用フィルムは、熱硬化性を有し、熱硬化後のガラス転移温度（Ｔｇ）が１５０～３００℃、好ましくは１７０～２８０℃、より好ましくは２２０～２７０℃である。本発明における、保護膜形成用フィルムの熱硬化後のガラス転移温度（Ｔｇ）は、周波数１１Ｈｚで測定した熱硬化後の保護膜形成用フィルム（保護膜）の動的粘弾性測定における－５０～３０℃の低温領域で損失正接tanδが最大値を示す温度を指す。
　保護膜形成用フィルムの熱硬化後のＴｇが１５０℃未満であると、通常１２０～１５０℃程度で行われる保護膜形成用フィルムの熱硬化工程において、保護膜形成用フィルムの流動性が高まり、保護膜形成用フィルムの硬化収縮に起因した応力が緩和され小さくなる。その結果、ウエハの反りの矯正が不十分となる。
　一方、保護膜形成用フィルムの熱硬化後のＴｇが３００℃を超えると、保護膜形成用フィルムや該フィルムを熱硬化して得られる保護膜が、ウエハやチップから剥離するおそれがあり、その結果、保護膜付チップの信頼性が低下する。
　保護膜形成用フィルムの熱硬化後のＴｇを上記範囲とすることで、該フィルムの熱硬化工程において、保護膜形成用フィルムが所定の剛性を有するため該フィルムの硬化収縮に起因した応力が緩和されず、ウエハや該ウエハを個片化して得られるチップの反りを矯正することができる。 [Film for forming a protective film]
The protective film-forming film of the present invention has thermosetting properties, and has a glass transition temperature (Tg) after thermosetting of 150 to 300 ° C, preferably 170 to 280 ° C, more preferably 220 to 270 ° C. In the present invention, the glass transition temperature (Tg) after thermosetting of the protective film-forming film is −50 to in the dynamic viscoelasticity measurement of the protective film-forming film (protective film) after thermosetting measured at a frequency of 11 Hz. It indicates the temperature at which the loss tangent tan δ exhibits a maximum value in a low temperature region of 30 ° C.
If the Tg after thermosetting of the protective film-forming film is less than 150 ° C., the fluidity of the protective film-forming film is increased in the thermosetting process of the protective film-forming film usually performed at about 120 to 150 ° C., Stress due to curing shrinkage of the protective film-forming film is relieved and reduced. As a result, the correction of the warpage of the wafer is insufficient.
On the other hand, if the Tg of the protective film-forming film after thermosetting exceeds 300 ° C., the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. As a result, the reliability of the chip with protective film decreases.
By setting the Tg after thermosetting of the protective film-forming film within the above range, the protective film-forming film has a predetermined rigidity in the thermosetting process of the film, so that stress due to curing shrinkage of the film is relieved. Instead, the warpage of the wafer or chips obtained by dividing the wafer into pieces can be corrected.
　また、保護膜形成用フィルムは、熱硬化後の２３℃における引張弾性率が０．５～１０ＧＰａ、好ましくは１～１０ＧＰａ、より好ましくは５ＧＰａを超え８ＧＰａ以下である。
　保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率が０．５ＧＰａ未満であると、保護膜形成用フィルムの硬化収縮に起因した応力を維持することができず、該応力が緩和され、ウエハの反りの矯正が不十分となる。一方、保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率が１０ＧＰａを超えると、保護膜形成用フィルムや該フィルムを熱硬化して得られる保護膜が、ウエハやチップから剥離するおそれがある。
　保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率を上記範囲とすることで、ウエハやチップの反りを矯正すると共に保護膜付チップの信頼性を向上させることができる。 The protective film-forming film has a tensile elastic modulus at 23 ° C. after thermosetting of 0.5 to 10 GPa, preferably 1 to 10 GPa, more preferably more than 5 GPa and 8 GPa or less.
If the tensile elastic modulus at 23 ° C. after thermal curing of the protective film-forming film is less than 0.5 GPa, stress due to curing shrinkage of the protective film-forming film cannot be maintained, and the stress is relieved. The correction of the warpage of the wafer becomes insufficient. On the other hand, if the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film exceeds 10 GPa, the protective film-forming film or the protective film obtained by thermosetting the film may be peeled off from the wafer or chip. There is.
By setting the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film within the above range, it is possible to correct the warpage of the wafer and the chip and improve the reliability of the chip with the protective film.
　また、保護膜形成用フィルムの１３０℃で２時間加熱時における熱収縮率は、好ましくは０．１～１０％、より好ましくは０．５～５％である。保護膜形成用フィルムの１３０℃で２時間加熱時における熱収縮率を上記範囲とすることで、ウエハの反りを矯正する効果（反り矯正性能）が向上する。なお、１３０℃で２時間加熱時における保護膜形成用フィルムの熱収縮率は、１３０℃の環境下に保護膜形成用フィルムを投入する前後の保護膜形成用フィルムの面積から下記式により求められる。 The thermal shrinkage rate of the protective film-forming film when heated at 130 ° C. for 2 hours is preferably 0.1 to 10%, more preferably 0.5 to 5%. By making the thermal shrinkage rate when the protective film-forming film is heated at 130 ° C. for 2 hours within the above range, the effect of correcting the warpage of the wafer (warpage correction performance) is improved. In addition, the thermal contraction rate of the protective film-forming film when heated at 130 ° C. for 2 hours is obtained from the area of the protective film-forming film before and after the protective film-forming film is put in an environment at 130 ° C. by the following formula. .
　熱収縮率（％）＝｛（投入前の保護膜形成用フィルムの面積）－（投入後の保護膜形成用フィルムの面積）｝／投入前の保護膜形成用フィルムの面積×１００ Heat shrinkage rate (%) = {(area of protective film forming film before loading) − (area of protective film forming film after loading)} / area of protective film forming film before loading × 100
　保護膜形成用フィルムに少なくとも要求される機能は、（１）シート形状維持性、（２）初期接着性および（３）硬化性である。なお、本発明の保護膜形成用フィルムは上述のとおり熱硬化性を有するが、熱以外の手段によって硬化する性質を有していてもよい。 At least the functions required for the protective film-forming film are (1) sheet shape maintenance, (2) initial adhesiveness, and (3) curability. In addition, although the film for protective film formation of this invention has thermosetting as above-mentioned, you may have the property hardened | cured by means other than a heat | fever.
 保護膜形成用フィルムには、バインダー成分の添加により（１）シート形状維持性および（３）硬化性を付与することができ、バインダー成分としては、重合体成分（Ａ）および熱硬化性成分（Ｂ）を含有する第１のバインダー成分または（Ａ）成分および（Ｂ）成分の性質を兼ね備えた熱硬化性重合体成分（ＡＢ）を含有する第２のバインダー成分を用いることができる。
 なお、保護膜形成用フィルムを硬化までの間被着体に仮着させておくための機能である（２）初期接着性は、感圧接着性であってもよく、熱により軟化して接着する性質であってもよい。（２）初期接着性は、通常バインダー成分の諸特性や、後述する無機フィラー（Ｃ）の配合量の調整などにより制御される。 The protective film-forming film can be provided with (1) sheet shape maintainability and (3) curability by adding a binder component. As the binder component, the polymer component (A) and the thermosetting component ( The first binder component containing B) or the second binder component containing the thermosetting polymer component (AB) having the properties of the component (A) and the component (B) can be used.
In addition, it is a function for temporarily attaching the protective film-forming film to the adherend until it is cured. (2) The initial adhesiveness may be pressure-sensitive adhesiveness, and is softened and bonded by heat. It may be a property to do. (2) 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.
（第１のバインダー成分）
 第１のバインダー成分は、重合体成分（Ａ）と熱硬化性成分（Ｂ）を含有することにより、保護膜形成用フィルムにシート形状維持性と熱硬化性を付与する。なお、第１のバインダー成分は、第２のバインダー成分と区別する便宜上、熱硬化性重合体成分（ＡＢ）を含有しない。 (First binder component)
A 1st binder component provides a sheet | seat shape maintenance property and thermosetting property to the film for protective film formation by containing a polymer component (A) and a thermosetting component (B). In addition, a 1st binder component does not contain a thermosetting polymer component (AB) for convenience which distinguishes from a 2nd binder component.
（Ａ）重合体成分
 重合体成分（Ａ）は、保護膜形成用フィルムにシート形状維持性を付与することを主目的として保護膜形成用フィルムに添加される。
 上記の目的を達成するため、重合体成分（Ａ）の重量平均分子量（Ｍｗ）は、通常２０，０００以上であり、２０，０００～３，０００，０００であることが好ましい。重量平均分子量（Ｍｗ）の値は、ゲル・パーミエーション・クロマトグラフィー法（ＧＰＣ）法（ポリスチレン標準）により測定される場合の値である。このような方法による測定は、たとえば、東ソー社製の高速ＧＰＣ装置「ＨＬＣ－８１２０ＧＰＣ」に、高速カラム「ＴＳＫ ｇｕｒｄ ｃｏｌｕｍｎ ＨXL－Ｈ」、「ＴＳＫ Ｇｅｌ ＧＭＨXL」、「ＴＳＫ Ｇｅｌ Ｇ２０００ ＨXL」（以上、全て東ソー社製）をこの順序で連結したものを用い、カラム温度：４０℃、送液速度：１.０ｍＬ／分の条件で、検出器を示差屈折率計として行われる。
 なお、後述する熱硬化性重合体成分（ＡＢ）と区別する便宜上、重合体成分（Ａ）は後述する硬化機能官能基を有しない。 (A) Polymer 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.
In order to achieve the above object, 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.
In addition, for convenience to distinguish from the thermosetting polymer component (AB) described later, the polymer component (A) does not have a curing functional functional group described later.
 重合体成分（Ａ）としては、アクリル系重合体、ポリエステル、フェノキシ樹脂（後述する熱硬化性重合体成分（ＡＢ）と区別する便宜上、エポキシ基を有しないものに限る。）、ポリカーボネート、ポリエーテル、ポリウレタン、ポリシロキサン、ゴム系重合体等を用いることができる。また、これらの２種以上が結合したもの、たとえば、水酸基を有するアクリル系重合体であるアクリルポリオールに、分子末端にイソシアネート基を有するウレタンプレポリマーを反応させることにより得られるアクリルウレタン樹脂等であってもよい。さらに、２種以上が結合した重合体を含め、これらの２種以上を組み合わせて用いてもよい。 Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins (for the purpose of distinguishing from thermosetting polymer components (AB) described later, those having no epoxy group), polycarbonates, and polyethers. Polyurethane, polysiloxane, rubber polymer, etc. can be used. Further, it is an acrylic urethane resin 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.
（Ａ１）アクリル系重合体
 重合体成分（Ａ）としては、アクリル系重合体（Ａ１）が好ましく用いられる。アクリル系重合体（Ａ１）のガラス転移温度（Ｔｇ）は、好ましくは－６０～５０℃、より好ましくは－５０～４０℃、さらに好ましくは－４０～３０℃の範囲にある。アクリル系重合体（Ａ１）のガラス転移温度が高いと保護膜形成用フィルムの初期接着性が低下し、被着体に転写できなくなることがある。また、アクリル系重合体（Ａ１）のガラス転移温度が低いと保護膜形成用フィルムと後述する支持シートとの剥離力が大きくなって保護膜形成用フィルムの転写不良が起こることがある。
 なお、アクリル系重合体のＴｇは、ＦＯＸの式から求めた値である。 (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. If the glass transition temperature of the acrylic polymer (A1) is high, the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend. In addition, when the glass transition temperature of the acrylic polymer (A1) is low, the peeling force between the protective film-forming film and a support sheet described later may increase, and transfer failure of the protective film-forming film may occur.
The Tg of the acrylic polymer is a value determined from the FOX equation.
 アクリル系重合体（Ａ１）の重量平均分子量（Ｍｗ）は、１００，０００～１，５００，０００であることが好ましい。アクリル系重合体（Ａ１）の重量平均分子量が高いと保護膜形成用フィルムの初期接着性が低下し、被着体に転写できなくなることがある。また、アクリル系重合体（Ａ１）の重量平均分子量が低いと保護膜形成用フィルムと支持シートとの密着性が高くなり、保護膜形成用フィルムの転写不良が起こることがある。 The weight average molecular weight (Mw) of the acrylic polymer (A1) is preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic polymer (A1) is high, the initial adhesiveness of the protective film-forming film is lowered, and it may not be transferred to the adherend. Further, when the weight average molecular weight of the acrylic polymer (A1) is low, the adhesion between the protective film-forming film and the support sheet is increased, which may cause transfer failure of the protective film-forming film.
 アクリル系重合体（Ａ１）は、少なくとも構成する単量体に、（メタ）アクリル酸エステルを含む。
 （メタ）アクリル酸エステルとしては、アルキル基の炭素数が１～１８であるアルキル（メタ）アクリレート、具体的にはメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、へプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、テトラデシル（メタ）アクリレート、オクタデシル（メタ）アクリレートなど；環状骨格を有する（メタ）アクリレート、具体的にはシクロアルキル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、イミド（メタ）アクリレートなどが挙げられる。また、後述する水酸基を有する単量体、カルボキシル基を有する単量体、アミノ基を有する単量体として例示するもののうち、（メタ）アクリル酸エステルであるものを例示することができる。 The acrylic polymer (A1) contains (meth) acrylic acid ester in at least a constituent monomer.
Examples of (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, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (Meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, etc .; (meth) acrylate having a cyclic skeleton, specifically cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, imide (meth) acrylate. Moreover, what is (meth) acrylic acid ester can be illustrated among what is illustrated as a monomer which has a hydroxyl group mentioned later, a monomer which has a carboxyl group, and a monomer which has an amino group.
 本発明においては、アクリル系重合体（Ａ１）を構成する単量体として、水酸基を有する（メタ）アクリル酸エステル、カルボキシル基を有する（メタ）アクリル酸エステルやアミノ基を有する（メタ）アクリル酸エステルを用いることで、保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率を所定の範囲に制御することが容易となる。 In the present invention, as a monomer constituting the acrylic polymer (A1), a (meth) acrylic acid ester having a hydroxyl group, a (meth) acrylic acid ester having a carboxyl group, or a (meth) acrylic acid having an amino group By using the ester, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film within a predetermined range.
 なお、本明細書で（メタ）アクリルは、アクリルおよびメタクリルの両者を包含する意味で用いることがある。 （In the present specification, (meth) acryl may be used to include both acrylic and methacrylic.
 アクリル系重合体（Ａ１）を構成する単量体として、水酸基を有する単量体を用いてもよい。水酸基を有する単量体としては、ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリル酸エステル；ビニルアルコール、Ｎ－メチロール（メタ）アクリルアミド等が挙げられる。 単 量 体 As a monomer constituting the acrylic polymer (A1), a monomer having a hydroxyl group may be used. Examples of monomers having a hydroxyl group include hydroxyl groups such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate (meth). Acrylic acid ester; vinyl alcohol, N-methylol (meth) acrylamide and the like.
 アクリル系重合体（Ａ１）を構成する単量体として、カルボキシル基を有する単量体を用いてもよい。カルボキシル基を有する単量体としては、２－（メタ）アクリロイロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート等のカルボキシル基を有する（メタ）アクリル酸エステル；（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸等が挙げられる。後述する熱硬化性成分（Ｂ）として、エポキシ系熱硬化性成分を用いる場合には、カルボキシル基とエポキシ系熱硬化性成分中のエポキシ基が反応してしまうため、カルボキシル基を有する単量体の使用量は少ないことが好ましい。 As the monomer constituting the acrylic polymer (A1), a monomer having a carboxyl group may be used. Examples of the monomer having a carboxyl group include (meth) acrylic acid esters having a carboxyl group such as 2- (meth) acryloyloxyethyl phthalate and 2- (meth) acryloyloxypropyl phthalate; Maleic acid, fumaric acid, itaconic acid and the like can be mentioned. When using an epoxy thermosetting component as the thermosetting component (B) described later, the carboxyl group and the epoxy group in the epoxy thermosetting component react with each other, so that the monomer having a carboxyl group The amount used is preferably small.
 アクリル系重合体（Ａ１）を構成する単量体として、アミノ基を有する単量体を用いてもよい。アミノ基を有する単量体単量体としては、モノメチルアミノ（メタ）アクリレート、モノエチルアミノ（メタ）アクリレート、ジエチルアミノ（メタ）アクリレート等のアミノ基を有する（メタ）アクリル酸エステル等が挙げられる。 As the monomer constituting the acrylic polymer (A1), a monomer having an amino group may be used. Examples of the monomer monomer having an amino group include (meth) acrylic acid esters having an amino group such as monomethylamino (meth) acrylate, monoethylamino (meth) acrylate, and diethylamino (meth) acrylate.
 アクリル系重合体（Ａ１）を構成する単量体として、このほか酢酸ビニル、スチレン、エチレン、α－オレフィン等を用いてもよい。 In addition, vinyl acetate, styrene, ethylene, α-olefin and the like may be used as the monomer constituting the acrylic polymer (A1).
 アクリル系重合体（Ａ１）は架橋されていてもよい。架橋は、架橋される前のアクリル系重合体（Ａ１）が水酸基等の架橋性官能基を有しており、保護膜形成用フィルムを形成するための組成物中に架橋剤を添加することで架橋性官能基と架橋剤の有する官能基が反応することにより行われる。アクリル系重合体（Ａ１）を架橋することにより、保護膜形成用フィルムの凝集力を調節することが可能となる。また、アクリル系重合体（Ａ１）の架橋密度を調整することで、保護膜形成用フィルムの熱硬化後のガラス転移温度や熱硬化後の２３℃における引張弾性率を制御することができる。架橋密度は後述する架橋剤の添加量で制御できる。 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. By crosslinking the acrylic polymer (A1), the cohesive force of the protective film-forming film can be adjusted. Further, by adjusting the crosslink density of the acrylic polymer (A1), the glass transition temperature of the protective film-forming film after thermosetting and the tensile elastic modulus at 23 ° C. after thermosetting can be controlled. The crosslinking density can be controlled by the addition amount of a crosslinking agent described later.
 架橋剤としては有機多価イソシアネート化合物、有機多価イミン化合物などが挙げられる。 Examples of the crosslinking agent include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
 有機多価イソシアネート化合物としては、芳香族多価イソシアネート化合物、脂肪族多価イソシアネート化合物、脂環族多価イソシアネート化合物およびこれらの有機多価イソシアネート化合物の三量体、ならびにこれら有機多価イソシアネート化合物とポリオール化合物とを反応させて得られる末端イソシアネートウレタンプレポリマー等を挙げることができる。 Examples of 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.
 有機多価イソシアネート化合物として、具体的には、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ジフェニルメタン－２，４’－ジイソシアネート、３－メチルジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、ジシクロヘキシルメタン－２，４’－ジイソシアネート、リジンイソシアネート、およびこれらの多価アルコールアダクト体が挙げられる。 Specific examples of the organic polyvalent isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-. Diisocyanate, diphenylmethane-2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, lysine isocyanate, and these Examples thereof include polyhydric alcohol adducts.
 有機多価イミン化合物として、具体的には、Ｎ，Ｎ’－ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキシアミド）、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート、テトラメチロールメタン－トリ－β－アジリジニルプロピオネートおよびＮ，Ｎ’－トルエン－２，４－ビス（１－アジリジンカルボキシアミド）トリエチレンメラミン等を挙げることができる。 Specific examples of organic polyvalent imine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylol. Mention may be made of methane-tri-β-aziridinylpropionate and N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine.
 架橋剤は架橋する前のアクリル系重合体（Ａ１）１００質量部に対して通常０．０１～２０質量部、好ましくは０．１～１０質量部、より好ましくは０．５～５質量部の比率で用いられる。 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.
 本発明において、保護膜形成用フィルムを構成する成分の含有量の態様について、重合体成分（Ａ）の含有量を基準として定める場合、重合体成分（Ａ）が架橋されたアクリル系重合体であるときは、その基準とする含有量は、架橋される前のアクリル系重合体の含有量である。 In the present invention, 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.
（Ｂ）熱硬化性成分
 熱硬化性成分（Ｂ）は、保護膜形成用フィルムに熱硬化性を付与することを主目的として保護膜形成用フィルムに添加される。
 熱硬化性成分（Ｂ）は、少なくとも加熱により反応する官能基を有する化合物を含有する。熱硬化性成分（Ｂ）が有する官能基同士が反応し、三次元網目構造が形成されることにより硬化が実現される。熱硬化性成分（Ｂ）は、重合体成分（Ａ）と組み合わせて用いるため、保護膜形成用フィルムを形成するための塗工用組成物の粘度を抑制し、取り扱い性を向上させる等の観点から、通常その重量平均分子量（Ｍｗ）は、１０，０００以下であり、１００～１０，０００であることが好ましい。 (B) Thermosetting component The thermosetting component (B) is added to the protective film-forming film mainly for the purpose of imparting thermosetting properties to the protective film-forming film.
The thermosetting component (B) contains at least a compound having a functional group that reacts by heating. Curing is realized by the functional groups of the thermosetting component (B) reacting to form a three-dimensional network structure. Since the thermosetting 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. Therefore, the weight average molecular weight (Mw) is usually 10,000 or less, preferably 100 to 10,000.
 熱硬化性成分（Ｂ）としては、たとえば、エポキシ系熱硬化性成分が好ましい。
 エポキシ系熱硬化性成分は、エポキシ基を有する化合物（Ｂ１１）（以下、「エポキシ化合物（Ｂ１１）」ということがある。）を含有し、エポキシ基を有する化合物（Ｂ１１）と熱硬化剤（Ｂ１２）を組み合わせたものを用いることが好ましく、さらに硬化促進剤（Ｂ１３）を組み合わせたものを用いることがより好ましい。 As the thermosetting component (B), for example, an epoxy thermosetting component is preferable.
The epoxy thermosetting component contains a compound (B11) having an epoxy group (hereinafter sometimes referred to as “epoxy compound (B11)”), a compound (B11) having an epoxy group, and a thermosetting agent (B12). ) Are preferably used, and more preferably a combination of a curing accelerator (B13).
（Ｂ１１）エポキシ基を有する化合物
 エポキシ化合物（Ｂ１１）としては、従来公知のものを用いることができる。具体的には、多官能系エポキシ樹脂や、ビスフェノールＡジグリシジルエーテルやその水添物、ｏ－クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェニレン骨格型エポキシ樹脂など、分子中に２官能以上有するエポキシ化合物が挙げられる。これらは１種単独で、または２種以上を組み合わせて用いることができる。 (B11) As a compound epoxy compound (B11) having an epoxy group , conventionally known compounds can be used. Specifically, polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenols Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as F-type epoxy resins and phenylene skeleton-type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.
（Ｂ１２）熱硬化剤
 熱硬化剤（Ｂ１２）は、エポキシ化合物（Ｂ１１）に対する硬化剤として機能する。好ましい熱硬化剤としては、１分子中にエポキシ基と反応しうる官能基を２個以上有する化合物が挙げられる。その官能基としてはフェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシル基および酸無水物などが挙げられる。これらのうち好ましくはフェノール性水酸基、アミノ基、酸無水物などが挙げられ、さらに好ましくはフェノール性水酸基、アミノ基が挙げられ、特に好ましくはアミノ基を有するアミン系硬化剤である。アミン系硬化剤は、少ない配合量であっても、保護膜形成用フィルムの熱硬化後のガラス転移温度を上述した範囲に調整することが容易である。他方、アミン系硬化剤以外の硬化剤、たとえばフェノール系硬化剤などの場合は、より多くの熱硬化剤を配合しなければ、保護膜形成用フィルムの熱硬化後のガラス転移温度を上述した範囲に調整することが困難である。熱硬化剤（Ｂ１２）の含有量が多いと、熱硬化性成分（Ｂ）全体の含有量も多くせざるを得ず、熱硬化性成分（Ｂ）の含有量が過大となる懸念がある。 (B12) Thermosetting agent The 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, phenolic hydroxyl groups and amino groups are more preferable, and amine-based curing agents having amino groups are particularly preferable. Even if it is a small compounding quantity, it is easy to adjust the glass transition temperature after the thermosetting of the film for protective film formation to the range mentioned above. On the other hand, in the case of a curing agent other than an amine curing agent, such as a phenol curing agent, the glass transition temperature after thermal curing of the protective film-forming film is the range described above unless more thermosetting agent is blended. It is difficult to adjust. When there is much content of a thermosetting agent (B12), content of the whole thermosetting component (B) must be increased, and there exists a possibility that content of a thermosetting component (B) may become excessive.
 フェノール系硬化剤の具体的な例としては、多官能系フェノール樹脂、ビフェノール、ノボラック型フェノール樹脂、ジシクロペンタジエン系フェノール樹脂、ザイロック型フェノール樹脂、アラルキルフェノール樹脂が挙げられる。
 アミン系硬化剤の具体的な例としては、ＤＩＣＹ（ジシアンジアミド）が挙げられる。
 これらは、１種単独で、または２種以上混合して使用することができる。 Specific examples of the phenolic curing agent include polyfunctional phenolic resin, biphenol, novolac type phenolic resin, dicyclopentadiene type phenolic resin, zylock type phenolic resin, and aralkylphenolic resin.
A specific example of the amine curing agent is DICY (dicyandiamide).
These can be used individually by 1 type or in mixture of 2 or more types.
 熱硬化剤（Ｂ１２）の含有量は、通常エポキシ化合物（Ｂ１１）１００質量部に対して、０．１～５００質量部程度である。本発明においては、エポキシ化合物（Ｂ１１）、熱硬化剤（Ｂ１２）および硬化促進剤（Ｂ１３）の含有量を調整することで、保護膜形成用フィルムの熱硬化後のガラス転移温度を制御できる。特に、熱硬化剤（Ｂ１２）としてアミン系硬化剤を用いた場合には、エポキシ化合物（Ｂ１１）の有するエポキシ基の量と、アミン系硬化剤の有する活性水素の量が、モル比（活性水素／エポキシ基）で、好ましくは０．４～１．５、より好ましくは０．５～１．３、特に好ましくは０．６～１．１であるときに、保護膜形成用フィルムの熱硬化後のガラス転移温度を上記範囲に制御することが容易となる。エポキシ化合物（Ｂ１１）の有するエポキシ基の量と、アミン系硬化剤の有する活性水素の量についてのモル比（活性水素／エポキシ基）を調整する観点から、アミン系硬化剤は保護膜形成用フィルム中に、エポキシ化合物（Ｂ１１）１００質量部に対して、５～２０質量部含まれるが好ましく、５～１５質量部含まれることが好ましい。 The content of the ignition curing agent (B12) is usually about 0.1 to 500 parts by mass with respect to 100 parts by mass of the epoxy compound (B11). In this invention, the glass transition temperature after the thermosetting of the film for protective film formation can be controlled by adjusting content of an epoxy compound (B11), a thermosetting agent (B12), and a hardening accelerator (B13). In particular, when an amine curing agent is used as the thermosetting agent (B12), the amount of epoxy groups possessed by the epoxy compound (B11) and the amount of active hydrogen possessed by the amine curing agent are in a molar ratio (active hydrogen / Epoxy group), preferably 0.4 to 1.5, more preferably 0.5 to 1.3, particularly preferably 0.6 to 1.1, when the protective film-forming film is thermally cured. It becomes easy to control the later glass transition temperature within the above range. From the viewpoint of adjusting the molar ratio (active hydrogen / epoxy group) of the amount of the epoxy group of the epoxy compound (B11) and the amount of active hydrogen of the amine-based curing agent, the amine-based curing agent is a film for forming a protective film. The content is preferably 5 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).
（Ｂ１３）硬化促進剤
 硬化促進剤（Ｂ１３）を、保護膜形成用フィルムの熱硬化の速度を調整するために用いてもよい。硬化促進剤（Ｂ１３）は、特に、熱硬化性成分（Ｂ）として、エポキシ系熱硬化性成分を用いるときに好ましく用いられる。 (B13) 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 (B).
 好ましい硬化促進剤としては、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの３級アミン類；２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾールなどのイミダゾール類；トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィンなどの有機ホスフィン類；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレートなどのテトラフェニルボロン塩などが挙げられる。これらは１種単独で、または２種以上混合して使用することができる。 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.
 硬化促進剤（Ｂ１３）は、エポキシ化合物（Ｂ１１）および熱硬化剤（Ｂ１２）の合計量１００質量部に対して、好ましくは１～１０質量部、さらに好ましくは５～１０質量部の量で含まれる。硬化促進剤（Ｂ１３）を上記範囲の量で含有することにより、高温度高湿度下に曝されても優れた接着性を有し、厳しいリフロー条件に曝された場合であっても高い信頼性を達成することができる。硬化促進剤（Ｂ１３）を添加することで、保護膜形成用フィルムの硬化後の接着性を向上させることができる。このような作用は硬化促進剤（Ｂ１３）の含有量が多いほど強まる。 The curing accelerator (B13) is contained in an amount of preferably 1 to 10 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). It is. 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. By adding the curing accelerator (B13), 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.
（第２のバインダー成分）
 第２のバインダー成分は、熱硬化性重合体成分（ＡＢ）を含有することにより、保護膜形成用フィルムにシート形状維持性と熱硬化性を付与する。 (Second binder component)
A 2nd binder component provides sheet shape maintenance property and thermosetting to the film for protective film formation by containing a thermosetting polymer component (AB).
（ＡＢ）熱硬化性重合体成分
 熱硬化性重合体成分は、硬化機能官能基を有する重合体である。硬化機能官能基は、互いに反応して三次元網目構造を構成しうる官能基であり、加熱により反応する官能基が挙げられる。
 硬化機能官能基は、熱硬化性重合体成分（ＡＢ）の骨格となる連続構造の単位中に付加していてもよいし、末端に付加していてもよい。硬化機能官能基が熱硬化性重合体成分（ＡＢ）の骨格となる連続構造の単位中に付加している場合、硬化機能官能基は側鎖に付加していてもよいし、主鎖に直接付加していてもよい。熱硬化性重合体成分（ＡＢ）の重量平均分子量（Ｍｗ）は、保護膜形成用フィルムにシート形状維持性を付与する目的を達成する観点から、通常２０，０００以上である。 (AB) Thermosetting polymer component The thermosetting 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 includes a functional group that reacts by heating.
The functional functional group may be added to the unit of the continuous structure that becomes the skeleton of the thermosetting polymer component (AB) or may be added to the terminal. When the curing functional group is added in the unit of the continuous structure that becomes the skeleton of the thermosetting polymer component (AB), the curing functional group may be added to the side chain or directly to the main chain. It may be added. The weight average molecular weight (Mw) of the thermosetting 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.
 加熱により反応する官能基としてはエポキシ基が挙げられる。エポキシ基を有する熱硬化性重合体成分（ＡＢ）としては、エポキシ基を有するフェノキシ樹脂が挙げられる。
 また、上述のアクリル系重合体（Ａ１）と同様の重合体であって、単量体として、エポキシ基を有する単量体を用いて重合したもの（エポキシ基含有アクリル系重合体）であってもよい。このような単量体としては、エポキシ基含有（メタ）アクリル酸エステルや非アクリル系エポキシ基含有単量体が挙げられ、エポキシ基含有（メタ）アクリル酸エステルとしては、たとえば、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、（３，４－エポキシシクロヘキシル）メチル（メタ）アクリレート、３－エポキシシクロ－２－ヒドロキシプロピル（メタ）アクリレート等が、非アクリル系エポキシ基含有単量体としては、たとえば、グリシジルクロトネート、アリルグリシジルエーテル等が挙げられる。エポキシ基含有単量体としては、エポキシ基含有（メタ）アクリル酸エステルが好ましく、中でもグリシジル（メタ）アクリレートが好ましい。
 エポキシ基含有アクリル系重合体を用いる場合、その好ましい態様はアクリル系重合体（Ａ１）と同様である。
 エポキシ基含有アクリル系重合体を用い、第２のバインダー成分に含まれるものとして後述する熱硬化剤がアミン系硬化剤である場合には、エポキシ基とアミン系硬化剤の有する活性水素とが反応することにより、保護膜形成用フィルムの熱硬化後のガラス転移温度に寄与し、該ガラス転移温度を上記範囲に制御することが容易になる。また、保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率の制御も容易になる。 An example of a functional group that reacts by heating is an epoxy group. Examples of the thermosetting polymer component (AB) having an epoxy group include a phenoxy resin having an epoxy group.
Moreover, 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. Examples of such monomers include epoxy group-containing (meth) acrylic acid esters and non-acrylic epoxy group-containing monomers. Examples of epoxy group-containing (meth) acrylic acid esters include glycidyl (meth) Non-acrylic epoxy group-containing monomers such as acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3-epoxycyclo-2-hydroxypropyl (meth) acrylate, etc. Examples thereof include glycidyl crotonate and allyl glycidyl ether. As the epoxy group-containing monomer, an epoxy group-containing (meth) acrylic acid ester is preferable, and glycidyl (meth) acrylate is particularly preferable.
When an epoxy group-containing acrylic polymer is used, the preferred embodiment is the same as that of the acrylic polymer (A1).
When an epoxy group-containing acrylic polymer is used and the thermosetting agent described later as being contained in the second binder component is an amine-based curing agent, the epoxy group reacts with active hydrogen possessed by the amine-based curing agent. By doing so, it contributes to the glass transition temperature after thermosetting of the protective film-forming film, and it becomes easy to control the glass transition temperature within the above range. In addition, it becomes easy to control the tensile elastic modulus at 23 ° C. after the thermosetting of the protective film-forming film.
 エポキシ基を有する熱硬化性重合体成分（ＡＢ）を用いる場合には、熱硬化性成分（Ｂ）としてエポキシ系熱硬化性成分を用いる場合と同様、熱硬化剤（Ｂ１２）や、硬化促進剤（Ｂ１３）を併用することが好ましい。 When the thermosetting polymer component (AB) having an epoxy group is used, the thermosetting agent (B12) or the curing accelerator is used as in the case of using the epoxy thermosetting component as the thermosetting component (B). It is preferable to use (B13) in combination.
 第２のバインダー成分は、熱硬化性重合体成分（ＡＢ）と併せて、上述の重合体成分（Ａ）や熱硬化性成分（Ｂ）を含有していてもよい。 The second binder component may contain the above-described polymer component (A) and thermosetting component (B) in combination with the thermosetting polymer component (AB).
 保護膜形成用フィルムが熱硬化性成分（Ｂ）および熱硬化性重合体成分（ＡＢ）のいずれか単独または両方を含有する場合には、保護膜形成用フィルムは熱硬化性を有することとなる。より十分な熱硬化性を保護膜形成用フィルムに付与し、併せて被着体の反り矯正機能をも向上させるためには、保護膜形成用フィルムが少なくとも熱硬化性成分（Ｂ）を含有していることが好ましい。しかしながら、保護膜形成用フィルムが熱硬化性成分（Ｂ）のみを含有する場合には、保護膜形成用フィルムのシート形状維持性が劣ることがある。そこで、保護膜形成用フィルムは、熱硬化性成分（Ｂ）と、重合体成分（Ａ）および熱硬化性重合体成分（ＡＢ）のいずれか単独または両方と、を含有することが好ましい。 When the protective film-forming film contains one or both of the thermosetting component (B) and the thermosetting polymer component (AB), the protective film-forming film has thermosetting properties. . In order to impart more sufficient thermosetting property to the protective film-forming film and improve the warpage correction function of the adherend, the protective film-forming film contains at least the thermosetting component (B). It is preferable. However, when the protective film-forming film contains only the thermosetting component (B), the sheet shape maintainability of the protective film-forming film may be inferior. Then, it is preferable that the film for protective film formation contains a thermosetting component (B) and any one or both of a polymer component (A) and a thermosetting polymer component (AB).
 この場合には、保護膜形成用フィルムには、重合体成分（Ａ）および熱硬化性重合体成分（ＡＢ）の合計１００質量部に対して、熱硬化性成分（Ｂ）が、好ましくは７０質量部よりも多く含まれ、より好ましくは８５質量部よりも多く含まれる。熱硬化性成分（Ｂ）の含有量が、下限についてこのような範囲であると、保護膜形成用フィルムの熱硬化後のガラス転移温度や熱硬化後の２３℃における引張弾性率を上述した範囲に調整しやすい。
 なお、本発明において、保護膜形成用フィルムを構成する成分の含有量の態様について、熱硬化性重合体成分（ＡＢ）の含有量を基準として定める場合に、熱硬化性重合体成分（ＡＢ）が架橋されたエポキシ基含有アクリル系重合体であるときは、その基準とする含有量は、架橋される前のエポキシ基含有アクリル系重合体の含有量である。 In this case, in the protective film-forming film, the thermosetting component (B) is preferably 70 with respect to a total of 100 parts by mass of the polymer component (A) and the thermosetting polymer component (AB). More than mass parts are contained, more preferably more than 85 parts by mass. When the content of the thermosetting component (B) is in such a range with respect to the lower limit, the glass transition temperature after thermosetting of the protective film-forming film and the tensile elastic modulus at 23 ° C. after thermosetting are described above. Easy to adjust.
In the present invention, when the content of the component constituting the protective film-forming film is determined based on the content of the thermosetting polymer component (AB), the thermosetting polymer component (AB) Is a crosslinked epoxy group-containing acrylic polymer, the reference content is the content of the epoxy group-containing acrylic polymer before being crosslinked.
 また、含有量の上限としては、重合体成分（Ａ）および熱硬化性重合体成分（ＡＢ）の合計１００質量部に対して、熱硬化性成分（Ｂ）が、好ましくは１３５質量部以下含まれる。熱硬化性成分（Ｂ）の含有量が、上限についてこのような範囲にあることで、保護膜形成用フィルムのシート形状維持性や、可撓性が良好に保たれる傾向がある。特に、保護膜形成用フィルムが後述する無機フィラー（Ｃ）を含有する場合は、無機フィラー（Ｃ）の含有量が多いと、保護膜形成用フィルムのシート形状維持性や可撓性が低下し、屈曲に対する耐性や取り扱い性が低下することがある。そのため、熱硬化性成分（Ｂ）の含有量が、上限についてこのような範囲にあることが特に好ましい。 Further, as the upper limit of the content, the thermosetting component (B) is preferably contained in an amount of 135 parts by mass or less with respect to 100 parts by mass in total of the polymer component (A) and the thermosetting polymer component (AB). It is. When the content of the thermosetting component (B) is in such a range with respect to the upper limit, the sheet shape maintainability and flexibility of the protective film-forming film tend to be kept good. In particular, when the protective film-forming film contains an inorganic filler (C) described later, if the content of the inorganic filler (C) is large, the sheet shape maintainability and flexibility of the protective film-forming film are reduced. In addition, resistance to bending and handleability may be reduced. Therefore, it is particularly preferable that the content of the thermosetting component (B) is in such a range with respect to the upper limit.
 さらに、熱硬化性成分（Ｂ）がエポキシ系熱硬化性成分である場合には、保護膜形成用フィルムには、重合体成分（Ａ）および熱硬化性重合体成分（ＡＢ）の合計１００質量部に対して、エポキシ化合物（Ｂ１１）が、好ましくは７０質量部以上含まれ、より好ましくは８５～１３０質量部含まれ、さらに好ましくは８５～１２０質量部含まれる。これにより、保護膜形成用フィルムの熱硬化後のガラス転移温度や、熱硬化後の２３℃における引張弾性率を上述の範囲に調整することが容易となる。 Furthermore, when the thermosetting component (B) is an epoxy thermosetting component, the protective film-forming film contains a total of 100 masses of the polymer component (A) and the thermosetting polymer component (AB). The epoxy compound (B11) is preferably contained in an amount of 70 parts by mass or more, more preferably 85 to 130 parts by mass, and still more preferably 85 to 120 parts by mass with respect to parts. Thereby, it becomes easy to adjust the glass transition temperature after thermosetting of the film for protective film formation, and the tensile elasticity modulus at 23 degreeC after thermosetting to the above-mentioned range.
 保護膜形成用フィルムには、バインダー成分のほか、以下の成分を含有させてもよい。 In addition to the binder component, the film for forming a protective film may contain the following components.
（Ｃ）無機フィラー
 保護膜形成用フィルムは、無機フィラー（Ｃ）を含有することが好ましい。無機フィラー（Ｃ）を保護膜形成用フィルムに配合することにより、熱硬化後の２３℃における引張弾性率を上述の範囲に調整することが容易となる。
 さらに、保護膜にレーザーマーキングを施すことにより、レーザー光により削り取られた部分に無機フィラー（Ｃ）が露出して、反射光が拡散するために白色に近い色を呈する。これにより、保護膜形成用フィルムが後述する着色剤（Ｄ）を含有する場合、レーザーマーキング部分と他の部分にコントラスト差が得られ、印字が明瞭になるという効果がある。 (C) The inorganic filler protective film-forming film preferably contains an inorganic filler (C). By mix | blending an inorganic filler (C) with the film for protective film formation, it becomes easy to adjust the tensile elasticity modulus in 23 degreeC after thermosetting in the above-mentioned range.
Furthermore, by applying laser marking to the protective film, 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.
 好ましい無機フィラーとしては、シリカ、アルミナ、タルク、炭酸カルシウム、酸化チタン、酸化鉄、炭化珪素、窒化ホウ素等の粉末、これらを球形化したビーズ、単結晶繊維およびガラス繊維等が挙げられる。これらのなかでも、シリカフィラーおよびアルミナフィラーが好ましい。上記無機フィラー（Ｃ）は単独でまたは２種以上を混合して使用することができる。
 上述の効果をより確実に得るための、無機フィラー（Ｃ）の含有量の範囲としては、保護膜形成用フィルムを構成する全固形分１００質量部に対して、好ましくは１０～７０質量部、より好ましくは４０～７０質量部、特に好ましくは５５～６５質量部である。無機フィラー（Ｃ）の含有量を上記範囲とすることで、熱硬化後の２３℃における引張弾性率を上述の範囲に調整することがいっそう容易となり、反り矯正機能が向上し、信頼性の高い保護膜付チップを得ることができる。
 また、無機フィラー（Ｃ）の平均粒子径は、好ましくは０．０２～５μｍ、より好ましくは０．０５～４．５μｍ、特に好ましくは０．１～４μｍである。無機フィラー（Ｃ）の平均粒子径を上記範囲とすることで、反り矯正機能が向上する。無機フィラー（Ｃ）の平均粒子径は、電子顕微鏡で無作為に選んだ無機フィラー（Ｃ）２０個の長軸径を測定し、その算術平均値として算出される個数平均粒子径とする。 Preferred inorganic fillers 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, glass fibers, and the like. Among these, 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 range of the content of the inorganic filler (C) for obtaining the above-mentioned effect more reliably is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film, More preferred is 40 to 70 parts by mass, and particularly preferred is 55 to 65 parts by mass. By making content of an inorganic filler (C) into the said range, it becomes much easier to adjust the tensile elasticity modulus in 23 degreeC after thermosetting in the above-mentioned range, a curvature correction function improves, and its reliability is high. A chip with a protective film can be obtained.
The average particle size of the inorganic filler (C) is preferably 0.02 to 5 μm, more preferably 0.05 to 4.5 μm, and particularly preferably 0.1 to 4 μm. By setting the average particle diameter of the inorganic filler (C) within the above range, the warp correction function is improved. The average particle diameter of the inorganic filler (C) is the number average particle diameter calculated as the arithmetic average value of 20 major axis diameters of 20 inorganic fillers (C) randomly selected with an electron microscope.
（Ｄ）着色剤
 保護膜形成用フィルムには、着色剤（Ｄ）を配合することができる。着色剤を配合することで、半導体装置を機器に組み込んだ際に、周囲の装置から発生する赤外線等による半導体装置の誤作動を防止することができる。また、レーザーマーキング等の手段により保護膜に刻印を行った場合に、文字、記号等のマークが認識しやすくなるという効果がある。すなわち、保護膜が形成された半導体装置や半導体チップでは、保護膜の表面に品番等が通常レーザーマーキング法（レーザー光により保護膜表面を削り取り印字を行う方法）により印字されるが、保護膜が着色剤（Ｄ）を含有することで、保護膜のレーザー光により削り取られた部分とそうでない部分のコントラスト差が充分に得られ、視認性が向上する。 (D) Colorant (D) can be mix | blended with the film for colorant protective film formation. 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. In addition, when 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). By containing the colorant (D), a sufficient difference in contrast between the portion of the protective film scraped by the laser beam and the portion not removed is obtained, and the visibility is improved.
 着色剤としては、有機または無機の顔料および染料が用いられる。これらの中でも電磁波や赤外線遮蔽性の点から黒色顔料が好ましい。黒色顔料としては、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が用いられるが、これらに限定されることはない。半導体装置の信頼性を高める観点からは、カーボンブラックが特に好ましい。着色剤（Ｄ）は１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
 着色剤（Ｄ）の配合量は、保護膜形成用フィルムを構成する全固形分１００質量部に対して、好ましくは０．１～３５質量部、さらに好ましくは０．５～２５質量部、特に好ましくは１～１５質量部である。 As the colorant, organic or inorganic pigments and dyes are used. Among these, black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties. Examples of 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.
（Ｅ）カップリング剤
 無機物と反応する官能基および有機官能基と反応する官能基を有するカップリング剤（Ｅ）を、保護膜形成用フィルムの被着体に対する接着性、密着性および／または保護膜の凝集性を向上させるために用いてもよい。また、カップリング剤（Ｅ）を使用することで、保護膜形成用フィルムを硬化して得られる保護膜の耐熱性を損なうことなく、その耐水性を向上させることができる。このようなカップリング剤としては、チタネート系カップリング剤、アルミネート系カップリング剤、シランカップリング剤等が挙げられる。これらのうちでも、シランカップリング剤が好ましい。 (E) Coupling agent Adhesiveness, adhesion, and / or protection of a coupling agent (E) having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group to an adherend of a protective film-forming film. It may be used to improve the cohesiveness of the film. Moreover, the water resistance can be improved by using a coupling agent (E), without impairing the heat resistance of the protective film obtained by hardening | curing the film for protective film formation. 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.
 シランカップリング剤としては、その有機官能基と反応する官能基が、重合体成分（Ａ）、熱硬化性成分（Ｂ）や熱硬化性重合体成分（ＡＢ）などが有する官能基と反応する基であるシランカップリング剤が好ましく使用される。
 このようなシランカップリング剤としてはγ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－（メタクリロキシプロピル）トリメトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－６－（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－６－（アミノエチル）－γ－アミノプロピルメチルジエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、γ－ウレイドプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルメチルジメトキシシラン、ビス（３－トリエトキシシリルプロピル）テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、イミダゾールシランなどが挙げられる。これらは１種単独で、または２種以上混合して使用することができる。 As a silane coupling agent, a functional group that reacts with the organic functional group reacts with a functional group that the polymer component (A), the thermosetting component (B), the thermosetting polymer component (AB), or the like has. A silane coupling agent which is a group is preferably used.
Such silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacryloxy). Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Methoxysilane , Methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. These can be used individually by 1 type or in mixture of 2 or more types.
 シランカップリング剤は、重合体成分（Ａ）、熱硬化性成分（Ｂ）および熱硬化性重合体成分（ＡＢ）の合計１００質量部に対して、通常０．１～２０質量部、好ましくは０．２～１０質量部、より好ましくは０．３～５質量部の割合で含まれる。シランカップリング剤の含有量が０．１質量部未満だと上記の効果が得られない可能性があり、２０質量部を超えるとアウトガスの原因となる可能性がある。 The silane coupling agent is usually 0.1 to 20 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the polymer component (A), the thermosetting component (B) and the thermosetting polymer component (AB). It is contained in a proportion of 0.2 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.
（Ｆ）汎用添加剤
 保護膜形成用フィルムには、上記の他に、必要に応じて各種添加剤が配合されてもよい。各種添加剤としては、レベリング剤、可塑剤、帯電防止剤、酸化防止剤、イオン捕捉剤、ゲッタリング剤、連鎖移動剤、剥離剤などが挙げられる。 (F) In addition to the above, various additives may be blended in the film for forming a general-purpose additive protective film as necessary. Examples of various additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, and the like.
　保護膜形成用フィルムは、初期接着性と熱硬化性とを有し、未硬化状態では半導体ウエハやチップ等に押圧することで容易に接着する。また押圧する際に保護膜形成用フィルムを加熱してもよい。そして熱硬化を経て最終的には耐衝撃性の高い保護膜を与えることができ、接着強度にも優れ、厳しい高温度高湿度条件下においても十分な保護機能を保持し得る。なお、保護膜形成用フィルムは単層構造であってもよく、また多層構造であってもよい。 The protective film-forming film has an initial adhesive property and a thermosetting property, and adheres easily by being pressed 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. Finally, a protective film having high impact resistance can be provided through thermosetting, excellent in adhesive strength, and can maintain a sufficient protective function even under severe high temperature and high humidity conditions. The protective film-forming film may have a single layer structure or a multilayer structure.
　保護膜形成用フィルムは、たとえば上記各成分を適宜の割合で混合して得られる組成物（保護膜形成用組成物）を用いて得られる。保護膜形成用組成物は予め溶媒で希釈しておいてもよく、また混合時に溶媒に加えてもよい。また、保護膜形成用組成物の使用時に、溶媒で希釈してもよい。
 かかる溶媒としては、酢酸エチル、酢酸メチル、ジエチルエーテル、ジメチルエーテル、アセトン、メチルエチルケトン、アセトニトリル、ヘキサン、シクロヘキサン、トルエン、ヘプタンなどが挙げられる。 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.
　保護膜形成用フィルムの厚さは特に限定されないが、好ましくは３～３００μｍ、より好ましくは５～２５０μｍ、特に好ましくは７～２００μｍである。 The thickness of the protective film-forming film is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and particularly preferably 7 to 200 μm.
 保護膜形成用フィルムにおける可視光線および／または赤外線と紫外線の透過性を示す尺度である、波長３００～１２００ｎｍにおける最大透過率は２０％以下であることが好ましく、０～１５％であることがより好ましく、０％を超え１０％以下であることがさらに好ましく、０．００１～８％であることが特に好ましい。波長３００～１２００ｎｍにおける保護膜形成用フィルムの最大透過率を上記範囲とすることで、可視光波長領域および／または赤外波長領域の透過性の低下が生じ、半導体装置の赤外線起因の誤作動の防止や、印字の視認性向上といった効果が得られる。波長３００～１２００ｎｍにおける保護膜形成用フィルムの最大透過率は、上記着色剤（Ｄ）により調整できる。なお、保護膜形成用フィルムの最大透過率は、ＵＶ－ｖｉｓスペクトル検査装置（（株）島津製作所製）を用いて、硬化後の保護膜形成用フィルム（厚み２５μｍ）の３００～１２００ｎｍでの全光線透過率を測定し、透過率の最も高い値（最大透過率）とした。 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%. By setting the maximum transmittance of the protective film-forming film at a wavelength of 300 to 1200 nm within the above range, the transmittance in the visible light wavelength region and / or the infrared wavelength region is lowered, and malfunction of the semiconductor device due to infrared light is caused. Effects such as prevention and improved visibility of printing can be obtained. 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 μm) after curing at 300 to 1200 nm. The light transmittance was measured and set to the highest value (maximum transmittance).
 本発明の保護膜形成用フィルムは、シリコンやガリウム－砒素等を材料とする半導体ウエハやチップを被着体として、それらの保護膜として使用される。 The film for forming a protective 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.
 本発明に係る保護膜形成用フィルムの製造方法は特に限定されない。
たとえば、保護膜形成用フィルムを工程フィルム上に製膜することができる。製膜は、工程フィルム上に保護膜形成用フィルムを形成するための組成物をロールナイフコーター、グラビアコーター、ダイコーター、リバースコーターなど一般に公知の方法にしたがって塗工し、乾燥させることによって行う。
 工程フィルムは、そのまま後述する支持シートやカバーフィルムとして用いることができる。また、保護膜形成用フィルムを、その製膜後に工程フィルムから支持シートやカバーフィルムに転写してもよい。工程フィルムが、支持シートまたはカバーフィルムのいずれか一方であり、かつ、転写される材料が、支持シートまたはカバーフィルムの他の一方であってもよい。 The manufacturing method of the film for protective film formation concerning this invention is not specifically limited.
For example, 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. Moreover, you may transfer the film for protective film formation from a process film to a support sheet or a cover film after the film formation. 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.
［保護膜形成用複合シート］
　保護膜形成用複合シートは、保護膜形成用フィルムの片面に支持シートを剥離可能に形成して得られる。保護膜形成用複合シートの形状は、枚葉のものに限られず、長尺の帯状のものであってもよく、これを巻収してもよい。支持シートとしては、剥離シートが挙げられ、また、後述する粘着シートを用いることができる。 [Composite sheet for protective film formation]
The composite sheet for forming a protective film is obtained by forming the support sheet so as to be peelable on one side of the film for forming a protective film. 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.
　保護膜形成用複合シートは、各種の被着体に貼付され、場合によっては、保護膜形成用複合シート上で被着体にダイシング等の所要の加工が施される。その後、保護膜形成用フィルムを被着体に固着残存させて支持シートを剥離する。すなわち、保護膜形成用フィルムを、支持シートから被着体に転写する工程を含むプロセスに使用される。 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.
　保護膜形成用フィルムは、支持シートと同形状とすることができる。また、保護膜形成用複合シートは、保護膜形成用フィルムが、ウエハと略同形状又はウエハの形状をそっくり含むことのできる形状に調製されたものであり、保護膜形成用フィルムよりも大きなサイズの支持シート上に積層されている、事前成形構成をとっていてもよい。 The protective film-forming film can have the same shape as the support sheet. In addition, 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 pre-molded configuration may be taken that is laminated on the support sheet.
 剥離シートとしては、たとえばポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレン テレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・（メタ）アクリル酸共重合体フィルム、エチレン・（メタ）アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等が用いられる。またこれらの架橋フィルムも用いられる。さらにこれらの積層フィルムであってもよい。 Examples of 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.
 剥離シートの保護膜形成用フィルムに接する面の表面張力は、好ましくは４０ｍＮ／ｍ以下、さらに好ましくは３７ｍＮ／ｍ以下、特に好ましくは３５ｍＮ／ｍ以下である。下限値は通常２５ｍＮ／ｍ程度である。このような表面張力が比較的低い剥離シートは、材質を適宜に選択して得ることが可能であるし、また剥離シートの表面に剥離剤を塗布して剥離処理を施すことで得ることもできる。 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. .
 剥離処理に用いられる剥離剤としては、アルキッド系、シリコーン系、フッ素系、不飽和ポリエステル系、ポリオレフィン系、ワックス系などが用いられるが、特にアルキッド系、シリコーン系、フッ素系の剥離剤が耐熱性を有するので好ましい。 As the release agent used for the release treatment, alkyd, silicone, fluorine, unsaturated polyester, polyolefin, wax, and the like are used. In particular, alkyd, silicone, and fluorine release agents are heat resistant. This is preferable.
 上記の剥離剤を用いて剥離シートの基体となるフィルム等の表面を剥離処理するためには、剥離剤をそのまま無溶剤で、または溶剤希釈やエマルション化して、グラビアコーター、メイヤーバーコーター、エアナイフコーター、ロールコーターなどにより塗布して、剥離剤が塗布された剥離シートを常温下または加熱下に供するか、または電子線により硬化させて剥離剤層を形成させればよい。 In order to release the surface of a film or the like as a substrate of a release sheet using the above release agent, 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.
　また、ウェットラミネーションやドライラミネーション、熱溶融ラミネーション、溶融押出ラミネーション、共押出加工などによりフィルムの積層を行うことにより剥離シートの表面張力を調整してもよい。すなわち、少なくとも一方の面の表面張力が、上述した剥離シートの保護膜形成用フィルムと接する面のものとして好ましい範囲内にあるフィルムを、当該面が保護膜形成用フィルムと接する面となるように、他のフィルムと積層した積層体を製造し、剥離シートとしてもよい。 Further, 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. Alternatively, a laminate laminated with another film may be manufactured and used as a release sheet.
　保護膜形成用複合シート上で被着体にダイシング等の所要の加工が施される場合には、基材上に粘着剤層を形成した粘着シートを支持シートとして用いることが好ましい。この態様においては、保護膜形成用フィルムは、支持シートに設けられた粘着剤層上に積層される。粘着シートの基材としては、剥離シートとして例示した上記のフィルムが挙げられる。粘着剤層は、保護膜形成用フィルムを剥離できる程度の粘着力を有する弱粘着性のものを使用してもよいし、エネルギー線照射により粘着力が低下するエネルギー線硬化性のものを使用してもよい。 When the adherend is subjected to required processing such as dicing on the protective film-forming composite sheet, an adhesive sheet having an adhesive layer formed on a substrate is preferably used as the support sheet. In this embodiment, the protective film-forming film is laminated on the pressure-sensitive adhesive layer provided on the support sheet. As a base material of an adhesive sheet, said film illustrated as a peeling sheet is mentioned. 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.
 粘着剤層は、従来より公知の種々の粘着剤（例えば、ゴム系、アクリル系、シリコーン系、ウレタン系、ビニルエーテル系などの汎用粘着剤、表面凹凸のある粘着剤、エネルギー線硬化型粘着剤、熱膨張成分含有粘着剤等）により形成できる。
 保護膜形成用複合シートの構成がかかる構成であると、保護膜形成用複合シートが、ダイシング工程において被着体を支持するためのダイシングシートとして機能する場合に支持シートと保護膜形成用フィルムの間の密着性が保たれ、ダイシング工程において保護膜形成用フィルム付チップが支持シートから剥がれることを抑制するという効果が得られる。保護膜形成用複合シートが、ダイシング工程において被着体を支持するためのダイシングシートとして機能する場合、ダイシング工程において保護膜形成用フィルム付ウエハに別途ダイシングシートを貼り合せてダイシングをする必要がなくなり、半導体装置の製造工程を簡略化できる。 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).
When the composition of the protective film-forming composite sheet is such a configuration, when the protective film-forming composite sheet functions as a dicing sheet for supporting the adherend in the dicing step, the support sheet and the protective film-forming film The adhesiveness between them is maintained, and the effect of suppressing the chip with the protective film-forming film from peeling off from the support sheet in the dicing step is obtained. When 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.
　保護膜形成用複合シートが事前成形構成をとる場合においては、保護膜形成用複合シートを次の第１、第２または第３の構成としてもよい。以下、保護膜形成用複合シート１００の各構成について図１～３を用いて説明する。 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. Hereinafter, each configuration of the protective film-forming composite sheet 100 will be described with reference to FIGS.
　第１の構成は、図１に示すように、保護膜形成用フィルム１０の片面に、基材１上に粘着剤層２が形成された粘着シート３が剥離可能に形成された構成である。第１の構成を採用する場合には、該粘着剤層をエネルギー線硬化型粘着剤で構成し、保護膜形成用フィルムが積層される領域に予めエネルギー線照射を行い、粘着性を低減させておく一方、他の領域はエネルギー線照射を行わず、粘着力を高いまま維持しておいてもよい。他の領域のみにエネルギー線照射を行わないようにするには、たとえば支持シートの他の領域に対応する領域に印刷等によりエネルギー線遮蔽層を設け、支持シート側からエネルギー線照射を行えばよい。 1st structure is the structure by which the adhesive sheet 3 in which the adhesive layer 2 was formed on the base material 1 was formed so that peeling was possible on the single side | surface of the film 10 for protective film formation, as shown in FIG. In the case of adopting the first configuration, the pressure-sensitive adhesive layer is composed of an energy ray-curable pressure-sensitive adhesive, and the region where the protective film-forming film is laminated is irradiated with energy rays in advance to reduce the adhesiveness. On the other hand, other regions may be maintained with high adhesive strength without being irradiated with energy rays. In order not to irradiate the energy beam only to other regions, for example, 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. .
　第２の構成は、図２に示すように、保護膜形成用複合シート１００の粘着剤層２上に、保護膜形成用フィルム１０と重ならない領域に別途治具接着層４を設けた構成である。治具接着層としては、芯材を有する両面粘着シートや、粘着剤の単層からなる層を採用することができる。 As shown in FIG. 2, 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. As a jig | 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 | adopted.
　第３の構成は、図３に示すように、保護膜形成用フィルム１０と粘着剤層２の間に、さらに保護膜形成用フィルムの形状をそっくり含むことのできる形状の界面接着調整層５を設けた構成である。界面接着調整層は、所定のフィルムであってもよいし、界面接着調整粘着剤層であってもよい。界面接着調整粘着剤層は、エネルギー線硬化性の粘着剤に予めエネルギー線照射を行い硬化させたものであることが好ましい。 As shown in FIG. 3, 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. This is a configuration provided. 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.
　保護膜形成用複合シートを、これらの第１から第３の構成とすることで、保護膜形成用フィルムを取り囲む領域においては、粘着剤層または治具接着層の十分な接着性により、保護膜形成用複合シートを治具に接着することができる。それとともに、保護膜形成用フィルムと粘着剤層または界面接着調整層との界面における接着性を制御し、保護膜形成用フィルムまたは保護膜の固着したチップのピックアップを容易とすることができる。 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. At the same time, 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.
　保護膜形成用複合シートが事前成形構成をとらない場合、すなわち、図４に示すように、保護膜形成用フィルム１０と支持シート（図４においては、基材１上に粘着剤層２が形成された粘着シート３）とを同形状とした場合において、保護膜形成用フィルム１０の表面の外周部には、治具接着層４が設けられていてもよい。治具接着層としては、上述したものと同じものを用いることができる。 When the protective film-forming composite sheet does not have a pre-molded configuration, that is, as shown in FIG. 4, the protective film-forming film 10 and the support sheet (in FIG. 4, the pressure-sensitive adhesive layer 2 is formed on the substrate 1). In the case where the pressure-sensitive adhesive sheet 3) has the same shape, a jig adhesive layer 4 may be provided on the outer peripheral portion of the surface of the protective film-forming film 10. As the jig adhesive layer, the same one as described above can be used.
 支持シートの厚さは、通常は１０～５００μｍ、好ましくは１５～３００μｍ、特に好ましくは２０～２５０μｍである。支持シートが基材上に粘着剤層を形成した粘着シートの場合には、支持シート中３～５０μｍが粘着剤層の厚さである。 The thickness of the heel support sheet is usually 10 to 500 μm, preferably 15 to 300 μm, particularly preferably 20 to 250 μm. In the case where the support sheet is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed on a substrate, the thickness of the pressure-sensitive adhesive layer is 3 to 50 μm in the support sheet.
　保護膜形成用フィルムの支持シートに貼付される面とは反対面には、カバーフィルムを仮着しておいてもよい。カバーフィルムは、支持シートが粘着シートである場合の粘着剤層や、治具接着層を覆っていてもよい。カバーフィルムは、上述の剥離シートと同じものを用いることができる。 A cover film may be temporarily attached to the surface opposite to the surface to be attached to the support sheet 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.
　カバーフィルムの膜厚は、通常は５～３００μｍ、好ましくは１０～２００μｍ、特に好ましくは２０～１５０μｍ程度である。 The film thickness of the cover film is usually about 5 to 300 μm, preferably about 10 to 200 μm, particularly preferably about 20 to 150 μm.
　このような保護膜形成用複合シートの保護膜形成用フィルムは、被着体の保護膜とすることができる。保護膜形成用フィルムはフェースダウン方式のチップ用半導体ウエハまたは半導体チップの裏面に貼付され、適当な手段により硬化されて封止樹脂の代替として半導体ウエハまたは半導体チップを保護する機能を有する。半導体ウエハに貼付した場合には、保護膜がウエハを補強する機能を有するためにウエハの破損等を防止しうる。 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. 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.
［半導体装置の製造方法］
 次に、本発明の保護膜形成用フィルムの利用方法について、上述した保護膜形成用複合シートを半導体装置の製造に適用した場合を例にとって説明する。 [Method for Manufacturing Semiconductor Device]
Next, a method for using the protective film-forming film of the present invention will be described taking as an example the case where the above-described protective film-forming composite sheet is applied to the manufacture of a semiconductor device.
 本発明における半導体装置の製造方法は、上記保護膜形成用複合シートの保護膜形成用フィルムを半導体ウエハに貼付し、保護膜を有する半導体チップを得る工程を含むことが好ましい。
 具体的には、表面に回路が形成された半導体ウエハの裏面に、保護膜形成用複合シートの保護膜形成用フィルムを貼付し、その後、裏面に保護膜を有する半導体チップを得る。該保護膜は、半導体ウエハまたは半導体チップの保護膜であることが好ましい。また、本発明における半導体装置の製造方法は、好ましくは、以下の工程（１）～（３）をさらに含み、保護膜形成用フィルムの有するウエハの反り矯正機能を発揮させるためには、工程（３）よりも前に工程（２）を行う。なお、上述したように、保護膜形成用複合シートを、ダイシング工程において被着体を支持するためのダイシングシートとして機能させる場合には、半導体装置の製造工程を簡略化する観点から、工程（３）を工程（１）の前に行うことが好ましい。
　工程（１）：保護膜形成用フィルムまたは保護膜と、支持シートとを剥離、
　工程（２）：保護膜形成用フィルムを硬化して保護膜を得る、
　工程（３）：半導体ウエハと、保護膜形成用フィルムまたは保護膜とをダイシング。 The method for manufacturing a semiconductor device according to the present invention 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. In addition, the method for manufacturing a semiconductor device according to the present invention preferably further includes the following steps (1) to (3), and in order to exert the function of correcting the warpage of the wafer included in the protective film-forming film, Step (2) is performed prior to 3). As described above, when the protective film-forming composite sheet functions as a dicing sheet for supporting the adherend in the dicing process, the process (3) is performed from the viewpoint of simplifying the manufacturing process of the semiconductor device. ) Is preferably performed before step (1).
Step (1): peeling off the protective film-forming film or protective film and the support sheet,
Step (2): The protective film-forming film is cured to obtain a protective film.
Step (3): Dicing the semiconductor wafer and the protective film-forming film or protective film.
 また、本発明における半導体装置の製造方法は、上記工程（１）～（３）の他に、下記の工程（４）をさらに含んでいてもよい。
 工程（４）：保護膜にレーザー印字。 In addition, the method for manufacturing a semiconductor device in the present invention may further include the following step (4) in addition to the above steps (1) to (3).
Step (4): Laser printing on the protective film.
　半導体ウエハはシリコンウエハであってもよく、またガリウム・砒素などの化合物半導体ウエハであってもよい。ウエハ表面への回路の形成はエッチング法、リフトオフ法などの従来より汎用されている方法を含む様々な方法により行うことができる。次いで、半導体ウエハの回路面の反対面（裏面）を研削する。研削法は特に限定はされず、グラインダーなどを用いた公知の手段で研削してもよい。裏面研削時には、表面の回路を保護するために回路面に、表面保護シートと呼ばれる粘着シートを貼付する。裏面研削は、ウエハの回路面側（すなわち表面保護シート側）をチャックテーブル等により固定し、回路が形成されていない裏面側をグラインダーにより研削する。ウエハの研削後の厚みは特に限定はされないが、通常は５０～５００μｍ程度である。 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. In the back surface grinding, 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 μm.
 その後、必要に応じ、裏面研削時に生じた破砕層を除去する。破砕層の除去は、ケミカルエッチングや、プラズマエッチングなどにより行われる。 Then, if necessary, remove the crushed layer generated during back grinding. The crushed layer is removed by chemical etching, plasma etching, or the like.
 次いで、半導体ウエハの裏面に、上記保護膜形成用複合シートの保護膜形成用フィルムを貼付する。その後、工程（１）～（３）を工程（１）、（２）、（３）の順、工程（２）、（１）、（３）の順または工程（２）、（３）、（１）の順のいずれかの順序で行う。このプロセスの詳細については、特開２００２－２８０３２９号公報に詳述されている。一例として、工程（１）、（２）、（３）の順で行う場合について説明する。 Next, a protective film-forming film of the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer. Thereafter, the steps (1) to (3) are performed in the order of the steps (1), (2), (3), the steps (2), (1), (3) or the steps (2), (3), It is performed in any order of the order of (1). Details of this process are described in detail in JP-A-2002-280329. As an example, the case where it performs in order of process (1), (2), (3) is demonstrated.
　まず、表面に回路が形成された半導体ウエハの裏面に、上記保護膜形成用複合シートの保護膜形成用フィルムを貼付する。次いで保護膜形成用フィルムから支持シートを剥離し、半導体ウエハと保護膜形成用フィルムとの積層体を得る。次いで保護膜形成用フィルムを硬化し、ウエハの全面に保護膜を形成する。具体的には、熱硬化により保護膜形成用フィルムを硬化する。この結果、ウエハ裏面に硬化樹脂からなる保護膜が形成され、ウエハ単独の場合と比べて強度が向上するので、薄くなったウエハの取扱い時の破損を低減できる。また、ウエハやチップの裏面に直接保護膜用の塗布液を塗布・被膜化するコーティング法と比較して、保護膜の厚さの均一性に優れる。 First, the protective film-forming film 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. Next, the support sheet is peeled from the protective film-forming film to obtain a laminate of the semiconductor wafer and the protective film-forming film. Next, the protective film-forming film is cured, and a protective film is formed on the entire surface of the wafer. Specifically, the protective film-forming film is cured by thermosetting. As a result, a protective film made of a cured resin is formed on the back surface of the wafer, and the strength is improved as compared with the case of the wafer alone, so that damage during handling of the thinned wafer can be reduced. In addition, the thickness of the protective film is excellent compared to a coating method in which a coating liquid for the protective film is directly applied to the back surface of the wafer or chip.
 次いで、半導体ウエハと保護膜との積層体を、ウエハ表面に形成された回路毎にダイシングする。ダイシングは、ウエハと保護膜をともに切断するように行われる。ウエハのダイシングは、ダイシングシートを用いた常法により行われる。この結果、ダイシングシート上に個片化された、裏面に保護膜を有する半導体チップ群が得られる。 Next, the laminated body of the semiconductor wafer and the protective film is diced for each circuit formed on the wafer surface. Dicing is performed so as to cut both the wafer and the protective film. The wafer is diced by a conventional method using a dicing sheet. As a result, a group of semiconductor chips that are separated on the dicing sheet and have a protective film on the back surface is obtained.
 次いで、保護膜にレーザー印字することが好ましい。レーザー印字はレーザーマーキング法により行われ、レーザー光の照射により保護膜の表面を削り取ることで保護膜に品番等をマーキングする。 Next, it is preferable to perform laser printing on the protective film. 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.
 最後に、裏面に保護膜を有する半導体チップ（保護膜付チップ）をコレット等の汎用手段によりピックアップすることで、保護膜付チップが得られる。そして、保護膜付チップをフェースダウン方式で所定の基台上に実装することで半導体装置を製造することができる。また、裏面に保護膜を有する半導体チップを、ダイパッド部または別の半導体チップなどの他の部材上（チップ搭載部上）に接着することで、半導体装置を製造することもできる。このような本発明によれば、厚みの均一性の高い保護膜を、チップ裏面に簡便に形成でき、ダイシング工程やパッケージングの後のクラックが発生しにくくなる。 Finally, a semiconductor chip having a protective film on the back surface (chip with protective film) is picked up by a general-purpose means such as a collet to obtain a chip with a protective film. Then, the semiconductor device can be manufactured by mounting the chip with protective film on a predetermined base by the face-down method. 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. According to the present invention as described above, 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.
 なお、半導体ウエハの裏面に、上記保護膜形成用複合シートの保護膜形成用フィルムを貼付した後、工程（３）を工程（１）の前に行う場合（工程（２）、（３）、（１）の順で行う場合）、保護膜形成用複合シートがダイシングシートとしての役割を果たすことができる。つまり、ダイシング工程の最中に半導体ウエハを支持するためのシートとして用いることができる。この場合、保護膜形成用複合シートの内周部に保護膜形成用フィルムを介して半導体ウエハが貼着され、保護膜形成用複合シートの外周部がリングフレーム等の他の治具と接合することで、半導体ウエハに貼付された保護膜形成用複合シートが装置に固定され、ダイシングが行われる。 In addition, after affixing the protective film-forming film of the protective film-forming composite sheet to the back surface of the semiconductor wafer, the step (3) is performed before the step (1) (steps (2), (3), When performing in the order of (1)), the composite sheet for forming a protective film can serve as a dicing sheet. That is, it can be used as a sheet for supporting the semiconductor wafer during the dicing process. In this case, the semiconductor wafer is bonded to the inner peripheral portion of the protective film forming composite sheet via the protective film forming film, and the outer peripheral portion of the protective film forming composite sheet is joined to another jig such as a ring frame. Thereby, the composite sheet for forming a protective film attached to the semiconductor wafer is fixed to the apparatus, and dicing is performed.
　本発明の保護膜形成用フィルムや該フィルムを用いた保護膜形成用複合シートは、上記のような使用方法の他、半導体化合物、ガラス、セラミックス、金属などの保護に使用することもできる。 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.
　以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例または比較例において、＜熱硬化後のガラス転移温度＞、＜熱硬化後の２３℃における引張弾性率＞、＜反り矯正性能評価＞、＜信頼性評価＞および＜ウエハ反り評価＞は以下のように測定・評価した。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. In the following examples or comparative examples, <glass transition temperature after thermosetting>, <tensile modulus at 23 ° C. after thermosetting>, <warping correction performance evaluation>, <reliability evaluation>, and <wafer warpage> Evaluation> was measured and evaluated as follows.
＜熱硬化後のガラス転移温度＞
 厚み４５μｍの保護膜形成用フィルムを４枚積層し、オーブン内において大気雰囲気化で熱硬化（１３０℃２時間）し、幅４．５ｍｍ、長さ２０．０ｍｍ、厚み０．１８ｍｍの短冊状に切断して試験片を作製した。
 粘弾性測定装置（ＴＡ　ｉｎｓｔｒｕｍｅｎｔｓ社製　ＤＭＡ　Ｑ８００）を用いて、引張モードにて、試験片のｔａｎδ（損失弾性率と貯蔵弾性率との比）を、周波数１１Ｈｚ、昇温速度３℃／分、大気雰囲気下で０～３００℃にて測定した。この温度範囲においてｔａｎδが最大値を示す温度を読み取り、保護膜形成用フィルムの熱硬化後のガラス転移温度（Ｔｇ）とした。 <Glass transition temperature after thermosetting>
Four protective film-forming films with a thickness of 45 μm are laminated and thermally cured (at 130 ° C. for 2 hours) in an oven to form a strip with a width of 4.5 mm, a length of 20.0 mm, and a thickness of 0.18 mm. The test piece was produced by cutting.
Using a viscoelasticity measuring apparatus (DMA instruments made by TA instruments, DMA Q800), in a tensile mode, the tan δ (ratio of loss elastic modulus to storage elastic modulus) of the test piece was set to a frequency of 11 Hz, a heating rate of 3 ° C./min, The measurement was performed at 0 to 300 ° C. in an air atmosphere. The temperature at which tan δ exhibited the maximum value in this temperature range was read and used as the glass transition temperature (Tg) after thermosetting of the protective film-forming film.
＜熱硬化後の２３℃における引張弾性率＞
 上記＜熱硬化後のガラス転移温度＞の測定で得られた測定データの２３℃における貯蔵弾性率を読み取り、保護膜形成用フィルムの熱硬化後の２３℃における引張弾性率とした。 <Tensile modulus at 23 ° C. after thermosetting>
The storage elastic modulus at 23 ° C. of the measurement data obtained by the above measurement of <glass transition temperature after thermosetting> was read, and the tensile elastic modulus at 23 ° C. after thermosetting of the protective film-forming film was obtained.
＜反り矯正性能評価＞
 厚み４５μｍの保護膜形成用フィルムを厚み３０μｍの銅箔に貼付した試験片（サイズ：１００ｍｍ×１００ｍｍ）を、オーブン内において大気雰囲気下で熱硬化（１３０℃２時間）した。
 その後、保護膜形成用フィルムの熱硬化に伴う収縮により、保護膜形成用フィルムを貼付した面を内側にして丸まった銅箔のその丸まった形状において、それらの点を結んだ距離が最大値となる２の点をとり、その距離を測定した。この距離が小さいほど銅箔が大きく反っていることを意味し、保護膜形成用フィルムの熱収縮による応力が大きいことから、反り矯正能力が高いと判断できる。 <Evaluation of warpage correction performance>
A test piece (size: 100 mm × 100 mm) in which a film for forming a protective film having a thickness of 45 μm was attached to a copper foil having a thickness of 30 μm was thermally cured (at 130 ° C. for 2 hours) in an atmosphere in an oven.
Then, due to the shrinkage accompanying thermal curing of the protective film-forming film, the distance between the points is the maximum value in the rounded shape of the copper foil that is rounded with the surface on which the protective film-forming film is attached inside. The following two points were taken and the distance was measured. It means that the copper foil is greatly warped as the distance is smaller, and the stress due to thermal shrinkage of the protective film-forming film is larger, so that it can be judged that the warp correction ability is high.
＜信頼性評価＞
１．保護膜付チップの製造
 ＃２０００研磨したシリコンウエハ（２００ｍｍ径、厚さ３５０μｍ）の研磨面に、保護膜形成用複合シートの保護膜形成用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、次いで、支持シートを剥離した。その後、１３０℃２時間加熱して保護膜形成用フィルムを硬化し、シリコンウエハと保護膜の積層体を得た。
 上記で得られた積層体の保護膜側をダイシングテープ（リンテック社製　Ａｄｗｉｌｌ　Ｄ－６８６Ｈ）に貼付し、ダイシング装置（ディスコ社製　ＤＦＤ６５１）を使用して、３ｍｍ×３ｍｍのサイズにダイシングして信頼性評価用の保護膜付チップを得た。 <Reliability evaluation>
1. Production of chip with protective film # 2000 Polished protective film-forming film of composite sheet for protective film formation on a polished silicon wafer (200 mm diameter, 350 μm thickness) tape mounter (Adwill RAD-3600 F / 12) was applied while heating to 70 ° C., and then the support sheet was peeled off. Thereafter, the protective film-forming film was cured by heating at 130 ° C. for 2 hours to obtain a laminate of a silicon wafer and a protective film.
The protective film side of the laminate obtained above is affixed to a dicing tape (Adwill D-686H manufactured by Lintec Corporation), and is diced to a size of 3 mm × 3 mm using a dicing apparatus (DFD651 manufactured by Disco Corporation). A chip with a protective film for property evaluation was obtained.
２．信頼性評価
 得られた保護膜付チップを、８５℃、相対湿度８５％の条件下に１６８時間放置して吸湿させた後、最高温度２６０℃、加熱時間１分間のＩＲリフロー（リフロー炉：相模理工製　ＷＬ－１５－２０ＤＮＸ型）を３回行った。さらに、この保護膜付チップを冷熱衝撃装置（ＥＳＰＥＣ社製　ＴＳＥ－１１Ａ）内に設置し、－４０℃で１０分間保持後１２５℃で１０分間保持するサイクルを１０００サイクル繰り返した。
 その後、冷熱衝撃装置から取り出した保護膜付チップについて、走査型超音波探傷装置（日立建機ファインテック社製　Ｈｙｅ－Ｆｏｃｕｓ）および断面観察により、半導体チップと保護膜との接合部における剥離や保護膜におけるクラックの有無を観察した。
 ２５個の保護膜付チップについて上記評価を行い、接合部の剥離または保護膜のクラックが発生した個数（不良数）を数えた。不良数が少ないほど、保護膜形成用フィルムの信頼性が高いことを示す。 2. Reliability evaluation The obtained chip with protective film was allowed to absorb moisture for 168 hours under conditions of 85 ° C. and 85% relative humidity, and then IR reflow (reflow oven: Sagami, with a maximum temperature of 260 ° C. and a heating time of 1 minute) Riko WL-15-20DNX type) was performed three times. Further, this protective film-coated chip was placed in a thermal shock apparatus (TSE-11A manufactured by ESPEC), held at −40 ° C. for 10 minutes, and then held at 125 ° C. for 10 minutes for 1000 cycles.
Then, for the chip with protective film taken out from the thermal shock apparatus, peeling and protection at the junction between the semiconductor chip and the protective film by scanning ultrasonic flaw detector (Hy-Focus manufactured by Hitachi Construction Machinery Finetech Co., Ltd.) and cross-sectional observation The presence or absence of cracks in the film was observed.
The above evaluation was performed on 25 chips with a protective film, and the number of defects (number of defects) in which peeling of the joints or cracks in the protective film occurred was counted. The smaller the number of defects, the higher the reliability of the protective film-forming film.
＜ウエハ反り評価＞
 ２００μｍの厚みを有し、回路面側（表面側）に凹形状に反り（反り量：１０ｍｍ）が生じている８インチ回路付ウエハを準備した（図５参照）。
 次いで、ウエハの裏面に保護膜形成用フィルムを貼付し、１３０℃２時間熱硬化した。
 その後、得られたウエハの反り量が２ｍｍ以下であった場合を「良好」、ウエハの反り量が２ｍｍを超えた場合を「不良」と評価した。ウエハの反り量が２ｍｍ以下であれば、一般的なウエハマウンターでの搬送が可能である。 <Wafer warpage evaluation>
An 8-inch wafer with a circuit having a thickness of 200 μm and having a concave warpage (warpage amount: 10 mm) on the circuit surface side (surface side) was prepared (see FIG. 5).
Next, a protective film-forming film was attached to the back surface of the wafer, and heat cured at 130 ° C. for 2 hours.
Then, the case where the amount of warpage of the obtained wafer was 2 mm or less was evaluated as “good”, and the case where the amount of warpage of the wafer exceeded 2 mm was evaluated as “bad”. If the amount of warpage of the wafer is 2 mm or less, it can be transferred by a general wafer mounter.
［保護膜形成用組成物］
 保護膜形成用組成物を構成する各成分を下記に示す。
（Ａ１－１）重合体成分：ｎ－ブチルアクリレート５５質量部、メチルアクリレート１５質量部、グリシジルメタクリレート２０質量部、及び２－ヒドロキシエチルアクリレート１０質量部を共重合してなるアクリル系重合体（重量平均分子量：９０万、ガラス転移温度：－２８℃）
（Ａ１－２）重合体成分：ｎ－ブチルアクリレート５５質量部、メチルアクリレート３５質量部、及び２－ヒドロキシエチルアクリレート１０質量部を共重合してなるアクリル系重合体（重量平均分子量：９０万、ガラス転移温度：－３１℃）
（Ｂ１１－１）ビスフェノールＡ型エポキシ樹脂（三菱化学製ｊＥＲ８２８、エポキシ当量１８４～１９４ｇ／ｅｑ）
（Ｂ１１－２）ビスフェノールＡ型エポキシ樹脂（三菱化学製ｊＥＲ１０５５、エポキシ当量８００～９００ｇ／ｅｑ）
（Ｂ１１－３）ジシクロペンタジエン型エポキシ樹脂（大日本インキ化学工業（株）製エピクロンＨＰ－７２００ＨＨ、エポキシ当量２５５～２６０ｇ／ｅｑ）
（Ｂ１１－４）ｏ－クレゾールノボラック型エポキシ樹脂（日本化薬製ＥＯＣＮ－１０４Ｓ、エポキシ当量２１３～２２３ｇ／ｅｑ）
（Ｂ１２）熱活性潜在性エポキシ樹脂硬化剤（ジシアンジアミド（ＡＤＥＫＡ製アデカハードナーＥＨ－３６３６ＡＳ、活性水素量２１ｇ／ｅｑ））
（Ｂ１３）硬化促進剤：２－フェニル－４，５－ジヒドロキシメチルイミダゾール（四国化成工業社製キュアゾール２ＰＨＺ）
（Ｃ－１）シリカフィラー（アドマテックス製ＳＣ２０５０ＭＡ、平均粒子径０．５μｍ）
（Ｃ－２）シリカフィラー（平均粒子径３μｍ）
（Ｃ－３）シリカフィラー（タツモリ製ＳＶ－１０、平均粒子径８μｍ）
（Ｄ）着色剤：カーボンブラック（三菱化学社製　＃ＭＡ６５０、平均粒径２８ｎｍ）
（Ｅ）シランカップリング剤（日本ユニカー製Ａ－１１１０） [Composition for forming protective film]
Each component which comprises the composition for protective film formation is shown below.
(A1-1) Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 15 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight) (Average molecular weight: 900,000, glass transition temperature: -28 ° C)
(A1-2) Polymer component: acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 35 parts by mass of methyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 900,000, Glass transition temperature: -31 ° C)
(B11-1) Bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent of 184 to 194 g / eq)
(B11-2) Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation jER1055, epoxy equivalent 800-900 g / eq)
(B11-3) Dicyclopentadiene type epoxy resin (Dainippon Ink & Chemicals, Inc. Epicron HP-7200HH, epoxy equivalent 255-260 g / eq)
(B11-4) o-cresol novolac epoxy resin (EOCN-104S manufactured by Nippon Kayaku, epoxy equivalent 213 to 223 g / eq)
(B12) Thermally active latent epoxy resin curing agent (dicyandiamide (Adeka Hardener EH-3636AS manufactured by ADEKA, active hydrogen amount 21 g / eq))
(B13) Curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ manufactured by Shikoku Kasei Kogyo Co., Ltd.)
(C-1) Silica filler (Admatechs SC2050MA, average particle size 0.5 μm)
(C-2) Silica filler (average particle size 3 μm)
(C-3) Silica filler (Tatsumori SV-10, average particle size 8 μm)
(D) Colorant: Carbon black (Mitsubishi Chemical Corporation # MA650, average particle size 28 nm)
(E) Silane coupling agent (Nihon Unicar A-1110)
（実施例及び比較例）
 上記成分を表１に記載の配合量で配合し、保護膜形成用組成物を得た。表１における各成分の配合量は固形分換算の質量部を示し、本発明において固形分とは溶媒以外の全成分をいう。
 表１に記載の組成の保護膜形成用組成物を、メチルエチルケトンにて固形分濃度が６１質量％となるように希釈し、支持シート（リンテック社製ＳＰ－ＰＥＴ３８１１、厚さ３８μｍ）の剥離処理面上に乾燥後厚みが４５μｍになるように塗布・乾燥（乾燥条件：オーブンにて１２０℃、２分間）して、支持シート上に保護膜形成用フィルムを形成し、保護膜形成用複合シートを得た。その後、保護膜形成用フィルムと剥離シート（ポリエチレンテレフタレートフィルム（リンテック社製ＳＰ－ＰＥＴ３８１０３１、厚さ３８μｍ）の剥離処理面とを貼り合せて、剥離シートの貼り合された保護膜形成用複合シートを得た。各評価結果を表２に示す。 (Examples and Comparative Examples)
The said component was mix | blended with the compounding quantity of Table 1, and the composition for protective film formation was obtained. The compounding quantity of each component in Table 1 shows the mass part of solid content conversion, and solid content means all components other than a solvent in this invention.
The protective film-forming composition having the composition shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration was 61% by mass, and the release-treated surface of the support sheet (SP-PET3811 manufactured by Lintec, thickness 38 μm) Coating and drying (drying conditions: 120 ° C. in an oven for 2 minutes) to a thickness of 45 μm after drying, forming a protective film-forming film on the support sheet, and forming a protective film-forming composite sheet Obtained. Thereafter, the protective film-forming film and the release sheet (polyethylene terephthalate film (SP-PET 381031, manufactured by Lintec Corporation, thickness 38 μm) are bonded together to form a protective film-forming composite sheet having the release sheet attached thereto. Each evaluation result is shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 １：基材
 ２：粘着剤層
 ３：粘着シート（支持シート）
 ４：治具接着層
 ５：界面接着調整層
 １０：保護膜形成用フィルム
 １００：保護膜形成用複合シート 1: Base material 2: Adhesive layer 3: Adhesive sheet (support sheet)
4: Jig adhesion layer 5: Interfacial adhesion adjustment layer 10: Film for protective film formation 100: Composite sheet for protective film formation

Claims (7)

  1. 　熱硬化性を有し、
    　熱硬化後のガラス転移温度が１５０～３００℃であり、
    　熱硬化後の２３℃における引張弾性率が０．５～１０ＧＰａである保護膜形成用フィルム。     Thermosetting,
    The glass transition temperature after thermosetting is 150 to 300 ° C.,
    A protective film-forming film having a tensile elastic modulus at 23 ° C. of 0.5 to 10 GPa after thermosetting.
  2. 　エポキシ化合物およびアミン系硬化剤を含有してなる熱硬化性成分が含まれる請求項１に記載の保護膜形成用フィルム。 The protective film-forming film according to claim 1, comprising a thermosetting component comprising an epoxy compound and an amine curing agent.
  3. 　さらに重合体成分および熱硬化性重合体成分のいずれか単独または両方を含有し、重合体成分および熱硬化性重合体成分の合計１００質量部に対して、熱硬化性成分を１３５質量部以下含む請求項２に記載の保護膜形成用フィルム。 Furthermore, it contains any one or both of the polymer component and the thermosetting polymer component, and includes 135 parts by mass or less of the thermosetting component with respect to 100 parts by mass in total of the polymer component and the thermosetting polymer component. The protective film-forming film according to claim 2.
  4. 　保護膜形成用フィルムには無機フィラーが含まれ、
    　無機フィラーの含有量が、保護膜形成用フィルムを構成する全固形分１００質量部に対して１０～７０質量部である請求項１～３のいずれかに記載の保護膜形成用フィルム。     The protective film-forming film contains an inorganic filler,
    The protective film-forming film according to any one of claims 1 to 3, wherein the content of the inorganic filler is 10 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film-forming film.
  5. 　無機フィラーの平均粒径が０．０２～５μｍである請求項４に記載の保護膜形成用フィルム。 The protective film-forming film according to claim 4, wherein the inorganic filler has an average particle size of 0.02 to 5 μm.
  6. 　保護膜形成用フィルムには熱硬化性重合体成分が含まれ、
    　熱硬化性重合体成分は、構成する単量体としてエポキシ基含有単量体を含むアクリル系重合体である請求項１～５のいずれかに記載の保護膜形成用フィルム。     The protective film-forming film contains a thermosetting polymer component,
    6. The protective film-forming film according to claim 1, wherein the thermosetting polymer component is an acrylic polymer containing an epoxy group-containing monomer as a constituent monomer.
  7. 　請求項１～６のいずれかに記載の保護膜形成用フィルムの片面に支持シートを剥離可能に形成してなる保護膜形成用複合シート。
    　     A composite sheet for forming a protective film, comprising a support sheet detachably formed on one side of the film for forming a protective film according to any one of claims 1 to 6.
PCT/JP2014/058038 2013-03-22 2014-03-24 Protective film-forming film and protective film-forming composite sheet WO2014148642A1 (en)

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