WO2023157907A1 - Film for forming protective coating, composite sheet for forming protective coating, protective coating-equipped semiconductor chip, and semiconductor device - Google Patents

Film for forming protective coating, composite sheet for forming protective coating, protective coating-equipped semiconductor chip, and semiconductor device Download PDF

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Publication number
WO2023157907A1
WO2023157907A1 PCT/JP2023/005403 JP2023005403W WO2023157907A1 WO 2023157907 A1 WO2023157907 A1 WO 2023157907A1 JP 2023005403 W JP2023005403 W JP 2023005403W WO 2023157907 A1 WO2023157907 A1 WO 2023157907A1
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Prior art keywords
protective film
forming
film
protective
elastic modulus
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PCT/JP2023/005403
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French (fr)
Japanese (ja)
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和恵 上村
康貴 渡邉
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リンテック株式会社
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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26

Definitions

  • the present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, a semiconductor chip with a protective film, and a semiconductor device.
  • semiconductor devices have been manufactured using a so-called face down mounting method in which a semiconductor chip is mounted on a substrate with the circuit surface facing the substrate.
  • electrodes such as bumps formed on the circuit surface of the semiconductor chip are joined to the substrate.
  • a protective film may be formed on the The protective film plays a role of protecting the semiconductor chip from external impacts and the like during the manufacturing process of the semiconductor chip and after the semiconductor chip is mounted.
  • the protective film can be used for identification, decoration, etc. of semiconductor chips by laser printing.
  • the protective film can also function as a light shielding layer that prevents malfunction of the circuit.
  • a protective film is formed using the film for protective film formation, for example.
  • a curable film made of a thermosetting or energy ray-curable resin composition is used from the viewpoint of mechanical strength, heat resistance, and the like.
  • a curable film for forming a protective film is applied to an object to be protected, such as a semiconductor wafer or a semiconductor chip, and then cured to form a protective film made of the cured product.
  • Patent Document 1 discloses a chip protection film characterized by having a curable protective film-forming layer having a pencil hardness of 5H or more after curing.
  • the present invention has been made in view of the above problems, and provides a film for forming a protective film capable of forming a protective film having both flame retardancy and adhesiveness, and a film for forming a protective film using the film for forming a protective film.
  • An object of the present invention is to provide a composite sheet for semiconductor devices, a semiconductor chip with a protective film, and a semiconductor device.
  • the present inventors focused on the storage elastic modulus E' of the protective film-forming film, and the copper foil peel strength and flame retardancy of the cured product of the protective film-forming film, and have completed the present invention. That is, the present invention relates to the following [1] to [14].
  • [1] A curable film for forming a protective film The minimum value of the storage elastic modulus E′ in the temperature range of 23 to 150° C. is 1.0 MPa or more, and the ratio of the storage elastic modulus E′ (80) at 80° C. to the storage elastic modulus E′ (130) at 130° C.
  • [E'(80)/E'(130)] is 1.25 or more
  • the cured product of the protective film-forming film has a copper foil peel strength of 3.0 N/10 mm or more
  • Requirement (1) Cut the protective film obtained by curing the protective film-forming film into a size of 200 mm long side ⁇ 50 mm short side, and store it for 48 hours in an environment with a temperature of 23 ° C. and a relative humidity of 50%.
  • the short side direction is wound around a cylindrical rod with a diameter of 12.7 mm, a marked line is provided at a position 125 mm from one end in the long side direction, and the other end and the marked line After a section (75 mm section) is taped to create a cylindrical protective membrane, the bar is withdrawn.
  • thermosetting properties The film for forming a protective film according to any one of the above [1] to [4], wherein the film for forming a protective film has thermosetting properties.
  • the film for forming a protective film is formed using a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin.
  • the (A) thermoplastic resin is an acrylic resin.
  • thermosetting resin (B) is an epoxy resin.
  • a protective film-forming composite sheet comprising a substrate, an adhesive layer, and the protective film-forming film according to any one of [1] to [10] in this order.
  • a semiconductor chip with a protective film having a protective film that is a cured product of the film for forming a protective film according to any one of [1] to [10] above.
  • a semiconductor device having the semiconductor chip with a protective film according to [13] above.
  • a protective film-forming film capable of forming a protective film having both flame retardancy and adhesiveness, a protective film-forming composite sheet using the protective film-forming film, a semiconductor chip with a protective film, and a semiconductor device can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the protective film-forming composite sheet of the first embodiment of the present invention
  • FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the protective film-forming composite sheet of the second aspect of the present invention
  • FIG. 4 is a schematic cross-sectional view showing another example of the configuration of the protective film-forming composite sheet of the second aspect of the present invention.
  • the number average molecular weight (Mn) and the mass average molecular weight (Mw) are values converted to standard polystyrene measured by gel permeation chromatography (GPC), specifically described in Examples. It is a value measured based on the method.
  • energy ray means an electromagnetic wave or charged particle beam that has energy quanta.
  • energy rays include ultraviolet rays, radiation, electron beams, and the like.
  • Ultraviolet rays can be applied using an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a black light, an LED lamp, or the like.
  • the electron beam can be generated by an electron beam accelerator or the like.
  • energy ray-curable means the property of curing by irradiation with energy rays
  • non-energy ray-curable means the property of not curing even when irradiated with energy rays. and includes thermosetting and non-setting.
  • thermosetting means a property of curing by heating
  • non-curing means a property of not curing by heating, irradiation of energy rays, or the like.
  • (meth)acrylic acid refers to both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • circuit surface of the semiconductor wafer and semiconductor chip refers to the surface on which the circuit is formed
  • back surface of the semiconductor wafer and semiconductor chip refers to the surface opposite to the circuit surface
  • the “thickness” of an object means the thickness of the entire object. For example, when the object consists of multiple layers, the sum of all layers that make up the object means the thickness of
  • the "object” as used herein means a film for forming a protective film, a release film, a substrate, an adhesive layer, and the like, which will be described later.
  • the thickness in this specification is a value measured based on the method described in Examples.
  • solid content refers to the components contained in the target composition, excluding diluent solvents such as water and organic solvents.
  • the protective film-forming film of the present embodiment is a curable protective film-forming film having a minimum storage elastic modulus E' of 1.0 MPa or more in a temperature range of 23 to 150 ° C., and at 80 ° C.
  • the ratio [E'(80)/E'(130)] of the storage elastic modulus E'(80) and the storage elastic modulus E'(130) at 130°C is 1.25 or more, and the protective film-forming film A film for forming a protective film, which has a copper foil peel strength of 3.0 N/10 mm or more and satisfies the following requirement (1).
  • Requirement (1) Cut the protective film obtained by curing the protective film-forming film into a size of 200 mm long side ⁇ 50 mm short side, and store it for 48 hours in an environment with a temperature of 23 ° C. and a relative humidity of 50%. After that, the short side direction is wound around a cylindrical rod with a diameter of 12.7 mm, a marked line is provided at a position 125 mm from one end in the long side direction, and the other end and the part between the marked line After taping (at 75 mm) to create a cylindrical protective membrane, the bar is withdrawn.
  • the protective film-forming film of the present embodiment is curable, preferably thermosetting or energy ray curable, and more preferably thermosetting.
  • the "protective film-forming film” means a film before curing
  • the "protective film” means a film after curing the protective film-forming film.
  • the curing conditions of the protective film-forming film when forming a cured product of the protective film-forming film, which is the object of measuring the copper foil peel strength, and when forming the protective film which is the test object of the above requirement (1) may be conditions under which the reaction of the curable components in the protective film-forming film can be substantially completed.
  • the conditions described in ⁇ Curing Conditions for Protective Film-Forming Film> or the conditions described in Examples may be employed.
  • the protective film-forming film of the present embodiment is applied to an object to be protected, such as a semiconductor wafer or a semiconductor chip, and then cured to form a protective film that protects the object from external impact or the like.
  • the protective film-forming film of the present embodiment is attached to the back surface of a semiconductor wafer, and is useful for manufacturing a semiconductor chip with a protective film. Since the protective film formed from the protective film-forming film of the present embodiment has both flame retardancy and adhesiveness, the protective film formed from the protective film-forming film of the present embodiment was provided.
  • the object to be protected is excellent in safety, and the formed protective film is excellent in protecting the object to be protected.
  • the protective film-forming film of the present embodiment may consist of only one layer, or may consist of multiple layers of two or more layers.
  • the layers constituting the multiple layers may be the same or different.
  • the protective film-forming film of the present embodiment has a storage elastic modulus E' minimum value of 1.0 MPa or more in a temperature range of 23 to 150 ° C., and a storage elastic modulus E' at 80 ° C. (80) and at 130 ° C.
  • the ratio [E'(80)/E'(130)] to the storage modulus E'(130) is 1.25 or more.
  • the protective film-forming film of the present embodiment has good rigidity, and the protective film In addition to being excellent in handleability as a forming film, the mechanical strength and adhesiveness of the protective film, which is a cured product thereof, are improved, and the protective property of the object to be protected is improved.
  • the storage elastic modulus E' in the present embodiment is measured under the following conditions, and more specific examples of the measuring method are as described in Examples.
  • Measuring device Using a dynamic viscoelasticity measuring device, measurement mode: tension mode, frequency: 11 Hz, measurement temperature range: -20 to 150°C, temperature increase rate: 3°C/min. Moreover, the values of the storage elastic modulus E'(80) and the storage elastic modulus E'(130) shall be specified according to the following method. [Method for specifying storage elastic modulus E′ (80) and storage elastic modulus E′ (130)] Regarding the storage modulus E' (80), it may be difficult to strictly measure the storage modulus E' at exactly 80.0 ° C. due to the characteristics of the measuring device.
  • the storage elastic modulus E′ measured at the measurement temperature closest to 80.0° C. is specified as “80° C. storage elastic modulus E′ (80)”. That is, when the storage elastic modulus E' values are plotted at the measurement temperatures of 79.1°C, 80.2°C, and 81.5°C, the storage elastic modulus E' at 80.2°C is expressed as "storage elastic modulus at 80°C Let the rate be E'(80)'. When there are two measured temperatures closest to 80.0°C, such as 79.5°C and 80.5°C, the average value of the two points is specified as the storage elastic modulus E'(80). .
  • the minimum value of the storage elastic modulus E′ of the protective film-forming film of the present embodiment in the temperature range of 23 to 150° C. is preferably 1.1 MPa or more, preferably 100 MPa or less, more preferably 10 MPa or less. , and more preferably 5 MPa or less.
  • the minimum value of the storage elastic modulus E′ in the temperature range of 23 to 150° C. is within the above range, the handleability of the protective film-forming film and the flame retardancy and adhesiveness of the protective film tend to be well balanced. be.
  • the ratio [E'(80)/E'(130)] of the storage elastic modulus E' is preferably 1.27 or more, more preferably 1.29 or more, and preferably 3.00 or less. It is preferably 2.50 or less, more preferably 2.20 or less.
  • the ratio [E'(80)/E'(130)] of the storage elastic modulus E' is within the above range, the balance between the handleability of the protective film-forming film and the flame retardancy and adhesiveness of the protective film is improved. It tends to get better.
  • the temperature at which the storage elastic modulus E′ exhibits the minimum value in the temperature range of 23 to 150°C is not particularly limited, but is preferably 90 to 148°C, more preferably 95 to 145°C, and still more preferably 100 to 140°C. .
  • the temperature at which the storage elastic modulus E′ reaches the minimum value in the temperature range of 23 to 150° C. is within the above range, the storage stability and curability of the protective film-forming film tend to be well balanced.
  • the copper foil peel strength of the cured product of the protective film forming film of the present embodiment is 3.0 N/10 mm or more.
  • the copper foil peel strength of the present embodiment is measured by the following measuring method, and more specific examples of the measuring method are as described in Examples.
  • Method for measuring peel strength of copper foil On the surface of the film for forming a protective film of this embodiment, a copper foil with a long side of 50 mm ⁇ a short side of 10 mm ⁇ a thickness of 150 ⁇ m is applied, and one end of the long side of the copper foil is 10 mm. It is pasted using a laminator while leaving it as a pasting part.
  • the protective film-forming film is cured to form a laminate in which the silicon wafer, the protective film which is a cured product of the protective film-forming film, and the copper foil are laminated in the thickness direction, and the copper foil is formed.
  • the measurement sample is attached to a tensile tester, the unattached portion of the copper foil is gripped with a gripper, and the copper foil is peeled off in a 90° direction at a peeling speed of 50 mm / min. Get strength.
  • the copper foil peel strength of the protective film forming film of the present embodiment is preferably 4.0 N/10 mm or more, more preferably 5.0 N/10 mm or more, and still more preferably 6.0 N/10 mm. More preferably, it is 7.0 N/10 mm or more.
  • the upper limit of the copper foil peel strength of the film for forming a protective film of the present embodiment is preferably as high as possible, but from the viewpoint of ease of manufacture, it may be 20 N/10 mm or less, or 15 N/10 mm or less. It may be 10N/10mm or less.
  • the protective film-forming film of the present embodiment is preferably formed using a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin.
  • the resin composition used for forming the protective film-forming film of the present embodiment may be referred to as "protective film-forming resin composition”.
  • the protective film-forming resin composition is a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin. Each component contained in the protective film-forming resin composition will be described in detail below.
  • thermoplastic resin By including (A) the thermoplastic resin in the protective film-forming resin composition, the protective film-forming film of the present embodiment is excellent in flexibility before curing and adhesion to an object to be protected.
  • thermoplastic resin may be used alone or in combination of two or more.
  • Thermoplastic resins include, for example, acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, polybutene resins, polybutadiene resins, and polystyrene resins. Among these, acrylic resins are preferred.
  • the raw material monomer of the acrylic resin preferably contains a (meth)acrylic acid ester.
  • the raw material monomers for the acrylic resin may be used singly or in combination of two or more.
  • Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate ) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate,
  • the raw material monomer of the acrylic resin contains an alkyl (meth)acrylate.
  • the number of carbon atoms in the alkyl group constituting the alkyl (meth)acrylate alkyl ester is not particularly limited, but is preferably 1-18, more preferably 1-10, and still more preferably 1-4. If the alkyl group constituting the alkyl ester of alkyl (meth)acrylate can take n-, sec-, tert- or iso-form depending on the carbon position having a free valence, it may be in any form. good.
  • the content of the alkyl (meth)acrylate in the raw material monomer of the acrylic resin is not particularly limited, but is preferably 50 to 97% by mass, more preferably 60 to 93%, based on the raw material monomer (100% by mass) of the acrylic resin. % by mass, more preferably 70 to 90% by mass.
  • the raw material monomers for the acrylic resin preferably contain a hydroxyl group-containing (meth)acrylate together with the alkyl (meth)acrylate.
  • the content of the hydroxyl group-containing (meth)acrylate in the raw material monomer of the acrylic resin is not particularly limited, but the raw material monomer of the acrylic resin (100 mass %), preferably 2 to 50% by mass, more preferably 6 to 40% by mass, and still more preferably 10 to 30% by mass.
  • the raw material monomer of the acrylic resin may or may not contain a monomer other than the (meth)acrylic acid ester.
  • monomers other than (meth)acrylic acid esters include (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, acryloylmorpholine, styrene, acrylamide, and N-methylolacrylamide.
  • the mass average molecular weight (Mw) of the thermoplastic resin is not particularly limited, but is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, still more preferably 150, 000 to 1,000,000.
  • Mw mass average molecular weight
  • the mass average molecular weight (Mw) of the thermoplastic resin is at least the above lower limit, the shape stability of the protective film-forming film tends to be better.
  • the mass average molecular weight (Mw) of the thermoplastic resin (A) is equal to or less than the above upper limit, the film for forming a protective film easily follows the uneven surface of the object to be protected, and the object to be protected and the protective film forming There is a tendency that the generation of voids and the like between the film and the film is further suppressed.
  • the glass transition temperature (Tg) of the thermoplastic resin (hereinafter also simply referred to as “Tg”) is not particularly limited, but is preferably ⁇ 60 to 70° C., more preferably ⁇ 30 to 50° C., still more preferably -10 to 20°C.
  • Tg glass transition temperature
  • the protective film-forming film tends to have better cohesive strength. Further, when the Tg of the thermoplastic resin (A) is equal to or less than the above upper limit, the flexibility and adhesiveness of the protective film-forming film tend to be improved.
  • the Tg of an acrylic resin can be obtained by calculation using the Fox formula shown below.
  • 1/Tg (W1/Tg1)+(W2/Tg2)+...+(Wm/Tgm)
  • Tg is the glass transition temperature of the acrylic resin
  • the glass transition temperature of the homopolymer of each monomer in the above Fox formula the values described in Kobunshi Data Handbook, Adhesive Handbook, or Polymer Handbook can be used.
  • methyl acrylate homopolymer has a Tg of 10°C
  • 2-hydroxyethyl acrylate homopolymer has a Tg of -15°C
  • 2-ethylhexyl acrylate has a Tg of -70°C
  • 2-ethylhexyl methacrylate has a Tg of -10°C.
  • Tg can also be calculated
  • the thermoplastic resin may have a functional group.
  • the functional group include vinyl group, (meth)acryloyl group, amino group, hydroxy group, carboxy group, isocyanate group and the like.
  • the functional group may be bonded to another compound via (H) a cross-linking agent, which will be described later, or (H) without a cross-linking agent. It may be directly bound to another compound. The reliability of the protective film tends to be better when (A) the thermoplastic resin bonds with another compound via (H) the cross-linking agent or directly with the functional group.
  • an acrylic resin having a functional group is preferable, and an acrylic resin having a hydroxy group as a functional group is more preferable.
  • the content of (A) the thermoplastic resin in the protective film-forming resin composition is not particularly limited, but is preferably 5 to 80 mass with respect to the solid content (100 mass%) of the protective film-forming resin composition. %, more preferably 7 to 50% by mass, still more preferably 10 to 30% by mass.
  • thermosetting resin By containing (B) a thermosetting resin in the protective film-forming resin composition, the protective film-forming film of the present embodiment has thermosetting properties, and the protective film is excellent in mechanical strength, heat resistance, etc. can be formed.
  • the thermosetting resin may be used alone or in combination of two or more.
  • Thermosetting resins include, for example, epoxy resins, phenol resins, melamine resins, urea resins, and thermosetting polyimide resins. Among these, epoxy resins are preferred. As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable.
  • Examples of the epoxy resin include known ones, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and hydrogenated products thereof; phenol novolak type epoxy resin, cresol novolak type epoxy resin, ortho novolac type epoxy resins such as cresol novolak type epoxy resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins; dicyclopentadiene type epoxy resins; biphenyl type epoxy resins; naphthalene type epoxy resins; Among these, dicyclopentadiene-type epoxy resins, bisphenol-type epoxy resins, and naphthalene-type epoxy resins are preferable from the viewpoints of handleability, heat resistance, and the like of the protective film-forming film.
  • bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and hydrogenated products thereof
  • phenol novolak type epoxy resin cresol novolak type epoxy resin, ortho novolac type epoxy resins such as
  • the number average molecular weight (Mn) of the epoxy resin is not particularly limited, but is preferably 200 to 30,000, more preferably 250, from the viewpoint of the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film. ⁇ 10,000, more preferably 300 to 3,000.
  • the epoxy equivalent of the epoxy resin is not particularly limited, it is preferably 100 to 1,500 g/eq, more preferably 130 to 1, from the viewpoints of the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film. , 200 g/eq, more preferably 160 to 1,000 g/eq.
  • epoxy equivalent means the number of grams (g/eq) of an epoxy resin containing 1 gram equivalent of epoxy groups, and can be measured according to JIS K 7236:2001.
  • the content of the epoxy resin in the protective film-forming resin composition is not particularly limited, but is preferably 2 to 60% by mass, more preferably 2 to 60% by mass, based on the solid content (100% by mass) of the protective film-forming resin composition. is 4 to 40% by mass, more preferably 7 to 20% by mass.
  • the content of the epoxy resin is at least the above lower limit, the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film tend to be better.
  • the content of the epoxy resin is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
  • the content of the (B) thermosetting resin in the protective film-forming resin composition is not particularly limited, but is preferably 2 to 60 with respect to the solid content (100% by mass) of the protective film-forming resin composition. % by mass, more preferably 4 to 40% by mass, and even more preferably 7 to 20% by mass.
  • the content of the thermosetting resin is at least the above lower limit, the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film tend to be better.
  • the content of the thermosetting resin (B) is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
  • the protective film-forming resin composition preferably further contains (C) an inorganic filler.
  • the protective film-forming film of the present embodiment has excellent shape retention, and the protective film-forming film of the present embodiment
  • the protective film formed from is excellent in flame retardancy, low thermal expansion, low hygroscopicity, and the like.
  • An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
  • inorganic fillers examples include silica, talc, calcium carbonate, titanium white, red iron oxide, and silicon carbide. Among these, silica and alumina are preferred, and silica is more preferred.
  • the shape of the inorganic filler (C) is not particularly limited, and may be, for example, spherical, pulverized, or fibrous, but preferably spherical.
  • the inorganic filler may be surface-modified with a surface treatment agent or the like. As the surface treatment agent, the (I) coupling agent described later can be used.
  • the average particle size (D 50 ) of the inorganic filler (C) is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and still more preferably 0.3 to 1 ⁇ m.
  • the average particle size (D 50 ) of the inorganic filler is obtained by measuring the particle size distribution by the Coulter counter method using a multisizer three machine (manufactured by Beckman Coulter, Inc.) or the like.
  • the content of (C) the inorganic filler in the protective film-forming resin composition is not particularly limited, but is preferably 50% by mass or more with respect to the solid content (100% by mass) of the protective film-forming resin composition. , more preferably 53% by mass or more, still more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.
  • the content of the inorganic filler is at least the above lower limit, the shape retention of the protective film-forming film, the flame retardancy of the protective film, low thermal expansion, and low hygroscopicity tend to be better. . Further, when the content of the inorganic filler (C) is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
  • the protective film-forming resin composition preferably further contains (D) a flame retardant.
  • a flame retardant By including (D) the flame retardant in the protective film-forming resin composition, the protective film formed from the protective film-forming film of the present embodiment has excellent flame retardancy.
  • a flame retardant may be used individually by 1 type, and may use 2 or more types together.
  • Flame retardants include, for example, halogen-based compounds, compounds containing phosphorus atoms, compounds containing nitrogen atoms, compounds containing phosphorus atoms and nitrogen atoms, and inorganic flame retardants other than these.
  • compounds containing a phosphorus atom and a nitrogen atom are preferable from the viewpoint of flame retardancy and adhesiveness of the protective film.
  • a compound containing a phosphorus atom and a nitrogen atom is hereinafter referred to as "(D1) a compound containing a phosphorus atom and a nitrogen atom".
  • the resin composition for forming a protective film contains (D1) a compound containing a phosphorus atom and a nitrogen atom, it tends to be possible to form a protective film that satisfactorily achieves both flame retardancy and adhesiveness.
  • the phosphorus atoms and nitrogen atoms contained in component (D1) contribute to flame retardancy, and the compound is used as (A) a thermoplastic resin, (B) a thermosetting resin, etc.
  • the compound containing a phosphorus atom and a nitrogen atom may be used alone or in combination of two or more.
  • the number of phosphorus atoms that the compound containing a phosphorus atom and a nitrogen atom has in one molecule is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 3 to 5. , particularly preferably 3 or 4.
  • the number of nitrogen atoms in one molecule of the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 3 to 5. , particularly preferably 3 or 4.
  • the content of the phosphorus atom in the compound containing a phosphorus atom and a nitrogen atom is not particularly limited. 30% by mass, more preferably 7 to 20% by mass, still more preferably 10 to 15% by mass.
  • the content of nitrogen atoms in the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, but (D1) the compound containing a phosphorus atom and a nitrogen atom (100 mass%) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 4 to 10% by mass.
  • the compound containing a phosphorus atom and a nitrogen atom is preferably a compound containing a bond between a phosphorus atom and a nitrogen atom from the viewpoint of further improving the flame retardancy of the protective film.
  • the compound containing a bond between a phosphorus atom and a nitrogen atom is an organic compound containing a bond between a phosphorus atom and a nitrogen atom from the viewpoint of forming a protective film that achieves both flame retardancy and adhesion. is preferred, and a compound containing a structure represented by the following general formula (D-1) is more preferred.
  • R 1 represents a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group.
  • a plurality of R 1 may be the same or different.
  • n represents an integer of 3 to 20.
  • -* 1 and -* 2 represent a bond with another atom, bond -* 1 and bond -* 2 are linked to each other, You may form a ring structure.
  • Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R 1 in the general formula (D-1) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted An alkynyl group and the like can be mentioned. These aliphatic hydrocarbon groups may be linear or branched. Although the number of carbon atoms in the substituted or unsubstituted aliphatic hydrocarbon group is not particularly limited, it is preferably 1-10, more preferably 2-8, still more preferably 3-5.
  • an aliphatic hydrocarbon group when an aliphatic hydrocarbon group has a substituent, the carbon number of a substituent shall not be included in the said carbon number.
  • substituents which the aliphatic hydrocarbon group may have include halogen atoms, hydroxy groups, carboxy groups, alkoxy groups, cyano groups, aromatic hydrocarbon groups and the like.
  • aromatic hydrocarbon group as a substituent are the same as the aromatic hydrocarbon group represented by R 1 described later.
  • substituted or unsubstituted aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted naphthyl groups.
  • the number of carbon atoms in the substituted or unsubstituted aromatic hydrocarbon group is not particularly limited, it is preferably 6-12, more preferably 6-8.
  • the aromatic hydrocarbon group has a substituent, the carbon number of the substituent is not included in the number of carbon atoms.
  • substituents that the aromatic hydrocarbon group may have include halogen atoms, hydroxy groups, carboxy groups, alkoxy groups, cyano groups, and aliphatic hydrocarbon groups.
  • the aliphatic hydrocarbon group as a substituent includes the same aliphatic hydrocarbon groups as those represented by R 1 described above.
  • R 1 in general formula (D-1) above is preferably a substituted or unsubstituted phenyl group, more preferably an unsubstituted phenyl group.
  • n in the above general formula (D-1) is not particularly limited, it is preferably an integer of 3-15, more preferably an integer of 3-10, and still more preferably an integer of 3-5.
  • -* 1 and -* 2 in the above general formula (D-1) represent bonds with other atoms.
  • the bond-* 1 and bond-* 2 in the general formula (D-1) may be linked to each other to form a cyclic structure, preferably a cyclic structure.
  • "a compound containing a structure represented by general formula (D-1)” is synonymous with "a compound represented by general formula (D-1)".
  • Examples of compounds containing a phosphorus atom and a nitrogen atom include phosphazene compounds.
  • phosphazene compound means a compound containing alternating phosphorus atoms and nitrogen atoms, each phosphorus atom having two substituents.
  • the phosphazene compound may be either an organic compound or an inorganic compound, but is preferably an organic compound.
  • phosphazene compound examples include cyclic phosphazene compounds, chain phosphazene compounds, and the like, and cyclic phosphazene compounds are preferred.
  • Cyclic phosphazene compounds include, for example, cyclic phenoxyphosphazene compounds such as hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene, dodecafenoxycyclohexaphosphazene, and tetradecafenoxycycloheptaphosphazene; hexapropoxycyclotriphosphazene; cyclic propoxyphosphazene compounds such as , octapropoxycyclotetraphosphazene, decapropoxycyclopentaphosphazene, dodecapropoxycyclohexaphosphazene, and tetradecapropoxycycloheptaphosphazene; Among these,
  • the molecular weight of (D1) the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, it is preferably 300 to 3,000, more preferably 400 to 1,500, still more preferably 500 to 800.
  • (D1) When the molecular weight of the compound containing a phosphorus atom and a nitrogen atom is at least the above lower limit, volatilization of the compound containing (D1) a phosphorus atom and a nitrogen atom can be suppressed during the production process and curing process of the protective film-forming film. There is a tendency.
  • the content of (D1) the compound containing a phosphorus atom and a nitrogen atom in the protective film-forming resin composition is not particularly limited, but is preferably based on the solid content (100 mass%) of the protective film-forming resin composition. Is 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 2.5 to 13% by mass, even more preferably 3 to 11% by mass, even more preferably 3 to 8% by mass, particularly preferably It is 3 to 5% by mass.
  • the content of (D1) the compound containing a phosphorus atom and a nitrogen atom in the protective film-forming resin composition is not particularly limited.
  • the ratio of the content of the (C) inorganic filler to the content of the compound containing (D1) a phosphorus atom and a nitrogen atom in the protective film-forming resin composition [(C) component/(D1) component] is particularly limited. However, it is preferably 2 to 40, more preferably 3 to 35, even more preferably 4 to 30, and particularly preferably 5 to 25, based on mass.
  • the content ratio [component (C)/component (D1)] is within the above range, the protective film tends to have a better balance of flame retardancy, adhesiveness, low thermal expansion and low hygroscopicity.
  • the content of the (D) flame retardant in the protective film-forming resin composition is not particularly limited, but is preferably 1 to 20% by mass based on the solid content (100% by mass) of the protective film-forming resin composition. , More preferably 2 to 15% by mass, still more preferably 2.5 to 13% by mass, still more preferably 3 to 11% by mass, still more preferably 3 to 8% by mass, particularly preferably 3 to 5% by mass.
  • the content of the (D) flame retardant in the protective film-forming resin composition is not particularly limited, but the total amount of the components excluding the inorganic filler and the colorant among the solids of the protective film-forming resin composition ( 100% by mass), preferably 5 to 70% by mass, more preferably 7 to 60% by mass, even more preferably 8 to 50% by mass, even more preferably 9 to 40% by mass, and even more preferably 14 to 35% by mass, particularly preferably 19 to 30% by mass.
  • the content of the flame retardant is at least the above lower limit, the flame retardancy of the protective film tends to be better.
  • the content of the flame retardant (D) is equal to or less than the above upper limit, the adhesiveness of the protective film tends to be better.
  • Examples of (D) flame retardants other than the component (D1) include halogen-based compounds such as chlorine-based flame retardants containing chlorine atoms and brominated flame-retardants containing bromine atoms; Phosphorus atom-containing compounds such as acid metal salts; Nitrogen atom-containing compounds such as triazine ring-containing compounds and isocyanurate ring-containing compounds; Inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and antimony compounds; are mentioned.
  • the protective film-forming resin composition may contain (E) a curing accelerator.
  • the protective film-forming film of the present embodiment tends to have better curability.
  • the curing accelerator may be used alone or in combination of two or more.
  • Curing accelerators include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like organic phosphines; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and the like.
  • imidazoles are preferred, and 2-phenyl-4,5-dihydroxymethylimidazole is more preferred.
  • the content of (E) the curing accelerator in the protective film-forming resin composition is not particularly limited, but (B) thermosetting It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 1 to 3 parts by mass, based on 100 parts by mass of the resin.
  • thermosetting It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 1 to 3 parts by mass, based on 100 parts by mass of the resin.
  • the content of the curing accelerator is at least the above lower limit, the curability of the protective film-forming film tends to be better. Further, when the content of (E) the curing accelerator is equal to or less than the above upper limit, the homogeneity of the cured product tends to be better.
  • the protective film-forming resin composition may contain (F) a colorant.
  • the resin composition for forming a protective film contains (F) a coloring agent, so that the protective film formed from the film for forming a protective film of the present embodiment is endowed with laser printability, light shielding properties, design properties, and the like. can be done.
  • (F) Colorants may be used alone or in combination of two or more.
  • Colorants include known ones, and examples thereof include inorganic pigments, organic pigments, organic dyes, and the like.
  • inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
  • organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine dyes.
  • the content of the (F) coloring agent in the protective film-forming resin composition is not particularly limited, but from the viewpoint of obtaining an appropriate coloring effect. Therefore, the solid content (100% by mass) of the resin composition for forming a protective film is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, and still more preferably 0.1 to 5% by weight, particularly preferably 1 to 3% by weight.
  • the protective film-forming resin composition contains (B) an epoxy resin as the thermosetting resin, it may further contain (G) an epoxy resin curing agent.
  • the protective film-forming resin composition contains (G) the epoxy resin curing agent, the protective film-forming film of the present embodiment tends to have better curability.
  • the epoxy resin curing agent may be used alone or in combination of two or more.
  • the epoxy resin curing agent includes, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule.
  • the functional group capable of reacting with an epoxy group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an anhydride group of an acid group.
  • a phenolic hydroxyl group, an amino group, and an anhydride-modified acid group are preferable, and a phenolic hydroxyl group and an amino group are more preferable.
  • Examples of the (G) epoxy resin curing agent having a phenolic hydroxyl group include phenolic curing agents such as biphenol, novolac type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin.
  • Examples of the (G) epoxy resin curing agent having an amino group include amine-based curing agents such as dicyandiamide.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, more preferably 70 to 200, and still more preferably 80 to 120. .
  • the content of (G) epoxy resin curing agent in the protective film-forming resin composition is not particularly limited. From the viewpoint of improving the curability of the film, it is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and still more preferably 0.7 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. 50 parts by weight, particularly preferably 1 to 10 parts by weight.
  • the protective film-forming resin composition may contain (H) a cross-linking agent.
  • H a cross-linking agent.
  • the crosslinking agent may be used alone or in combination of two or more.
  • Examples of the (H) cross-linking agent include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. is mentioned.
  • organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds (hereinafter, these compounds are collectively abbreviated as "aromatic polyisocyanate compounds, etc.” trimers, isocyanurates and adducts of the above aromatic polyvalent isocyanate compounds; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds and the like with polyol compounds, etc. are mentioned.
  • the above-mentioned "adduct” means a reaction product of the above aromatic polyvalent isocyanate compound and the like with a low-molecular-weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. means. Specific examples thereof include a tolylene diisocyanate adduct of trimethylolpropane, which will be described later.
  • organic polyvalent isocyanate compounds include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4′-diisocyanate 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; Compounds in which one or more selected from the group consisting of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of hydroxyl groups; lysine diisocyanate and the like.
  • organic polyvalent imine compounds examples include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylolmethane- Tri- ⁇ -aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene melamine and the like.
  • the (H) cross-linking agent is preferably an organic polyvalent isocyanate compound, and consists of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in all or part of the hydroxyl groups of a polyol such as trimethylolpropane.
  • a compound to which one or more selected from the group is added is more preferred, and a tolylene diisocyanate adduct of trimethylolpropane is even more preferred.
  • thermoplastic resin When an organic polyvalent isocyanate compound is used as the cross-linking agent, (A) the thermoplastic resin preferably has a hydroxy group. When the (H) cross-linking agent has an isocyanate group and the (A) thermoplastic resin has a hydroxy group, the reaction between the (H) cross-linking agent and the (A) thermoplastic resin results in a cross-linked structure in the film for forming a protective film. can be easily introduced.
  • the content of the (H) cross-linking agent in the protective film-forming resin composition is not particularly limited, but initial adhesion of the protective film-forming film From the viewpoint of improving the force and cohesive force, it is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the (A) thermoplastic resin having a functional group. , more preferably 0.5 to 5 parts by mass.
  • the protective film-forming resin composition may contain (I) a coupling agent.
  • the protective film-forming resin composition contains (I) the coupling agent, the dispersibility of the (C) inorganic filler tends to improve, and the adhesiveness, water resistance, etc. of the protective film tend to improve.
  • Coupling agents may be used alone or in combination of two or more.
  • Coupling agents include, for example, silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred.
  • the (I) coupling agent for example, one having a functional group capable of reacting with (A) a thermoplastic resin or (B) a thermosetting resin having a functional group is preferable.
  • the functional group include glycidyl group, amino group, mercapto group, vinyl group, (meth)acryloyl group, hydroxy group, carboxy group, imidazole group and the like. Among these, those having a glycidyl group are preferable.
  • Coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-amino Ethylamino)propylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
  • the content of (I) the coupling agent in the protective film-forming resin composition is not particularly limited, but (A) the thermoplastic resin And (B) with respect to 100 parts by mass of the total amount of the thermosetting resin, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, still more preferably 0.01 to 0.1 parts by mass is.
  • the content of (I) the coupling agent is at least the above lower limit, the dispersibility of the (C) inorganic filler, the adhesiveness of the protective film, the water resistance, etc. tend to be better.
  • the content of (I) the coupling agent is equal to or less than the above upper limit, outgassing tends to be further suppressed.
  • the protective film-forming resin composition may contain a solvent.
  • a solvent may be used individually by 1 type, and may use 2 or more types together.
  • solvents examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, 2-methylpropan-1-ol and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone.
  • ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone; Among these, toluene, ethyl acetate, and methyl ethyl ketone are preferred.
  • the protective film-forming resin composition may or may not contain components other than the components described above.
  • Other components include, for example, resin components other than the above components, plasticizers, antistatic agents, antioxidants, gettering agents, and the like.
  • resin components other than the above components plasticizers, antistatic agents, antioxidants, gettering agents, and the like.
  • one type may be used alone, or two or more types may be used in combination.
  • the content of other components in the protective film-forming resin composition is not particularly limited, and may be appropriately selected according to the purpose.
  • the protective film-forming resin composition can be produced by blending the constituent components.
  • the order of addition in blending each component is not particularly limited, and two or more components may be added simultaneously or sequentially.
  • any component other than the solvent may be used after being diluted with the solvent, or may be mixed with other components without being diluted with the solvent.
  • the method of mixing each component is not particularly limited, and for example, a method of mixing by rotating a stirrer, a stirring blade, etc.; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves; can be selected as appropriate.
  • the temperature and time for adding and mixing each component are not particularly limited, and may be appropriately adjusted according to the components used.
  • the thickness of the protective film-forming film of the present embodiment is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 3 to 75 ⁇ m, still more preferably 5 to 50 ⁇ m.
  • the thickness of the protective film-forming film is at least the above lower limit, the protective function of the protective film tends to be better.
  • the thickness of the film for forming a protective film is equal to or less than the above upper limit value, the economical efficiency tends to be excellent, and processing such as cutting of the protective film tends to be facilitated.
  • the shape of the protective film-forming film of the present embodiment is not particularly limited, but from the viewpoint of being attached to a circular semiconductor wafer, it may be circular in plan view.
  • the protective film-forming film has a circular shape in plan view, its diameter is, for example, 200 mm (for 8-inch wafer), 300 mm (for 12-inch wafer), and the like.
  • the protective film-forming film of the present embodiment can be attached to an object to be protected by pressing it against the object to be protected.
  • the film for forming a protective film may be heated, if necessary.
  • Examples of objects to be protected to which the protective film forming film of the present embodiment is attached include semiconductor wafers and semiconductor chips.
  • a protective film-forming film is attached to a semiconductor wafer, for example, a semiconductor wafer with a protective film is formed by applying and curing the protective film-forming film to the back surface of the semiconductor wafer, and then the semiconductor wafer with a protective film is attached. By singulating, a semiconductor chip with a protective film having a protective film on the back surface can be obtained.
  • Examples of semiconductor wafers include silicon wafers; wafers of gallium arsenide, silicon carbide, sapphire, lithium tantalate, lithium niobate, gallium nitride, indium phosphide, etc.; glass wafers; Examples of semiconductor chips include those obtained by singulating the above semiconductor wafer.
  • the semiconductor wafer or semiconductor chip to which the film for forming a protective film of the present embodiment is attached is preferably one after back grinding.
  • the thickness of the semiconductor wafer or semiconductor chip after back grinding is not particularly limited, but is preferably 5 to 150 ⁇ m, more preferably 7 to 100 ⁇ m, still more preferably 10 to 45 ⁇ m.
  • the curing conditions after the protective film-forming film is attached to the object to be protected are not particularly limited, and may be appropriately determined according to the type of the protective film-forming film.
  • the heating temperature for thermosetting the protective film-forming film may be, for example, 100 to 200°C, 110 to 180°C, or 120 to 170°C.
  • the heating time for thermosetting the protective film-forming film may be, for example, 0.5 to 5 hours, 0.7 to 4 hours, or 1 to 3 hours. good too.
  • the illuminance of the ultraviolet rays may be, for example, 30 to 500 mW/cm 2 , and 40 to 420 mW/cm 2 . or 50 to 340 mW/cm 2 .
  • the amount of ultraviolet light may be, for example, 100 to 2,000 mJ/cm 2 , 125 to 1,000 mJ/cm 2 , or 150 to 500 mJ/cm 2 .
  • the timing of attaching the protective film-forming film of the present embodiment to an object to be protected and the timing of curing are not particularly limited, and may be appropriately determined according to the process for applying the protective film-forming film of the present embodiment. For example, in the process of manufacturing semiconductor chips by grinding the backside of a semiconductor wafer and then singulating it, any process from grinding the backside of the semiconductor wafer to mounting the singulated semiconductor chips on a substrate may be performed. At this time, the film for forming a protective film may be attached to a semiconductor wafer or a semiconductor chip and cured to form a protective film.
  • a film for forming a protective film is attached to the back surface of the semiconductor wafer, Preferably, a semiconductor wafer with a protective film is formed by curing.
  • Known singulation methods such as a blade dicing method, a laser dicing method, and a stealth dicing (registered trademark) method can be applied as a method for singulating the semiconductor wafer with a protective film.
  • a semiconductor chip with a protective film is obtained by singulating the semiconductor wafer with a protective film.
  • the protective film-forming film can be produced, for example, by forming a protective film-forming resin composition into a film. Specifically, for example, the protective film-forming resin composition is applied onto a support sheet such as a release film, and dried as necessary to form a protective film-forming film on the support sheet. can be done.
  • the protective film-forming composite sheet of the first aspect of the present embodiment has a structure in which the protective film-forming film of the present embodiment is sandwiched between two release films.
  • peeling film means a film having a function to be peeled off, and in order to protect the film for forming a protective film before being attached to an object to be protected, it is attached to the surface of the film for forming a protective film. It can be attached.
  • Preferred aspects of the protective film-forming film included in the protective film-forming composite sheet of the first aspect are as described above.
  • FIG. 1 is a cross-sectional view schematically showing an example of the protective film-forming composite sheet of the first embodiment. It should be noted that the drawings used in the following description may show the essential parts in an enlarged manner for convenience, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as the actual ones.
  • the protective film-forming composite sheet 1 shown in FIG. 1 has a first release film 111 on one surface 10a of the protective film-forming film 10 and a second release film 112 on the other surface 10b.
  • a composite sheet for forming a protective film having such a structure is suitable for storage as a roll, for example.
  • the first release film 111 and the second release film 112 may be the same or different.
  • the first peeling film 111 and the second peeling film 112 may have different peeling forces required when peeling them from the protective film forming film 10 .
  • release film examples include a release film base material coated with a release agent.
  • Base materials for release films include, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylate copolymer film, polystyrene film, polycarbonate film, transparent films such as polyimide films and fluororesin films; crosslinked films thereof; films obtained by coloring these films; opaque films; These may be used as a single layer or as a laminate of two or more layers.
  • release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins; long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins;
  • the release agent may be used alone or in combination of two or more.
  • the thickness of the release film is not particularly limited, it is preferably 10 to 500 ⁇ m, more preferably 15 to 300 ⁇ m, still more preferably 20 to 100 ⁇ m.
  • the thickness of the release film is at least the above lower limit, the deformation resistance of the protective film-forming composite sheet tends to be better.
  • the thickness of the release film is equal to or less than the above upper limit value, appropriate flexibility is obtained, and the handleability of the protective film-forming composite sheet tends to be better.
  • the protective film-forming composite sheet of the first aspect can be produced according to the above-described [Production method of protective film-forming film]. Specifically, for example, the object to be coated with the protective film-forming resin composition is the release-treated surface of the release film, and after forming the protective film-forming film on the release film, the protective film-forming film is applied. By attaching the release-treated surface of another release film to the exposed surface, the protective film-forming composite sheet of the first aspect can be produced.
  • the protective film-forming composite sheet of the second aspect of the present embodiment is a protective film-forming composite sheet having a substrate, an adhesive layer, and the protective film-forming film of the present embodiment in this order.
  • Preferred aspects of the protective film-forming film included in the protective film-forming composite sheet of the second embodiment are as described above.
  • the protective film-forming composite sheet of the second aspect has a substrate and an adhesive layer in addition to the protective film-forming film. Therefore, for example, when the film for forming a protective film of the composite sheet for forming a protective film of the second embodiment is adhered to a semiconductor wafer and cured to form a protective film, the protective film is supported by the substrate via the pressure-sensitive adhesive layer. A semiconductor wafer is obtained. A semiconductor wafer with a protective film supported by a substrate via an adhesive layer can be singulated by fixing the surface on the substrate side, for example. That is, the protective film-forming composite sheet of the second aspect can be used as one in which a protective film-forming film and a dicing sheet having a substrate and an adhesive layer are integrated.
  • the protective film-forming composite sheet of the second aspect may consist of only the base material, the adhesive layer and the protective film-forming film, but other than the base material, the pressure-sensitive adhesive layer and the protective film-forming film You may have a component of.
  • Other constituent members include, for example, a release film laminated on the surface of the protective film-forming film opposite to the pressure-sensitive adhesive layer. Preferred aspects of the release film that the protective film-forming composite sheet of the second aspect may have are as described above.
  • FIGS. 2 and 3 are cross-sectional views schematically showing examples of the protective film-forming composite sheet of the second embodiment.
  • the same constituent elements as those shown in already explained figures are denoted by the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.
  • a release film 11 is further laminated on the surface 10a (upper surface) of the protective film-forming film 10 and the surface 13a (upper surface) of the pressure-sensitive adhesive layer 13 .
  • the back surface of a semiconductor wafer (not shown) is attached to a central part of the front surface 10a of the protective film-forming film 10 with the release film 11 removed.
  • the area near the peripheral edge of the protective film forming film 10 is used by being attached to a jig such as a ring frame.
  • the jig adhesive layer 14 may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may be structural.
  • the back surface of a semiconductor wafer (not shown) is adhered to the front surface 10a of the protective film forming film 10 in a state in which the release film 11 is removed, and an adhesive layer 14 for a jig is attached.
  • the upper surface of the surface 14a of is attached to a jig such as a ring frame for use.
  • the protective film-forming composite sheet of the second aspect of the present embodiment is not limited to those shown in FIGS.
  • the configuration of the parts may be changed or deleted, or other configurations may be added to those described above.
  • Examples of constituent materials of the base material include various resins.
  • Examples of the resin constituting the base material include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin, and the like.
  • Polyolefins other than polyethylene Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (Copolymer obtained using ethylene as a monomer); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (Resins obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylic ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluor
  • the substrate contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). good too.
  • the base material may be subjected to a surface treatment in order to improve adhesion with other layers such as an adhesive layer.
  • surface treatment methods include sandblasting, unevenness treatment by solvent treatment, etc.; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and other oxidation. treatment; primer treatment; and the like.
  • those subjected to electron beam irradiation treatment are preferable from the viewpoint of suppressing the generation of fragments of the base material due to blade friction when the composite sheet for forming a protective film is applied to blade dicing.
  • the substrate may be composed of only one layer, or may be composed of multiple layers of two or more layers. When the substrate is composed of multiple layers, each layer constituting the multiple layers may be the same as or different from each other. Furthermore, the base material prevents the base material from adhering to other sheets and the base material from adhering to the adsorption table when the antistatic coating layer and the composite sheet for forming a protective film are stacked and stored, for example. It may have a layer or the like for doing.
  • the thickness of the substrate is not particularly limited, it is preferably 40 to 300 ⁇ m, more preferably 50 to 200 ⁇ m, still more preferably 60 to 150 ⁇ m. When the thickness of the substrate is within the above range, the composite sheet for protective film formation tends to have better flexibility and sticking properties.
  • the adhesive layer is a layer having adhesiveness provided between the substrate and the film for forming a protective film.
  • the pressure-sensitive adhesive layer may consist of only one layer, or may consist of multiple layers of two or more layers. When the pressure-sensitive adhesive layer consists of multiple layers, each layer constituting the multiple layers may be the same or different.
  • adhesive resins constituting the adhesive layer include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether resins, polycarbonate resins, and ester resins.
  • adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether resins, polycarbonate resins, and ester resins.
  • acrylic resins are preferable from the viewpoint of exhibiting excellent adhesive strength.
  • the "adhesive resin” is a concept that includes both a resin having adhesiveness and a resin having adhesiveness. , resins that exhibit adhesiveness when used in combination with other components such as additives; resins that exhibit adhesiveness in the presence of triggers such as heat and water; and the like.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is preferably 3 to 30 ⁇ m, more preferably 4 to 20 ⁇ m, still more preferably 5 to 17 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is at least the above lower limit, the tack and adhesive strength tend to be better.
  • the thickness of the pressure-sensitive adhesive layer is equal to or less than the above upper limit, there is a tendency that blade dicing aptitude and pick-up aptitude when applying the composite sheet for forming a protective film to blade dicing become better.
  • the adhesive layer may be formed using an energy ray-curable adhesive or may be formed using a non-energy ray-curable adhesive.
  • the non-energy ray-curable adhesive includes thermosetting adhesives and non-curable adhesives.
  • the protective film-forming composite sheet of the second aspect can be produced by sequentially laminating each layer constituting the protective film-forming composite sheet so as to have a corresponding positional relationship. Each layer can be formed in conformity with the above-described [Production method of film for forming protective film].
  • a protective film-forming resin composition may be applied to the surface of the pressure-sensitive adhesive layer laminated on the substrate to form a protective film-forming film on the pressure-sensitive adhesive layer, A film for forming a protective film is formed in advance on the release-treated surface of the release film, and the exposed surface of the film for forming a protective film is attached to the surface of the adhesive layer laminated on the substrate to form a protective film.
  • a film may be laminated onto the adhesive layer.
  • the composition may be applied to the surface of the substrate to form the adhesive layer, or the adhesive layer formed on the release-treated surface of the release film. The release film may be removed after the exposed surface of is attached to the surface of the substrate.
  • the protective film-forming composite sheet of the second embodiment has arbitrary layers such as an intermediate layer, the arbitrary layers may be provided at required positions according to the above method.
  • the protective film-attached semiconductor chip of the present embodiment is a protective film-attached semiconductor chip having a protective film that is a cured product of the protective film-forming film of the present embodiment.
  • the protective film-forming film used for forming the protective film of the semiconductor chip with a protective film according to the present embodiment, the protective film formed from the protective film-forming film, and the preferred aspects of the semiconductor chip are described above.
  • the size of the semiconductor chip in plan view is not particularly limited, it is preferably less than 600 mm 2 , more preferably less than 400 mm 2 , and still more preferably less than 300 mm 2 .
  • planar view means viewing in a thickness direction.
  • the shape of the semiconductor chip in plan view may be a square or an elongated shape such as a rectangle.
  • the semiconductor chip with a protective film of this embodiment can be manufactured by the method described in the method of using the film for forming a protective film of this embodiment.
  • the semiconductor device of this embodiment is a semiconductor device having the semiconductor chip with the protective film of this embodiment.
  • Examples of the semiconductor device of this embodiment include a semiconductor package formed by flip-chip connecting the semiconductor chip with a protective film of this embodiment to a substrate having a circuit.
  • the release sheet was peeled off from the film for forming a protective film with a double-sided release film obtained in each example, and a plurality of films for forming a protective film were laminated so as to have a thickness of 200 ⁇ m.
  • a rectangle (thickness: 200 ⁇ m) of 30 mm ⁇ 4 mm in plan view was cut from the laminate of the protective film-forming film thus obtained, and this was used as a measurement sample for the storage elastic modulus E′.
  • a dynamic viscoelasticity measurement device manufactured by Orientec Co., Ltd., trade name "Rheovibron DDV-II-EP1" was used, measurement mode: tensile mode, frequency: 11 Hz, measurement temperature range:
  • the storage elastic modulus E' was measured under conditions of -20 to 150°C and a heating rate of 3°C/min.
  • the sample was fixed by fixing jigs up to 5 mm from both ends of the long side, and the measurement was performed with a distance between the fixing jigs of 20 mm.
  • Table 1 shows the ratio [E'(80)/E'(130)] of the storage modulus E'(80) at 80.degree. C. and the storage modulus E'(130) at 130.degree.
  • Table 1 shows the ratio [E'(80)/E'(130)] of the storage modulus E'(80) at 80.degree. C. and the storage modulus E'(130) at 130.degree.
  • the light release film was peeled off from the protective film forming film with a double-sided release film obtained in each example, and the exposed surface of the protective film forming film was treated with a piece of silicon wafer (thickness 350 ⁇ m having a No. 2,000 polished surface). (silicon wafer) using a roll laminator heated to 70°C.
  • the heavy release film was peeled off from the surface of the attached protective film forming film opposite to the silicon wafer, and a film of 50 mm long side ⁇ 10 mm short side ⁇ 150 ⁇ m thick was applied to the exposed surface of the film for forming a surface protective film. was applied using a roll laminator heated to 70°C.
  • the film for forming a protective film is thermally cured by heating at 140° C. for 2 hours, and a silicon wafer, a protective film which is a cured product of the film for forming a protective film, and a copper foil are laminated in their thickness direction. A laminated body was formed, and this was used as a measurement sample for the copper foil peel strength.
  • the measurement sample obtained above is attached to a universal tensile tester (manufactured by Shimadzu Corporation, trade name "AG-XPlus”), the unattached portion of the copper foil is gripped with a grip, and the copper foil is The peel strength of the copper foil was obtained by peeling it off in the 90° direction at a peeling speed of 50 mm/min.
  • a universal tensile tester manufactured by Shimadzu Corporation, trade name "AG-XPlus
  • the film for forming a protective film with a double-sided release film obtained in each example is heated at 140° C. for 2 hours to thermally cure the film for forming a protective film to form a protective film that is a cured product of the film for forming a protective film. Then, it was cut into a size of 200 mm long side ⁇ 50 mm short side, and the release films on both sides of the protective film were peeled off. The resulting protective film was stored for 48 hours in an environment of a temperature of 23° C. and a relative humidity of 50%.
  • a marked line was provided at a position of 125 mm, and a portion (75 mm portion) between one end and the marked line was taped to prepare a cylindrical protective film, after which the bar was pulled out. Next, the cylindrical protective film is placed with the taped end facing upward, and the end is crushed and closed flat so that air does not escape from the upper end.
  • the protective film obtained above is formed on the release-treated surface of a heavy release film (manufactured by Lintec Corporation, trade name "SP-PET502150", a polyethylene terephthalate film having a thickness of 50 ⁇ m and one side of which is release-treated with a silicone resin). was applied using a knife coater and dried at 100° C. for 2 minutes to form a 25 ⁇ m-thick protective film-forming film on the heavy release film.
  • a heavy release film manufactured by Lintec Corporation, trade name "SP-PET502150"
  • SP-PET502150 a polyethylene terephthalate film having a thickness of 50 ⁇ m and one side of which is release-treated with a silicone resin
  • the release-treated surface of a light release film (manufactured by Lintec Co., Ltd., trade name "SP-PET381130", a polyethylene terephthalate film with a thickness of 38 ⁇ m and one side of which is release-treated with a silicone resin) is attached to the protective film-forming film.
  • a film for forming a protective film with a double-sided release film having a configuration in which the film for forming a protective film was sandwiched between two release films was produced by laminating them together.
  • the protective film-forming film obtained in each example was evaluated by the methods described above. Table 1 shows the results.
  • B)-1 Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name “Epiclon HP-7200HH”, epoxy equivalent 255 to 260 g/eq)
  • B)-2 Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “jER1055”, epoxy equivalent 800 to 900 g/eq)
  • B)-3 Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “jER828”, epoxy equivalent 184 to 194 g/eq)
  • Reference Signs List 1 1A, 1B protective film-forming composite sheet 10 protective film-forming film 10a, 10b release film side surface of protective film-forming film 11 release film, REFERENCE SIGNS LIST 111 First release film 112 Second release film 12 Base material 13 Adhesive layer 13a Protective film forming film side surface of adhesive layer 14 Jig adhesive layer 14a Peeling film side surface of jig adhesive layer

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Abstract

The present invention relates to: a curable film for forming a protective coating, wherein the storage modulus E' at all temperatures in the temperature range of 23-150°C is 1 MPa or more, the ratio [E'(80)/E'(130)] of the storage modulus E'(80) at 80°C and the storage modulus E'(130) at 130°C is 1.25 or more, the copper-foil peel strength of a cured product of said film for forming a protective coating is 3.0 N/10 mm or more, and requirement (1) is satisfied; a composite sheet for forming a protective coating using said film for forming a protective coating; a protective coating-equipped semiconductor chip; and a semiconductor device.

Description

保護膜形成用フィルム、保護膜形成用複合シート、保護膜付き半導体チップ及び半導体装置Films for forming protective films, composite sheets for forming protective films, semiconductor chips and semiconductor devices with protective films
　本発明は、保護膜形成用フィルム、保護膜形成用複合シート、保護膜付き半導体チップ及び半導体装置に関する。 The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, a semiconductor chip with a protective film, and a semiconductor device.
　近年、回路面を基板側に向けた状態で半導体チップを基板上に実装する、いわゆるフェースダウン（ｆａｃｅ　ｄｏｗｎ）方式と呼ばれる実装法を適用し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、半導体チップの回路面に形成されたバンプ等の電極を基板と接合するため、半導体チップの回路面とは反対側の裏面が剥き出しの状態にならないように、半導体チップの裏面に保護膜が形成されることがある。
　保護膜は、半導体チップの製造過程及び半導体チップの実装後に、外部衝撃等から半導体チップを保護する役割を担う。また、保護膜は、レーザー印字による半導体チップの識別、装飾等に利用可能である。さらに、保護膜は、回路の誤動作を防止する遮光層としても機能し得る。 2. Description of the Related Art In recent years, semiconductor devices have been manufactured using a so-called face down mounting method in which a semiconductor chip is mounted on a substrate with the circuit surface facing the substrate.
In the face-down method, electrodes such as bumps formed on the circuit surface of the semiconductor chip are joined to the substrate. A protective film may be formed on the
The protective film plays a role of protecting the semiconductor chip from external impacts and the like during the manufacturing process of the semiconductor chip and after the semiconductor chip is mounted. In addition, the protective film can be used for identification, decoration, etc. of semiconductor chips by laser printing. Furthermore, the protective film can also function as a light shielding layer that prevents malfunction of the circuit.
　保護膜は、例えば、保護膜形成用フィルムを用いて形成される。保護膜形成用フィルムとしては、機械強度、耐熱性等の観点から、熱硬化性又はエネルギー線硬化性を有する樹脂組成物からなる硬化性のフィルムが使用されている。硬化性の保護膜形成用フィルムは、半導体ウエハ、半導体チップ等の保護対象物に貼付された後、硬化されることによって、その硬化物からなる保護膜が形成されている。
　例えば、特許文献１には、硬化後の鉛筆硬度が５Ｈ以上である硬化性保護膜形成層を有することを特徴とするチップ保護用フィルムが開示されている。 A protective film is formed using the film for protective film formation, for example. As the protective film-forming film, a curable film made of a thermosetting or energy ray-curable resin composition is used from the viewpoint of mechanical strength, heat resistance, and the like. A curable film for forming a protective film is applied to an object to be protected, such as a semiconductor wafer or a semiconductor chip, and then cured to form a protective film made of the cured product.
For example, Patent Document 1 discloses a chip protection film characterized by having a curable protective film-forming layer having a pencil hardness of 5H or more after curing.
特開２００９－１４７２７７号公報JP 2009-147277 A
　ところで、近年、安全性向上の観点から、電子部品に対する難燃性の要求レベルが高まっている。プラスチック製品の難燃性を向上させるための難燃剤としては、従来からハロゲン系難燃剤が使用されてきたが、ハロゲン系難燃剤は焼却時に有毒な物質を排出する疑いが持たれ、使用を控える動きが進んでいる。
　しかしながら、本発明者等の検討によると、ハロゲン系難燃剤の代替難燃剤を用いて保護膜形成用フィルムの難燃化を図ると、保護膜形成用フィルムから形成される保護膜の難燃性と接着性とを両立させることが困難になることが判明している。 By the way, in recent years, from the viewpoint of improving safety, the level of flame retardancy required for electronic components is increasing. Halogen-based flame retardants have long been used as flame retardants to improve the flame resistance of plastic products. movement is underway.
However, according to the study of the present inventors, if the flame retardant of the film for forming a protective film is made using a flame retardant alternative to a halogen-based flame retardant, the flame retardancy of the protective film formed from the film for forming a protective film It has been found that it becomes difficult to achieve both adhesion and adhesion.
　本発明は、上記問題点に鑑みてなされたものであって、難燃性と接着性とを両立する保護膜を形成できる保護膜形成用フィルム、該保護膜形成用フィルムを用いた保護膜形成用複合シート、保護膜付き半導体チップ及び半導体装置を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a film for forming a protective film capable of forming a protective film having both flame retardancy and adhesiveness, and a film for forming a protective film using the film for forming a protective film. An object of the present invention is to provide a composite sheet for semiconductor devices, a semiconductor chip with a protective film, and a semiconductor device.
　本発明者等は、保護膜形成用フィルムの貯蔵弾性率Ｅ’、保護膜形成用フィルムの硬化物の銅箔ピール強度及び難燃性に着目し、本発明を完成するに至った。
　すなわち、本発明は、下記［１］～［１４］に関する。
［１］硬化性を有する保護膜形成用フィルムであり、
　２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が１．０ＭＰａ以上、かつ、８０℃における貯蔵弾性率Ｅ’（８０）と１３０℃における貯蔵弾性率Ｅ’（１３０）との比［Ｅ’（８０）／Ｅ’（１３０）］が１．２５以上であり、
　前記保護膜形成用フィルムの硬化物の銅箔ピール強度が３．０Ｎ／１０ｍｍ以上であり、
　下記の要件（１）を満たす、保護膜形成用フィルム。
要件（１）：保護膜形成用フィルムを硬化させて得られた保護膜を、長辺２００ｍｍ×短辺５０ｍｍの大きさに裁断し、温度２３℃、相対湿度５０％の環境下で４８時間保管した後、短辺方向を直径１２．７ｍｍの円筒状の棒に巻き、長辺方向の一方の端部から１２５ｍｍの位置に標線を設け、もう一方の端部と前記標線との間の部分（７５ｍｍの部分）をテープで留めて円筒状の保護膜を作製した後、前記棒を引き抜く。該円筒状の保護膜を、前記テープで留めた側の端部を上側にして、該上側の端部から空気が抜けないように該端部を閉じた状態でクランプに垂直に取付け、米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）のＵＬ９４ＶＴＭ試験（薄手材料垂直燃焼試験）に準拠して、前記円筒状の保護膜の下端から１０ｍｍの位置にバーナーの筒を設置し、前記円筒状の保護膜の下端の中央において２０ｍｍの青色炎による３秒間の１回目の接炎試験を行い、炎が消えた場合は同じ条件で２回目の接炎試験を行い、１回目及び２回目の接炎試験において炎が前記標線を超えない。
［２］前記２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が、１００ＭＰａ以下である、上記［１］に記載の保護膜形成用フィルム。
［３］前記２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値を示す温度が、９０～１４８℃である、上記［１］又［２］に記載の保護膜形成用フィルム。
［４］前記貯蔵弾性率Ｅ’の比［Ｅ’（８０）／Ｅ’（１３０）］が、３．００以下である、上記［１］～［３］のいずれかに記載の保護膜形成用フィルム。
［５］前記保護膜形成用フィルムが熱硬化性を有する、上記［１］～［４］のいずれかに記載の保護膜形成用フィルム。
［６］前記保護膜形成用フィルムが、（Ａ）熱可塑性樹脂と、（Ｂ）熱硬化性樹脂と、を含有する樹脂組成物を用いて形成された、上記［１］～［５］のいずれかに記載の保護膜形成用フィルム。
［７］前記（Ａ）熱可塑性樹脂が、アクリル樹脂である、上記［６］に記載の保護膜形成用フィルム。
［８］前記（Ｂ）熱硬化性樹脂が、エポキシ樹脂である、上記［６］又は［７］に記載の保護膜形成用フィルム。
［９］厚さが、１～１００μｍである、上記［１］～［８］のいずれかに記載の保護膜形成用フィルム。
［１０］半導体ウエハの裏面に貼付され、保護膜付き半導体チップの製造に用いられる、上記［１］～［９］のいずれかに記載の保護膜形成用フィルム。
［１１］上記［１］～［１０］のいずれかに記載の保護膜形成用フィルムが、２枚の剥離フィルムに挟持された構成を有する、保護膜形成用複合シート。
［１２］基材と、粘着剤層と、上記［１］～［１０］のいずれかに記載の保護膜形成用フィルムと、をこの順で有する、保護膜形成用複合シート。
［１３］上記［１］～［１０］のいずれかに記載の保護膜形成用フィルムの硬化物である保護膜を有する、保護膜付き半導体チップ。
［１４］上記［１３］に記載の保護膜付き半導体チップを有する、半導体装置。 The present inventors focused on the storage elastic modulus E' of the protective film-forming film, and the copper foil peel strength and flame retardancy of the cured product of the protective film-forming film, and have completed the present invention.
That is, the present invention relates to the following [1] to [14].
[1] A curable film for forming a protective film,
The minimum value of the storage elastic modulus E′ in the temperature range of 23 to 150° C. is 1.0 MPa or more, and the ratio of the storage elastic modulus E′ (80) at 80° C. to the storage elastic modulus E′ (130) at 130° C. [E'(80)/E'(130)] is 1.25 or more,
The cured product of the protective film-forming film has a copper foil peel strength of 3.0 N/10 mm or more,
A protective film-forming film that satisfies the following requirement (1).
Requirement (1): Cut the protective film obtained by curing the protective film-forming film into a size of 200 mm long side × 50 mm short side, and store it for 48 hours in an environment with a temperature of 23 ° C. and a relative humidity of 50%. After that, the short side direction is wound around a cylindrical rod with a diameter of 12.7 mm, a marked line is provided at a position 125 mm from one end in the long side direction, and the other end and the marked line After a section (75 mm section) is taped to create a cylindrical protective membrane, the bar is withdrawn. Mount the cylindrical protective membrane vertically on the clamp with the taped end up and the end closed to prevent air from escaping from the upper end; In accordance with the UL94 VTM test (thin material vertical burning test) of the UL94 test (combustion test of plastic materials for parts of equipment) specified by Writers Laboratories (UL), 10 mm from the lower end of the cylindrical protective film A burner cylinder is installed at the position, and the first flame contact test is performed for 3 seconds with a 20 mm blue flame at the center of the lower end of the cylindrical protective film. A flame test is performed and the flame does not exceed the above marked line in the first and second flame contact tests.
[2] The film for forming a protective film according to [1] above, wherein the minimum value of the storage elastic modulus E' in the temperature range of 23 to 150°C is 100 MPa or less.
[3] The film for forming a protective film according to [1] or [2] above, wherein the temperature at which the storage elastic modulus E' has a minimum value in the temperature range of 23 to 150°C is 90 to 148°C.
[4] The protective film formation according to any one of the above [1] to [3], wherein the ratio [E'(80)/E'(130)] of the storage elastic modulus E' is 3.00 or less. Film for.
[5] The film for forming a protective film according to any one of the above [1] to [4], wherein the film for forming a protective film has thermosetting properties.
[6] Any of the above [1] to [5], wherein the film for forming a protective film is formed using a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin. A film for forming a protective film according to any one of the above.
[7] The film for forming a protective film according to [6] above, wherein the (A) thermoplastic resin is an acrylic resin.
[8] The film for forming a protective film according to the above [6] or [7], wherein the thermosetting resin (B) is an epoxy resin.
[9] The film for forming a protective film according to any one of [1] to [8], which has a thickness of 1 to 100 μm.
[10] The film for forming a protective film according to any one of the above [1] to [9], which is attached to the back surface of a semiconductor wafer and used for manufacturing a semiconductor chip with a protective film.
[11] A composite sheet for forming a protective film, wherein the film for forming a protective film according to any one of [1] to [10] is sandwiched between two release films.
[12] A protective film-forming composite sheet comprising a substrate, an adhesive layer, and the protective film-forming film according to any one of [1] to [10] in this order.
[13] A semiconductor chip with a protective film, having a protective film that is a cured product of the film for forming a protective film according to any one of [1] to [10] above.
[14] A semiconductor device having the semiconductor chip with a protective film according to [13] above.
　本発明によると、難燃性と接着性とを両立する保護膜を形成できる保護膜形成用フィルム、該保護膜形成用フィルムを用いた保護膜形成用複合シート、保護膜付き半導体チップ及び半導体装置を提供することができる。 According to the present invention, a protective film-forming film capable of forming a protective film having both flame retardancy and adhesiveness, a protective film-forming composite sheet using the protective film-forming film, a semiconductor chip with a protective film, and a semiconductor device can be provided.
本発明の第一態様の保護膜形成用複合シートの構成の一例を示す模式的断面図である。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of the configuration of the protective film-forming composite sheet of the first embodiment of the present invention; 本発明の第二態様の保護膜形成用複合シートの構成の一例を示す模式的断面図である。FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the protective film-forming composite sheet of the second aspect of the present invention. 本発明の第二態様の保護膜形成用複合シートの構成の別の例を示す模式的断面図である。FIG. 4 is a schematic cross-sectional view showing another example of the configuration of the protective film-forming composite sheet of the second aspect of the present invention.
　本明細書において、数平均分子量（Ｍｎ）及び質量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法に基づいて測定した値である。 In the present specification, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are values converted to standard polystyrene measured by gel permeation chromatography (GPC), specifically described in Examples. It is a value measured based on the method.
　本明細書において、好ましい数値範囲（例えば、含有量等の範囲）について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、「好ましくは１０～９０、より好ましくは３０～６０」という記載から、「好ましい下限値（１０）」と「より好ましい上限値（６０）」とを組み合わせて、「１０～６０」とすることもできる。 In this specification, the lower and upper limits described stepwise for preferable numerical ranges (for example, ranges of contents, etc.) can be independently combined. For example, from the statement "preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)" and "more preferred upper limit (60)" to "10 to 60" can also
　本明細書において、「エネルギー線」とは、電磁波又は荷電粒子線の中でエネルギー量子を有するものを意味する。エネルギー線の例としては、紫外線、放射線、電子線等が挙げられる。紫外線は、無電極ランプ、高圧水銀ランプ、メタルハライドランプ、キセノンランプ、ブラックライト、ＬＥＤランプ等を用いて照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。 As used herein, the term "energy ray" means an electromagnetic wave or charged particle beam that has energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be applied using an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a black light, an LED lamp, or the like. The electron beam can be generated by an electron beam accelerator or the like.
　また、本明細書において、「エネルギー線硬化性」とは、エネルギー線を照射することによって硬化する性質を意味し、「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味し、熱硬化性及び非硬化性を包含する。「熱硬化性」とは、加熱することによって硬化する性質を意味し、「非硬化性」とは、加熱又はエネルギー線の照射等によって硬化しない性質を意味する。 Further, in this specification, "energy ray-curable" means the property of curing by irradiation with energy rays, and "non-energy ray-curable" means the property of not curing even when irradiated with energy rays. and includes thermosetting and non-setting. The term "thermosetting" means a property of curing by heating, and the term "non-curing" means a property of not curing by heating, irradiation of energy rays, or the like.
　本明細書において、例えば、「（メタ）アクリル酸」とは、「アクリル酸」と「メタクリル酸」の双方を示し、他の類似用語も同様である。 In this specification, for example, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.
　本明細書において、半導体ウエハ及び半導体チップの「回路面」とは回路が形成されている面を指し、半導体ウエハ及び半導体チップの「裏面」とは回路面とは反対側の面を指す。 In this specification, the "circuit surface" of the semiconductor wafer and semiconductor chip refers to the surface on which the circuit is formed, and the "back surface" of the semiconductor wafer and semiconductor chip refers to the surface opposite to the circuit surface.
　本明細書において、ある対象物の「厚さ」とは、当該対象物全体の厚さを意味し、例えば、当該対象物が複数層からなる場合、当該対象物を構成するすべての層の合計の厚さを意味する。ここでの「対象物」とは、後述する保護膜形成用フィルム、剥離フィルム、基材、粘着剤層等を意味する。
　本明細書における厚さは、実施例に記載の方法に基づいて測定した値である。 As used herein, the “thickness” of an object means the thickness of the entire object. For example, when the object consists of multiple layers, the sum of all layers that make up the object means the thickness of The "object" as used herein means a film for forming a protective film, a release film, a substrate, an adhesive layer, and the like, which will be described later.
The thickness in this specification is a value measured based on the method described in Examples.
　本明細書において、「固形分」とは、対象となる組成物に含まれる成分のうち、水、有機溶媒等の希釈溶媒を除いた成分を指す。 As used herein, the term "solid content" refers to the components contained in the target composition, excluding diluent solvents such as water and organic solvents.
　本明細書に記載されている作用機序は推測であって、本発明の効果を奏する機序を限定するものではない。 The mechanism of action described in this specification is speculation and does not limit the mechanism of the effects of the present invention.
［保護膜形成用フィルム］
　本実施形態の保護膜形成用フィルムは、硬化性を有する保護膜形成用フィルムであり、２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が１．０ＭＰａ以上、かつ、８０℃における貯蔵弾性率Ｅ’（８０）と１３０℃における貯蔵弾性率Ｅ’（１３０）との比［Ｅ’（８０）／Ｅ’（１３０）］が１．２５以上であり、前記保護膜形成用フィルムの硬化物の銅箔ピール強度が３．０Ｎ／１０ｍｍ以上であり、下記の要件（１）を満たす、保護膜形成用フィルムである。
要件（１）：保護膜形成用フィルムを硬化させて得られた保護膜を、長辺２００ｍｍ×短辺５０ｍｍの大きさに裁断し、温度２３℃、相対湿度５０％の環境下で４８時間保管した後、短辺方向を直径１２．７ｍｍの円筒状の棒に巻き、長辺方向の一方の端部から１２５ｍｍの位置に標線を設け、もう一方の端部と標線との間の部分（７５ｍｍの部分）をテープで留めて円筒状の保護膜を作製した後、前記棒を引き抜く。該円筒状の保護膜を、前記テープで留めた側の端部を上側にして、該上側の端部から空気が抜けないように該端部を閉じた状態でクランプに垂直に取付け、米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）のＵＬ９４ＶＴＭ試験（薄手材料垂直燃焼試験）に準拠して、前記円筒状の保護膜の下端から１０ｍｍの位置にバーナーの筒を設置し、前記円筒状の保護膜の下端の中央において２０ｍｍの青色炎による３秒間の１回目の接炎試験を行い、炎が消えた場合は同じ条件で２回目の接炎試験を行い、１回目及び２回目の接炎試験において炎が前記標線を超えない。
　なお、上記要件（１）のより具体的な測定方法の例は、実施例に記載の通りである。 [Film for protective film formation]
The protective film-forming film of the present embodiment is a curable protective film-forming film having a minimum storage elastic modulus E' of 1.0 MPa or more in a temperature range of 23 to 150 ° C., and at 80 ° C. The ratio [E'(80)/E'(130)] of the storage elastic modulus E'(80) and the storage elastic modulus E'(130) at 130°C is 1.25 or more, and the protective film-forming film A film for forming a protective film, which has a copper foil peel strength of 3.0 N/10 mm or more and satisfies the following requirement (1).
Requirement (1): Cut the protective film obtained by curing the protective film-forming film into a size of 200 mm long side × 50 mm short side, and store it for 48 hours in an environment with a temperature of 23 ° C. and a relative humidity of 50%. After that, the short side direction is wound around a cylindrical rod with a diameter of 12.7 mm, a marked line is provided at a position 125 mm from one end in the long side direction, and the other end and the part between the marked line After taping (at 75 mm) to create a cylindrical protective membrane, the bar is withdrawn. Mount the cylindrical protective membrane vertically on the clamp with the taped end up and the end closed to prevent air from escaping from the upper end; In accordance with the UL94 VTM test (thin material vertical burning test) of the UL94 test (combustion test of plastic materials for parts of equipment) specified by Writers Laboratories (UL), 10 mm from the lower end of the cylindrical protective film A burner cylinder is installed at the position, and the first flame contact test is performed for 3 seconds with a 20 mm blue flame at the center of the lower end of the cylindrical protective film. A flame test is performed and the flame does not exceed the above marked line in the first and second flame contact tests.
In addition, examples of more specific measurement methods for the requirement (1) are as described in Examples.
　本実施形態の保護膜形成用フィルムは、硬化性を有するものであり、熱硬化性又はエネルギー線硬化性を有するものが好ましく、熱硬化性を有するものがより好ましい。ここで、本明細書において、「保護膜形成用フィルム」とは硬化前のものを意味し、「保護膜」とは、保護膜形成用フィルムを硬化させた後のものを意味する。 The protective film-forming film of the present embodiment is curable, preferably thermosetting or energy ray curable, and more preferably thermosetting. Here, in this specification, the "protective film-forming film" means a film before curing, and the "protective film" means a film after curing the protective film-forming film.
　なお、上記銅箔ピール強度の測定対象である保護膜形成用フィルムの硬化物を形成する際の保護膜形成用フィルムの硬化条件及び上記要件（１）の試験対象である保護膜を形成する際の保護膜形成用フィルムの硬化条件は、保護膜形成用フィルム中の硬化性成分の反応が実質的に終了し得る条件とすればよく、保護膜形成用フィルムの種類に応じて、例えば、後述する＜保護膜形成用フィルムの硬化条件＞に記載の条件、或いは、実施例に記載の条件等を採用すればよい。 The curing conditions of the protective film-forming film when forming a cured product of the protective film-forming film, which is the object of measuring the copper foil peel strength, and when forming the protective film which is the test object of the above requirement (1) The curing conditions for the protective film-forming film in (1) may be conditions under which the reaction of the curable components in the protective film-forming film can be substantially completed. The conditions described in <Curing Conditions for Protective Film-Forming Film> or the conditions described in Examples may be employed.
　本実施形態の保護膜形成用フィルムは、半導体ウエハ、半導体チップ等の保護対象物に貼付され、その後、硬化されることによって、保護対象物を外部衝撃等から保護する保護膜になる。特に、本実施形態の保護膜形成用フィルムは、半導体ウエハの裏面に貼付され、保護膜付き半導体チップを製造するのに有用である。
　本実施形態の保護膜形成用フィルムから形成される保護膜は、難燃性と接着性とを両立するものであるため、本実施形態の保護膜形成用フィルムから形成される保護膜を設けた保護対象物は安全性に優れると共に、形成された保護膜は保護対象物の保護性に優れる。 The protective film-forming film of the present embodiment is applied to an object to be protected, such as a semiconductor wafer or a semiconductor chip, and then cured to form a protective film that protects the object from external impact or the like. In particular, the protective film-forming film of the present embodiment is attached to the back surface of a semiconductor wafer, and is useful for manufacturing a semiconductor chip with a protective film.
Since the protective film formed from the protective film-forming film of the present embodiment has both flame retardancy and adhesiveness, the protective film formed from the protective film-forming film of the present embodiment was provided. The object to be protected is excellent in safety, and the formed protective film is excellent in protecting the object to be protected.
　本実施形態の保護膜形成用フィルムは、１層のみからなるものであってもよく、２層以上の複数層からなるものであってもよい。本実施形態の保護膜形成用フィルムが複数層からなる場合、複数層を構成する各層は、互いに同一であってもよく、異なっていてもよい。 The protective film-forming film of the present embodiment may consist of only one layer, or may consist of multiple layers of two or more layers. When the protective film-forming film of the present embodiment is composed of multiple layers, the layers constituting the multiple layers may be the same or different.
〔貯蔵弾性率Ｅ’〕
　本実施形態の保護膜形成用フィルムは、２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が１．０ＭＰａ以上、かつ、８０℃における貯蔵弾性率Ｅ’（８０）と１３０℃における貯蔵弾性率Ｅ’（１３０）との比［Ｅ’（８０）／Ｅ’（１３０）］が１．２５以上である。
　貯蔵弾性率Ｅ’の最小値及び比［Ｅ’（８０）／Ｅ’（１３０）］が上記範囲を満たすことによって、本実施形態の保護膜形成用フィルムは良好な剛性を有し、保護膜形成用フィルムとしての取り扱い性に優れると共に、その硬化物である保護膜の機械強度及び接着性が良好になり、保護対象物の保護性が良好になる。
　なお、本実施形態における貯蔵弾性率Ｅ’は、以下の条件によって測定されるものであり、より具体的な測定方法の例は、実施例に記載の通りである。
〔貯蔵弾性率Ｅ’の測定方法〕
　測定装置：動的粘弾性測定装置を用いて、測定モード：引張モード、周波数：１１Ｈｚで、測定温度範囲：－２０～１５０℃、昇温速度：３℃／ｍｉｎの条件で測定する。
　また、貯蔵弾性率Ｅ’（８０）及び貯蔵弾性率Ｅ’（１３０）の値は、以下の方法に従って特定するものとする。
〔貯蔵弾性率Ｅ’（８０）及び貯蔵弾性率Ｅ’（１３０）の特定方法〕
　貯蔵弾性率Ｅ’（８０）については、測定装置の特性上、厳格に８０．０℃丁度における貯蔵弾性率Ｅ’の測定が困難な場合があるため、７９．０～８１．０℃の温度範囲において測定された貯蔵弾性率Ｅ’のうち、最も８０．０℃に近い測定温度において測定された貯蔵弾性率Ｅ’を「８０℃における貯蔵弾性率Ｅ’（８０）」として特定する。すなわち貯蔵弾性率Ｅ’の値が、測定温度７９．１℃、８０．２℃、８１．５℃でプロットされた場合は、８０．２℃における貯蔵弾性率Ｅ’を「８０℃における貯蔵弾性率Ｅ’（８０）」とする。なお、７９．５℃と８０．５℃のように、８０．０℃に最も近い測定温度が２点存在する場合は、その２点の平均値を貯蔵弾性率Ｅ’（８０）として特定する。
　「１３０℃における貯蔵弾性率Ｅ’（１３０）」についても同様に、１２９．０～１３１．０の温度範囲において取得された貯蔵弾性率Ｅ’から、貯蔵弾性率Ｅ’（８０）の場合と同様の方法で、貯蔵弾性率Ｅ’（１３０）の値を特定する。 [Storage elastic modulus E′]
The protective film-forming film of the present embodiment has a storage elastic modulus E' minimum value of 1.0 MPa or more in a temperature range of 23 to 150 ° C., and a storage elastic modulus E' at 80 ° C. (80) and at 130 ° C. The ratio [E'(80)/E'(130)] to the storage modulus E'(130) is 1.25 or more.
By satisfying the above ranges for the minimum value and the ratio [E'(80)/E'(130)] of the storage elastic modulus E', the protective film-forming film of the present embodiment has good rigidity, and the protective film In addition to being excellent in handleability as a forming film, the mechanical strength and adhesiveness of the protective film, which is a cured product thereof, are improved, and the protective property of the object to be protected is improved.
In addition, the storage elastic modulus E' in the present embodiment is measured under the following conditions, and more specific examples of the measuring method are as described in Examples.
[Method for measuring storage elastic modulus E']
Measuring device: Using a dynamic viscoelasticity measuring device, measurement mode: tension mode, frequency: 11 Hz, measurement temperature range: -20 to 150°C, temperature increase rate: 3°C/min.
Moreover, the values of the storage elastic modulus E'(80) and the storage elastic modulus E'(130) shall be specified according to the following method.
[Method for specifying storage elastic modulus E′ (80) and storage elastic modulus E′ (130)]
Regarding the storage modulus E' (80), it may be difficult to strictly measure the storage modulus E' at exactly 80.0 ° C. due to the characteristics of the measuring device. Among the storage elastic moduli E′ measured in the range, the storage elastic modulus E′ measured at the measurement temperature closest to 80.0° C. is specified as “80° C. storage elastic modulus E′ (80)”. That is, when the storage elastic modulus E' values are plotted at the measurement temperatures of 79.1°C, 80.2°C, and 81.5°C, the storage elastic modulus E' at 80.2°C is expressed as "storage elastic modulus at 80°C Let the rate be E'(80)'. When there are two measured temperatures closest to 80.0°C, such as 79.5°C and 80.5°C, the average value of the two points is specified as the storage elastic modulus E'(80). .
Similarly, for "storage elastic modulus E'(130) at 130°C", from the storage elastic modulus E' obtained in the temperature range of 129.0 to 131.0, the storage elastic modulus E'(80) and In a similar manner, the value of storage modulus E'(130) is determined.
　本実施形態の保護膜形成用フィルムの、２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値は、好ましくは１．１ＭＰａ以上であり、また、好ましくは１００ＭＰａ以下、より好ましくは１０ＭＰａ以下、さらに好ましくは５ＭＰａ以下である。
　２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が上記範囲であると、保護膜形成用フィルムの取り扱い性、保護膜の難燃性及び接着性のバランスをより良好にし易い傾向にある。 The minimum value of the storage elastic modulus E′ of the protective film-forming film of the present embodiment in the temperature range of 23 to 150° C. is preferably 1.1 MPa or more, preferably 100 MPa or less, more preferably 10 MPa or less. , and more preferably 5 MPa or less.
When the minimum value of the storage elastic modulus E′ in the temperature range of 23 to 150° C. is within the above range, the handleability of the protective film-forming film and the flame retardancy and adhesiveness of the protective film tend to be well balanced. be.
　上記貯蔵弾性率Ｅ’の比［Ｅ’（８０）／Ｅ’（１３０）］は、好ましくは１．２７以上、より好ましくは１．２９以上であり、また、好ましくは３．００以下、より好ましくは２．５０以下、さらに好ましくは２．２０以下である。
　上記貯蔵弾性率Ｅ’の比［Ｅ’（８０）／Ｅ’（１３０）］が上記範囲であると、保護膜形成用フィルムの取り扱い性、保護膜の難燃性及び接着性のバランスをより良好にし易い傾向にある。 The ratio [E'(80)/E'(130)] of the storage elastic modulus E' is preferably 1.27 or more, more preferably 1.29 or more, and preferably 3.00 or less. It is preferably 2.50 or less, more preferably 2.20 or less.
When the ratio [E'(80)/E'(130)] of the storage elastic modulus E' is within the above range, the balance between the handleability of the protective film-forming film and the flame retardancy and adhesiveness of the protective film is improved. It tends to get better.
　２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値を示す温度は、特に限定されないが、好ましくは９０～１４８℃、より好ましくは９５～１４５℃、さらに好ましくは１００～１４０℃である。
　２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値を示す温度が上記範囲であると、保護膜形成用フィルムの保存安定性と硬化性とのバランスをより良好にし易い傾向にある。 The temperature at which the storage elastic modulus E′ exhibits the minimum value in the temperature range of 23 to 150°C is not particularly limited, but is preferably 90 to 148°C, more preferably 95 to 145°C, and still more preferably 100 to 140°C. .
When the temperature at which the storage elastic modulus E′ reaches the minimum value in the temperature range of 23 to 150° C. is within the above range, the storage stability and curability of the protective film-forming film tend to be well balanced.
〔銅箔ピール強度〕
　本実施形態の保護膜形成用フィルムの硬化物の銅箔ピール強度は、３．０Ｎ／１０ｍｍ以上である。
　なお、本実施形態の銅箔ピール強度は、以下の測定方法によって測定されるものであり、より具体的な測定方法の例は、実施例に記載の通りである。
〔銅箔ピール強度の測定方法〕
　本実施形態の保護膜形成用フィルムの表面に、長辺５０ｍｍ×短辺１０ｍｍ×厚さ１５０μｍの銅箔を、銅箔の長辺の一方の端部１０ｍｍを保護膜形成用フィルムに貼付しない未貼付部として残しながらラミネーターを用いて貼付する。次いで、保護膜形成用フィルムを硬化させ、シリコンウエハ、保護膜形成用フィルムの硬化物である保護膜及び銅箔が、これらの厚さ方向に積層された積層体を形成し、これを銅箔ピール強度の測定試料とする。該測定試料を、引張試験機に取り付け、上記銅箔の未貼付部を掴み具で把持し、該銅箔を、引き剥がし速度５０ｍｍ／分の条件で９０°方向に引き剥がすことによって銅箔ピール強度を取得する。 [Copper foil peel strength]
The copper foil peel strength of the cured product of the protective film forming film of the present embodiment is 3.0 N/10 mm or more.
Incidentally, the copper foil peel strength of the present embodiment is measured by the following measuring method, and more specific examples of the measuring method are as described in Examples.
[Method for measuring peel strength of copper foil]
On the surface of the film for forming a protective film of this embodiment, a copper foil with a long side of 50 mm × a short side of 10 mm × a thickness of 150 μm is applied, and one end of the long side of the copper foil is 10 mm. It is pasted using a laminator while leaving it as a pasting part. Next, the protective film-forming film is cured to form a laminate in which the silicon wafer, the protective film which is a cured product of the protective film-forming film, and the copper foil are laminated in the thickness direction, and the copper foil is formed. Use it as a test sample for peel strength. The measurement sample is attached to a tensile tester, the unattached portion of the copper foil is gripped with a gripper, and the copper foil is peeled off in a 90° direction at a peeling speed of 50 mm / min. Get strength.
　上記と同様の観点から、本実施形態の保護膜形成用フィルムの銅箔ピール強度は、好ましくは４．０Ｎ／１０ｍｍ以上、より好ましくは５．０Ｎ／１０ｍｍ以上、さらに好ましくは６．０Ｎ／１０ｍｍ以上、よりさらに好ましくは７．０Ｎ／１０ｍｍ以上である。
　また、本実施形態の保護膜形成用フィルムの銅箔ピール強度の上限値は、高いほど好ましいが、製造容易性の観点から、２０Ｎ／１０ｍｍ以下であってもよく、１５Ｎ／１０ｍｍ以下であってもよく、１０Ｎ／１０ｍｍ以下であってもよい。 From the same viewpoint as above, the copper foil peel strength of the protective film forming film of the present embodiment is preferably 4.0 N/10 mm or more, more preferably 5.0 N/10 mm or more, and still more preferably 6.0 N/10 mm. More preferably, it is 7.0 N/10 mm or more.
In addition, the upper limit of the copper foil peel strength of the film for forming a protective film of the present embodiment is preferably as high as possible, but from the viewpoint of ease of manufacture, it may be 20 N/10 mm or less, or 15 N/10 mm or less. It may be 10N/10mm or less.
　次に、本実施形態の保護膜形成用フィルムの形成に用いられる材料について説明する。
　本実施形態の保護膜形成用フィルムは、（Ａ）熱可塑性樹脂と、（Ｂ）熱硬化性樹脂と、を含有する樹脂組成物を用いて形成されたものであることが好ましい。
　なお、以下の説明において、本実施形態の保護膜形成用フィルムの形成に用いられる樹脂組成物を「保護膜形成用樹脂組成物」と称する場合がある。 Next, materials used for forming the protective film-forming film of the present embodiment will be described.
The protective film-forming film of the present embodiment is preferably formed using a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin.
In the following description, the resin composition used for forming the protective film-forming film of the present embodiment may be referred to as "protective film-forming resin composition".
〔保護膜形成用樹脂組成物〕
　保護膜形成用樹脂組成物は、（Ａ）熱可塑性樹脂と、（Ｂ）熱硬化性樹脂と、を含有する樹脂組成物である。
　以下、保護膜形成用樹脂組成物が含有する各成分について詳細に説明する。 [Resin composition for forming protective film]
The protective film-forming resin composition is a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin.
Each component contained in the protective film-forming resin composition will be described in detail below.
＜（Ａ）熱可塑性樹脂＞
　保護膜形成用樹脂組成物が（Ａ）熱可塑性樹脂を含有することによって、本実施形態の保護膜形成用フィルムは硬化前の柔軟性、保護対象物への接着性に優れるものになる。
　（Ａ）熱可塑性樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(A) Thermoplastic resin>
By including (A) the thermoplastic resin in the protective film-forming resin composition, the protective film-forming film of the present embodiment is excellent in flexibility before curing and adhesion to an object to be protected.
(A) The thermoplastic resin may be used alone or in combination of two or more.
　（Ａ）熱可塑性樹脂としては、例えば、アクリル樹脂、ウレタン樹脂、フェノキシ樹脂、シリコーン樹脂、飽和ポリエステル樹脂、ポリブテン樹脂、ポリブタジエン樹脂、ポリスチレン樹脂等が挙げられる。これらの中でも、アクリル樹脂が好ましい。 (A) Thermoplastic resins include, for example, acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, polybutene resins, polybutadiene resins, and polystyrene resins. Among these, acrylic resins are preferred.
　アクリル樹脂の原料モノマーは、（メタ）アクリル酸エステルを含有することが好ましい。
　アクリル樹脂の原料モノマーは、１種を単独で用いてもよく、２種以上を併用してもよい。 The raw material monomer of the acrylic resin preferably contains a (meth)acrylic acid ester.
The raw material monomers for the acrylic resin may be used singly or in combination of two or more.
　（メタ）アクリル酸エステルとしては、例えば、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、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（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、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（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）アクリレート等のシクロアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート等のアラルキル（メタ）アクリレート；ジシクロペンテニル（メタ）アクリレート等のシクロアルケニル（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）アクリレート等のシクロアルケニルオキシアルキル（メタ）アクリレート；イミド（メタ）アクリレート；グリシジル（メタ）アクリレート等のグリシジル基含有（メタ）アクリレート；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、３－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、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリレート；Ｎ－メチルアミノエチル（メタ）アクリレート等の置換アミノ基含有（メタ）アクリレート；等が挙げられる。 Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate ) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl Cycloalkyl (meth)acrylates such as (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Dicyclopentenyloxyethyl (meth) cycloalkenyloxyalkyl (meth)acrylates such as acrylate; imide (meth)acrylate; glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2 -Hydroxy group-containing (meth)acrylate such as hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. ) acrylates; substituted amino group-containing (meth)acrylates such as N-methylaminoethyl (meth)acrylate;
　これらの中でも、アクリル樹脂の原料モノマーは、アルキル（メタ）アクリレートを含有することが好ましい。
　アルキル（メタ）アクリレートのアルキルエステルを構成するアルキル基の炭素数は、特に限定されないが、好ましくは１～１８、より好ましくは１～１０、さらに好ましくは１～４である。
　アルキル（メタ）アクリレートのアルキルエステルを構成するアルキル基は、遊離原子価を有する炭素位置によって、ｎ－、ｓｅｃ－、ｔｅｒｔ－又はｉｓｏ－の形態を取り得る場合は、いずれの形態であってもよい。
　アクリル樹脂の原料モノマー中におけるアルキル（メタ）アクリレートの含有量は、特に限定されないが、アクリル樹脂の原料モノマー（１００質量％）に対して、好ましくは５０～９７質量％、より好ましくは６０～９３質量％、さらに好ましくは７０～９０質量％である。 Among these, it is preferable that the raw material monomer of the acrylic resin contains an alkyl (meth)acrylate.
The number of carbon atoms in the alkyl group constituting the alkyl (meth)acrylate alkyl ester is not particularly limited, but is preferably 1-18, more preferably 1-10, and still more preferably 1-4.
If the alkyl group constituting the alkyl ester of alkyl (meth)acrylate can take n-, sec-, tert- or iso-form depending on the carbon position having a free valence, it may be in any form. good.
The content of the alkyl (meth)acrylate in the raw material monomer of the acrylic resin is not particularly limited, but is preferably 50 to 97% by mass, more preferably 60 to 93%, based on the raw material monomer (100% by mass) of the acrylic resin. % by mass, more preferably 70 to 90% by mass.
　アクリル樹脂の原料モノマーは、アルキル（メタ）アクリレートと共に、ヒドロキシ基含有（メタ）アクリレートを含有することが好ましい。
　アクリル樹脂の原料モノマーがヒドロキシ基含有（メタ）アクリレートを含有する場合、アクリル樹脂の原料モノマー中におけるヒドロキシ基含有（メタ）アクリレートの含有量は、特に限定されないが、アクリル樹脂の原料モノマー（１００質量％）に対して、好ましくは２～５０質量％、より好ましくは６～４０質量％、さらに好ましくは１０～３０質量％である。 The raw material monomers for the acrylic resin preferably contain a hydroxyl group-containing (meth)acrylate together with the alkyl (meth)acrylate.
When the raw material monomer of the acrylic resin contains a hydroxyl group-containing (meth)acrylate, the content of the hydroxyl group-containing (meth)acrylate in the raw material monomer of the acrylic resin is not particularly limited, but the raw material monomer of the acrylic resin (100 mass %), preferably 2 to 50% by mass, more preferably 6 to 40% by mass, and still more preferably 10 to 30% by mass.
　アクリル樹脂の原料モノマーは、（メタ）アクリル酸エステル以外のモノマーを含有していてもよく、含有していなくてもよい。
　（メタ）アクリル酸エステル以外のモノマーとしては、例えば、（メタ）アクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、アクリロイルモルフォリン、スチレン、アクリルアミド、Ｎ－メチロールアクリルアミド等が挙げられる。 The raw material monomer of the acrylic resin may or may not contain a monomer other than the (meth)acrylic acid ester.
Examples of monomers other than (meth)acrylic acid esters include (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, acryloylmorpholine, styrene, acrylamide, and N-methylolacrylamide.
　（Ａ）熱可塑性樹脂の質量平均分子量（Ｍｗ）は、特に限定されないが、好ましくは１０，０００～２，０００，０００、より好ましくは１００，０００～１，５００，０００、さらに好ましくは１５０，０００～１，０００，０００である。
　（Ａ）熱可塑性樹脂の質量平均分子量（Ｍｗ）が上記下限値以上であると、保護膜形成用フィルムの形状安定性がより良好になる傾向にある。また、（Ａ）熱可塑性樹脂の質量平均分子量（Ｍｗ）が上記上限値以下であると、保護対象物の凹凸面に保護膜形成用フィルムが追従し易くなり、保護対象物と保護膜形成用フィルムとの間でボイド等の発生がより抑制される傾向にある。 (A) The mass average molecular weight (Mw) of the thermoplastic resin is not particularly limited, but is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, still more preferably 150, 000 to 1,000,000.
(A) When the mass average molecular weight (Mw) of the thermoplastic resin is at least the above lower limit, the shape stability of the protective film-forming film tends to be better. In addition, when the mass average molecular weight (Mw) of the thermoplastic resin (A) is equal to or less than the above upper limit, the film for forming a protective film easily follows the uneven surface of the object to be protected, and the object to be protected and the protective film forming There is a tendency that the generation of voids and the like between the film and the film is further suppressed.
　（Ａ）熱可塑性樹脂のガラス転移温度（Ｔｇ）（以下、単に「Ｔｇ」ともいう）は、特に限定されないが、好ましくは－６０～７０℃、より好ましくは－３０～５０℃、さらに好ましくは－１０～２０℃である。
　（Ａ）熱可塑性樹脂のＴｇが上記下限値以上であると、保護膜形成用フィルムの凝集力がより良好になる傾向にある。また、（Ａ）熱可塑性樹脂のＴｇが上記上限値以下であると、保護膜形成用フィルムの柔軟性及び接着性が向上する傾向にある。 (A) The glass transition temperature (Tg) of the thermoplastic resin (hereinafter also simply referred to as “Tg”) is not particularly limited, but is preferably −60 to 70° C., more preferably −30 to 50° C., still more preferably -10 to 20°C.
(A) When the Tg of the thermoplastic resin is at least the above lower limit, the protective film-forming film tends to have better cohesive strength. Further, when the Tg of the thermoplastic resin (A) is equal to or less than the above upper limit, the flexibility and adhesiveness of the protective film-forming film tend to be improved.
　例えば、アクリル樹脂のＴｇは、以下に示すＦｏｘの式を用いて計算から求めることができる。
　１／Ｔｇ＝（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）＋…＋（Ｗｍ／Ｔｇｍ）
（式中、Ｔｇはアクリル樹脂のガラス転移温度であり、Ｔｇ１，Ｔｇ２，…Ｔｇｍはアクリル樹脂の原料となる各単量体のホモポリマーのガラス転移温度であり、Ｗ１、Ｗ２、…Ｗｍは各単量体の質量分率である。ただし、Ｗ１＋Ｗ２＋…＋Ｗｍ＝１である。）
　上記Ｆｏｘの式における各単量体のホモポリマーのガラス転移温度は、高分子データ・ハンドブック、粘着ハンドブック又は、ポリマーハンドブック記載の値を用いることができる。例えば、メチルアクリレートホモポリマーのＴｇは１０℃、２－ヒドロキシエチルアクリレートホモポリマーのＴｇは－１５℃、２－エチルヘキシルアクリレートのＴｇは－７０℃、２－エチルヘキシルメタクリレートのＴｇは－１０℃である。
　また、Ｔｇは、ＪＩＳ　Ｋ　７１２１（２０１２）に準拠して求めることもできる。 For example, the Tg of an acrylic resin can be obtained by calculation using the Fox formula shown below.
1/Tg=(W1/Tg1)+(W2/Tg2)+...+(Wm/Tgm)
(Wherein, Tg is the glass transition temperature of the acrylic resin, Tg1, Tg2, . is the mass fraction of the monomer, where W1 + W2 + ... + Wm = 1.)
For the glass transition temperature of the homopolymer of each monomer in the above Fox formula, the values described in Kobunshi Data Handbook, Adhesive Handbook, or Polymer Handbook can be used. For example, methyl acrylate homopolymer has a Tg of 10°C, 2-hydroxyethyl acrylate homopolymer has a Tg of -15°C, 2-ethylhexyl acrylate has a Tg of -70°C, and 2-ethylhexyl methacrylate has a Tg of -10°C.
Moreover, Tg can also be calculated|required based on JISK7121 (2012).
　（Ａ）熱可塑性樹脂は、官能基を有していてもよい。当該官能基としては、例えば、ビニル基、（メタ）アクリロイル基、アミノ基、ヒドロキシ基、カルボキシ基、イソシアネート基等が挙げられる。
　（Ａ）熱可塑性樹脂が官能基を有する場合、該官能基は、例えば、後述する（Ｈ）架橋剤を介して他の化合物と結合してもよいし、（Ｈ）架橋剤を介さずに他の化合物と直接結合していてもよい。（Ａ）熱可塑性樹脂が官能基によって（Ｈ）架橋剤を介して又は直接他の化合物と結合することによって、保護膜の信頼性がより良好になる傾向にある。
　官能基を有する（Ａ）熱可塑性樹脂としては、官能基を有するアクリル樹脂が好ましく、官能基としてヒドロキシ基を有するアクリル樹脂がより好ましい。 (A) The thermoplastic resin may have a functional group. Examples of the functional group include vinyl group, (meth)acryloyl group, amino group, hydroxy group, carboxy group, isocyanate group and the like.
(A) When the thermoplastic resin has a functional group, the functional group may be bonded to another compound via (H) a cross-linking agent, which will be described later, or (H) without a cross-linking agent. It may be directly bound to another compound. The reliability of the protective film tends to be better when (A) the thermoplastic resin bonds with another compound via (H) the cross-linking agent or directly with the functional group.
As the (A) thermoplastic resin having a functional group, an acrylic resin having a functional group is preferable, and an acrylic resin having a hydroxy group as a functional group is more preferable.
　保護膜形成用樹脂組成物中における（Ａ）熱可塑性樹脂の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは５～８０質量％、より好ましくは７～５０質量％、さらに好ましくは１０～３０質量％である。
　（Ａ）熱可塑性樹脂の含有量が上記下限値以上であると、保護膜形成用フィルムの硬化前の柔軟性及び保護対象物への接着性がより良好になる傾向にある。また、（Ａ）熱可塑性樹脂の含有量が上記上限値以下であると、保護膜の難燃性、機械強度及び耐熱性がより良好になる傾向にある。 The content of (A) the thermoplastic resin in the protective film-forming resin composition is not particularly limited, but is preferably 5 to 80 mass with respect to the solid content (100 mass%) of the protective film-forming resin composition. %, more preferably 7 to 50% by mass, still more preferably 10 to 30% by mass.
(A) When the content of the thermoplastic resin is at least the above lower limit, the flexibility of the film for forming a protective film before curing and the adhesion to an object to be protected tend to be better. Further, when the content of (A) the thermoplastic resin is equal to or less than the above upper limit, the protective film tends to have better flame retardancy, mechanical strength and heat resistance.
＜（Ｂ）熱硬化性樹脂＞
　保護膜形成用樹脂組成物が（Ｂ）熱硬化性樹脂を含有することによって、本実施形態の保護膜形成用フィルムは熱硬化性を有するものになり、機械強度、耐熱性等に優れる保護膜を形成できるものになる。
　（Ｂ）熱硬化性樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(B) Thermosetting resin>
By containing (B) a thermosetting resin in the protective film-forming resin composition, the protective film-forming film of the present embodiment has thermosetting properties, and the protective film is excellent in mechanical strength, heat resistance, etc. can be formed.
(B) The thermosetting resin may be used alone or in combination of two or more.
　（Ｂ）熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、熱硬化性ポリイミド樹脂等が挙げられる。これらの中でも、エポキシ樹脂が好ましい。
　エポキシ樹脂としては、１分子中にエポキシ基を２個以上有するエポキシ樹脂が好ましい。
　エポキシ樹脂としては、公知のものが挙げられ、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂及びその水添物；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；フェノールアラルキル型エポキシ樹脂等のアラルキル型エポキシ樹脂；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；ナフタレン型エポキシ樹脂；等が挙げられる。
　これらの中でも、保護膜形成用フィルムの取り扱い性、耐熱性等の観点から、ジシクロペンタジエン型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂が好ましい。 (B) Thermosetting resins include, for example, epoxy resins, phenol resins, melamine resins, urea resins, and thermosetting polyimide resins. Among these, epoxy resins are preferred.
As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable.
Examples of the epoxy resin include known ones, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and hydrogenated products thereof; phenol novolak type epoxy resin, cresol novolak type epoxy resin, ortho novolac type epoxy resins such as cresol novolak type epoxy resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins; dicyclopentadiene type epoxy resins; biphenyl type epoxy resins; naphthalene type epoxy resins;
Among these, dicyclopentadiene-type epoxy resins, bisphenol-type epoxy resins, and naphthalene-type epoxy resins are preferable from the viewpoints of handleability, heat resistance, and the like of the protective film-forming film.
　エポキシ樹脂の数平均分子量（Ｍｎ）は、特に限定されないが、保護膜形成用フィルムの硬化性、並びに保護膜の機械強度及び耐熱性の観点から、好ましくは２００～３０，０００、より好ましくは２５０～１０，０００、さらに好ましくは３００～３，０００である。 The number average molecular weight (Mn) of the epoxy resin is not particularly limited, but is preferably 200 to 30,000, more preferably 250, from the viewpoint of the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film. ~10,000, more preferably 300 to 3,000.
　エポキシ樹脂のエポキシ当量は、特に限定されないが、保護膜形成用フィルムの硬化性、並びに保護膜の機械強度及び耐熱性の観点から、好ましくは１００～１，５００ｇ／ｅｑ、より好ましくは１３０～１，２００ｇ／ｅｑ、さらに好ましくは１６０～１，０００ｇ／ｅｑである。
　なお、本明細書において、「エポキシ当量」とは、１グラム当量のエポキシ基を含むエポキシ樹脂のグラム数（ｇ／ｅｑ）を意味し、ＪＩＳ　Ｋ　７２３６：２００１に従って測定することができる。 Although the epoxy equivalent of the epoxy resin is not particularly limited, it is preferably 100 to 1,500 g/eq, more preferably 130 to 1, from the viewpoints of the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film. , 200 g/eq, more preferably 160 to 1,000 g/eq.
As used herein, "epoxy equivalent" means the number of grams (g/eq) of an epoxy resin containing 1 gram equivalent of epoxy groups, and can be measured according to JIS K 7236:2001.
　保護膜形成用樹脂組成物中におけるエポキシ樹脂の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは２～６０質量％、より好ましくは４～４０質量％、さらに好ましくは７～２０質量％である。
　エポキシ樹脂の含有量が上記下限値以上であると、保護膜形成用フィルムの硬化性、並びに保護膜の機械強度及び耐熱性がより良好になる傾向にある。また、エポキシ樹脂の含有量が上記上限値以下であると、保護膜形成用フィルムの硬化前の柔軟性がより良好になる傾向にある。 The content of the epoxy resin in the protective film-forming resin composition is not particularly limited, but is preferably 2 to 60% by mass, more preferably 2 to 60% by mass, based on the solid content (100% by mass) of the protective film-forming resin composition. is 4 to 40% by mass, more preferably 7 to 20% by mass.
When the content of the epoxy resin is at least the above lower limit, the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film tend to be better. Moreover, when the content of the epoxy resin is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
　保護膜形成用樹脂組成物中における（Ｂ）熱硬化性樹脂の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは２～６０質量％、より好ましくは４～４０質量％、さらに好ましくは７～２０質量％である。
　（Ｂ）熱硬化性樹脂の含有量が上記下限値以上であると、保護膜形成用フィルムの硬化性、並びに保護膜の機械強度及び耐熱性がより良好になる傾向にある。また、（Ｂ）熱硬化性樹脂の含有量が上記上限値以下であると、保護膜形成用フィルムの硬化前の柔軟性がより良好になる傾向にある。 The content of the (B) thermosetting resin in the protective film-forming resin composition is not particularly limited, but is preferably 2 to 60 with respect to the solid content (100% by mass) of the protective film-forming resin composition. % by mass, more preferably 4 to 40% by mass, and even more preferably 7 to 20% by mass.
(B) When the content of the thermosetting resin is at least the above lower limit, the curability of the protective film-forming film and the mechanical strength and heat resistance of the protective film tend to be better. Moreover, when the content of the thermosetting resin (B) is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
＜（Ｃ）無機充填材＞
　保護膜形成用樹脂組成物は、さらに、（Ｃ）無機充填材を含有することが好ましい。
　保護膜形成用樹脂組成物が（Ｃ）無機充填材を含有することによって、本実施形態の保護膜形成用フィルムは形状維持性に優れるものになり、また、本実施形態の保護膜形成用フィルムから形成される保護膜は、難燃性、低熱膨張性、低吸湿性等に優れるものになる。
　（Ｃ）無機充填材は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(C) Inorganic filler>
The protective film-forming resin composition preferably further contains (C) an inorganic filler.
By containing (C) the inorganic filler in the protective film-forming resin composition, the protective film-forming film of the present embodiment has excellent shape retention, and the protective film-forming film of the present embodiment The protective film formed from is excellent in flame retardancy, low thermal expansion, low hygroscopicity, and the like.
(C) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
　（Ｃ）無機充填材としては、例えば、シリカ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化ケイ素等が挙げられる。これらの中でも、シリカ、アルミナが好ましく、シリカがより好ましい。
　（Ｃ）無機充填材の形状は特に限定されず、例えば、球状、破砕状、繊維状等であってもよいが、球状であることが好ましい。
　（Ｃ）無機充填材は、表面処理剤等によって表面改質を施したものであってもよい。表面処理剤としては、後述する（Ｉ）カップリング剤を使用することができる。 (C) Examples of inorganic fillers include silica, talc, calcium carbonate, titanium white, red iron oxide, and silicon carbide. Among these, silica and alumina are preferred, and silica is more preferred.
The shape of the inorganic filler (C) is not particularly limited, and may be, for example, spherical, pulverized, or fibrous, but preferably spherical.
(C) The inorganic filler may be surface-modified with a surface treatment agent or the like. As the surface treatment agent, the (I) coupling agent described later can be used.
　（Ｃ）無機充填材の平均粒子径（Ｄ５０）は、特に限定されないが、好ましくは０．１～１０μｍ、より好ましくは０．２～５μｍ、さらに好ましくは０．３～１μｍである。
　（Ｃ）無機充填材の平均粒子径（Ｄ５０）は、マルチサイザー・スリー機（ベックマン・コールター社製）等を用いて、コールターカウンター法による粒度分布の測定を行うことによって求められる。 The average particle size (D 50 ) of the inorganic filler (C) is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.3 to 1 μm.
(C) The average particle size (D 50 ) of the inorganic filler is obtained by measuring the particle size distribution by the Coulter counter method using a multisizer three machine (manufactured by Beckman Coulter, Inc.) or the like.
　保護膜形成用樹脂組成物中における（Ｃ）無機充填材の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは５０質量％以上、より好ましくは５３質量％以上、さらに好ましくは５５質量％以上であり、また、好ましくは９０質量％以下、より好ましくは８５質量％以下、さらに好ましくは８０質量％以下である。
　（Ｃ）無機充填材の含有量が上記下限値以上であると、保護膜形成用フィルムの形状維持性、保護膜の難燃性、低熱膨張性及び低吸湿性がより良好になる傾向にある。また、（Ｃ）無機充填材の含有量が上記上限値以下であると、保護膜形成用フィルムの硬化前の柔軟性がより良好になる傾向にある。 The content of (C) the inorganic filler in the protective film-forming resin composition is not particularly limited, but is preferably 50% by mass or more with respect to the solid content (100% by mass) of the protective film-forming resin composition. , more preferably 53% by mass or more, still more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.
(C) When the content of the inorganic filler is at least the above lower limit, the shape retention of the protective film-forming film, the flame retardancy of the protective film, low thermal expansion, and low hygroscopicity tend to be better. . Further, when the content of the inorganic filler (C) is equal to or less than the above upper limit, the flexibility of the film for forming a protective film before curing tends to be better.
＜（Ｄ）難燃剤＞
　保護膜形成用樹脂組成物は、さらに、（Ｄ）難燃剤を含有することが好ましい。
　保護膜形成用樹脂組成物が（Ｄ）難燃剤を含有することによって、本実施形態の保護膜形成用フィルムから形成される保護膜は、難燃性に優れるものになる。
　（Ｄ）難燃剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(D) Flame Retardant>
The protective film-forming resin composition preferably further contains (D) a flame retardant.
By including (D) the flame retardant in the protective film-forming resin composition, the protective film formed from the protective film-forming film of the present embodiment has excellent flame retardancy.
(D) A flame retardant may be used individually by 1 type, and may use 2 or more types together.
　（Ｄ）難燃剤としては、例えば、ハロゲン系化合物、リン原子を含む化合物、窒素原子を含む化合物、リン原子及び窒素原子を含む化合物、これら以外の無機系難燃剤等が挙げられる。これらの中でも、保護膜の難燃性及び接着性の観点から、リン原子及び窒素原子を含む化合物であることが好ましい。以下、リン原子及び窒素原子を含む化合物を「（Ｄ１）リン原子及び窒素原子を含む化合物」と称する。 (D) Flame retardants include, for example, halogen-based compounds, compounds containing phosphorus atoms, compounds containing nitrogen atoms, compounds containing phosphorus atoms and nitrogen atoms, and inorganic flame retardants other than these. Among these, compounds containing a phosphorus atom and a nitrogen atom are preferable from the viewpoint of flame retardancy and adhesiveness of the protective film. A compound containing a phosphorus atom and a nitrogen atom is hereinafter referred to as "(D1) a compound containing a phosphorus atom and a nitrogen atom".
（（Ｄ１）リン原子及び窒素原子を含む化合物）
　保護膜形成用樹脂組成物が（Ｄ１）リン原子及び窒素原子を含む化合物を含有することによって、難燃性と接着性とをより良好に両立する保護膜を形成できる傾向にある。
　その理由については定かではないが、（Ｄ１）成分に含まれるリン原子及び窒素原子が難燃性に寄与すると共に、当該化合物は、（Ａ）熱可塑性樹脂、（Ｂ）熱硬化性樹脂等との相溶性が高いため、保護膜形成用フィルム中において可塑剤のように作用し、保護膜形成用フィルムの保護対象物に対する密着性が向上することが一因と推察される。
　（Ｄ１）リン原子及び窒素原子を含む化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。 ((D1) a compound containing a phosphorus atom and a nitrogen atom)
When the resin composition for forming a protective film contains (D1) a compound containing a phosphorus atom and a nitrogen atom, it tends to be possible to form a protective film that satisfactorily achieves both flame retardancy and adhesiveness.
Although the reason for this is not clear, the phosphorus atoms and nitrogen atoms contained in component (D1) contribute to flame retardancy, and the compound is used as (A) a thermoplastic resin, (B) a thermosetting resin, etc. It is presumed that one of the reasons for this is that because of the high compatibility of , it acts like a plasticizer in the protective film-forming film, improving the adhesion of the protective film-forming film to the object to be protected.
(D1) The compound containing a phosphorus atom and a nitrogen atom may be used alone or in combination of two or more.
　（Ｄ１）リン原子及び窒素原子を含む化合物が１分子中に有するリン原子の数は、特に限定されないが、好ましくは１～２０個、より好ましくは２～１０個、さらに好ましくは３～５個、特に好ましくは３個又は４個である。
　（Ｄ１）リン原子及び窒素原子を含む化合物が１分子中に有する窒素原子の数は、特に限定されないが、好ましくは１～２０個、より好ましくは２～１０個、さらに好ましくは３～５個、特に好ましくは３個又は４個である。
　（Ｄ１）リン原子及び窒素原子を含む化合物中におけるリン原子及び窒素原子の数が、上記範囲であると、難燃性と接着性とをより良好に両立する保護膜を形成できる傾向にある。 (D1) The number of phosphorus atoms that the compound containing a phosphorus atom and a nitrogen atom has in one molecule is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 3 to 5. , particularly preferably 3 or 4.
(D1) The number of nitrogen atoms in one molecule of the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, but is preferably 1 to 20, more preferably 2 to 10, and still more preferably 3 to 5. , particularly preferably 3 or 4.
(D1) When the number of phosphorus atoms and nitrogen atoms in the compound containing phosphorus atoms and nitrogen atoms is within the above range, there is a tendency to form a protective film that satisfactorily achieves both flame retardancy and adhesiveness.
　（Ｄ１）リン原子及び窒素原子を含む化合物中における、リン原子の含有量は、特に限定されないが、（Ｄ１）リン原子及び窒素原子を含む化合物（１００質量％）に対して、好ましくは５～３０質量％、より好ましくは７～２０質量％、さらに好ましくは１０～１５質量％である。
　（Ｄ１）リン原子及び窒素原子を含む化合物中における、窒素原子の含有量は、特に限定されないが、（Ｄ１）リン原子及び窒素原子を含む化合物（１００質量％）に対して、好ましくは１～２０質量％、より好ましくは２～１５質量％、さらに好ましくは４～１０質量％である。
　（Ｄ１）リン原子及び窒素原子を含む化合物中におけるリン原子及び窒素原子の含有量が、上記範囲であると、難燃性と接着性とをより良好に両立する保護膜を形成できる傾向にある。 (D1) The content of the phosphorus atom in the compound containing a phosphorus atom and a nitrogen atom is not particularly limited. 30% by mass, more preferably 7 to 20% by mass, still more preferably 10 to 15% by mass.
(D1) The content of nitrogen atoms in the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, but (D1) the compound containing a phosphorus atom and a nitrogen atom (100 mass%) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 4 to 10% by mass.
(D1) When the content of the phosphorus atom and the nitrogen atom in the compound containing the phosphorus atom and the nitrogen atom is within the above range, there is a tendency to form a protective film that achieves both flame retardancy and adhesion. .
　（Ｄ１）リン原子及び窒素原子を含む化合物は、保護膜の難燃性をより向上させるという観点から、リン原子と窒素原子との結合を含む化合物であることが好ましい。 (D1) The compound containing a phosphorus atom and a nitrogen atom is preferably a compound containing a bond between a phosphorus atom and a nitrogen atom from the viewpoint of further improving the flame retardancy of the protective film.
　リン原子と窒素原子との結合を含む化合物は、難燃性と接着性とをより良好に両立する保護膜を形成するという観点から、リン原子と窒素原子との結合を含む有機化合物であることが好ましく、下記一般式（Ｄ－１）で表される構造を含む化合物であることがより好ましい。 The compound containing a bond between a phosphorus atom and a nitrogen atom is an organic compound containing a bond between a phosphorus atom and a nitrogen atom from the viewpoint of forming a protective film that achieves both flame retardancy and adhesion. is preferred, and a compound containing a structure represented by the following general formula (D-1) is more preferred.
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ１は、置換若しくは無置換の脂肪族炭化水素基、又は置換若しくは無置換の芳香族炭化水素基を示す。複数のＲ１は互いに同じであってもよく、異なっていてもよい。ｎは、３～２０の整数を示す。－＊１及び－＊２は、他の原子との結合手を示す。結合手－＊１と結合手－＊２とは互いに連結して、環状構造を形成してもよい。）
Figure JPOXMLDOC01-appb-C000001
(In the formula, R 1 represents a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group. A plurality of R 1 may be the same or different. n represents an integer of 3 to 20. -* 1 and -* 2 represent a bond with another atom, bond -* 1 and bond -* 2 are linked to each other, You may form a ring structure.)
　上記一般式（Ｄ－１）中のＲ１が示す置換若しくは無置換の脂肪族炭化水素基としては、例えば、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、置換若しくは無置換のアルキニル基等が挙げられる。これらの脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。
　置換若しくは無置換の脂肪族炭化水素基の炭素数は、特に限定されないが、好ましくは１～１０、より好ましくは２～８、さらに好ましくは３～５である。なお、脂肪族炭化水素基が置換基を有する場合、当該炭素数には、置換基の炭素数を含めないものとする。
　脂肪族炭化水素基が有していてもよい置換基としては、例えば、ハロゲン原子、ヒドロキシ基、カルボキシ基、アルコキシ基、シアノ基、芳香族炭化水素基等が挙げられる。置換基としての芳香族炭化水素基は、後述するＲ１が示す芳香族炭化水素基と同じものが挙げられる。 Examples of the substituted or unsubstituted aliphatic hydrocarbon group represented by R 1 in the general formula (D-1) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted An alkynyl group and the like can be mentioned. These aliphatic hydrocarbon groups may be linear or branched.
Although the number of carbon atoms in the substituted or unsubstituted aliphatic hydrocarbon group is not particularly limited, it is preferably 1-10, more preferably 2-8, still more preferably 3-5. In addition, when an aliphatic hydrocarbon group has a substituent, the carbon number of a substituent shall not be included in the said carbon number.
Examples of substituents which the aliphatic hydrocarbon group may have include halogen atoms, hydroxy groups, carboxy groups, alkoxy groups, cyano groups, aromatic hydrocarbon groups and the like. Examples of the aromatic hydrocarbon group as a substituent are the same as the aromatic hydrocarbon group represented by R 1 described later.
　置換若しくは無置換の芳香族炭化水素基としては、例えば、置換若しくは無置換のフェニル基、置換若しくは無置換のナフチル基等が挙げられる。
　置換若しくは無置換の芳香族炭化水素基の炭素数は、特に限定されないが、好ましくは６～１２、より好ましくは６～８である。なお、芳香族炭化水素基が置換基を有する場合、当該炭素数には、置換基の炭素数を含めないものとする。
　芳香族炭化水素基が有していてもよい置換基としては、例えば、ハロゲン原子、ヒドロキシ基、カルボキシ基、アルコキシ基、シアノ基、脂肪族炭化水素基等が挙げられる。置換基としての脂肪族炭化水素基は、上述したＲ１が示す脂肪族炭化水素基と同じものが挙げられる。 Examples of substituted or unsubstituted aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted naphthyl groups.
Although the number of carbon atoms in the substituted or unsubstituted aromatic hydrocarbon group is not particularly limited, it is preferably 6-12, more preferably 6-8. In addition, when the aromatic hydrocarbon group has a substituent, the carbon number of the substituent is not included in the number of carbon atoms.
Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms, hydroxy groups, carboxy groups, alkoxy groups, cyano groups, and aliphatic hydrocarbon groups. The aliphatic hydrocarbon group as a substituent includes the same aliphatic hydrocarbon groups as those represented by R 1 described above.
　上記選択肢の中でも、上記一般式（Ｄ－１）中のＲ１は、置換若しくは無置換のフェニル基であることが好ましく、無置換のフェニル基であることがより好ましい。 Among the above options, R 1 in general formula (D-1) above is preferably a substituted or unsubstituted phenyl group, more preferably an unsubstituted phenyl group.
　上記一般式（Ｄ－１）中のｎは、特に限定されないが、好ましくは３～１５の整数、より好ましくは３～１０の整数、さらに好ましくは３～５の整数である。 Although n in the above general formula (D-1) is not particularly limited, it is preferably an integer of 3-15, more preferably an integer of 3-10, and still more preferably an integer of 3-5.
　上記一般式（Ｄ－１）中の－＊１及び－＊２は、他の原子との結合手を示す。
　上記一般式（Ｄ－１）中の結合手－＊１と結合手－＊２とは互いに連結して、環状構造を形成してもよく、環状構造を形成することが好ましい。この場合、「一般式（Ｄ－１）で表される構造を含む化合物」とは、「一般式（Ｄ－１）で表される化合物」と同義である。 -* 1 and -* 2 in the above general formula (D-1) represent bonds with other atoms.
The bond-* 1 and bond-* 2 in the general formula (D-1) may be linked to each other to form a cyclic structure, preferably a cyclic structure. In this case, "a compound containing a structure represented by general formula (D-1)" is synonymous with "a compound represented by general formula (D-1)".
　上記一般式（Ｄ－１）中の結合手－＊１と結合手－＊２とが互いに連結していない場合、－＊１は、－Ｎ＝Ｐ（ＯＲ１）３又は－Ｎ＝Ｐ（Ｏ）（ＯＲ１）に結合することが好ましく、－＊２は、－Ｐ（ＯＲ１）３又は－Ｐ（Ｏ）（ＯＲ１）に結合することが好ましい。これらの基に含まれるＲ１の説明は、上記一般式（Ｄ－１）中のＲ１の説明の通りである。 When the bond -* 1 and the bond -* 2 in the general formula (D-1) are not connected to each other, -* 1 is -N=P(OR 1 ) 3 or -N=P( O)(OR 1 ) is preferably attached and -* 2 is preferably attached to -P(OR 1 ) 3 or -P(O)(OR 1 ). The description of R 1 contained in these groups is as described for R 1 in general formula (D-1) above.
　（Ｄ１）リン原子及び窒素原子を含む化合物としては、例えば、ホスファゼン化合物が挙げられる。ここで、本明細書において「ホスファゼン化合物」とは、リン原子と窒素原子を交互に含有し、それぞれのリン原子が２つの置換基を有する化合物を意味する。
　ホスファゼン化合物は、有機化合物又は無機化合物のいずれであってもよいが、有機化合物であることが好ましい。 (D1) Examples of compounds containing a phosphorus atom and a nitrogen atom include phosphazene compounds. As used herein, the term "phosphazene compound" means a compound containing alternating phosphorus atoms and nitrogen atoms, each phosphorus atom having two substituents.
The phosphazene compound may be either an organic compound or an inorganic compound, but is preferably an organic compound.
　ホスファゼン化合物としては、例えば、環状ホスファゼン化合物、鎖状ホスファゼン化合物等が挙げられ、環状ホスファゼン化合物が好ましい。
　環状ホスファゼン化合物としては、例えば、ヘキサフェノキシシクロトリホスファゼン、オクタフェノキシシクロテトラホスファゼン、デカフェノキシシクロペンタホスファゼン、ドデカフェノキシシクロヘキサホスファゼン、テトラデカフェノキシシクロヘプタホスファゼン等の環状フェノキシホスファゼン化合物；ヘキサプロポキシシクロトリホスファゼン、オクタプロポキシシクロテトラホスファゼン、デカプロポキシシクロペンタホスファゼン、ドデカプロポキシシクロヘキサホスファゼン、テトラデカプロポキシシクロヘプタホスファゼン等の環状プロポキシホスファゼン化合物；等が挙げられる。これらの中でも、環状フェノキシホスファゼン化合物が好ましく、ヘキサフェノキシシクロトリホスファゼンがより好ましい。 Examples of the phosphazene compound include cyclic phosphazene compounds, chain phosphazene compounds, and the like, and cyclic phosphazene compounds are preferred.
Cyclic phosphazene compounds include, for example, cyclic phenoxyphosphazene compounds such as hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene, dodecafenoxycyclohexaphosphazene, and tetradecafenoxycycloheptaphosphazene; hexapropoxycyclotriphosphazene; cyclic propoxyphosphazene compounds such as , octapropoxycyclotetraphosphazene, decapropoxycyclopentaphosphazene, dodecapropoxycyclohexaphosphazene, and tetradecapropoxycycloheptaphosphazene; Among these, cyclic phenoxyphosphazene compounds are preferred, and hexaphenoxycyclotriphosphazene is more preferred.
　（Ｄ１）リン原子及び窒素原子を含む化合物の分子量は、特に限定されないが、好ましくは３００～３，０００、より好ましくは４００～１，５００、さらに好ましくは５００～８００である。
　（Ｄ１）リン原子及び窒素原子を含む化合物の分子量が上記下限値以上であると、保護膜形成用フィルムの製造過程及び硬化過程において（Ｄ１）リン原子及び窒素原子を含む化合物の揮発を抑制できる傾向にある。（Ｄ１）リン原子及び窒素原子を含む化合物の分子量が上記上限値以下であると、保護膜形成用フィルム中における（Ｄ１）リン原子及び窒素原子を含む化合物の分散性がより良好になる傾向にある。 Although the molecular weight of (D1) the compound containing a phosphorus atom and a nitrogen atom is not particularly limited, it is preferably 300 to 3,000, more preferably 400 to 1,500, still more preferably 500 to 800.
(D1) When the molecular weight of the compound containing a phosphorus atom and a nitrogen atom is at least the above lower limit, volatilization of the compound containing (D1) a phosphorus atom and a nitrogen atom can be suppressed during the production process and curing process of the protective film-forming film. There is a tendency. When the molecular weight of (D1) the compound containing a phosphorus atom and a nitrogen atom is equal to or less than the above upper limit, the dispersibility of the compound containing (D1) a phosphorus atom and a nitrogen atom in the film for forming a protective film tends to be better. be.
　保護膜形成用樹脂組成物中における（Ｄ１）リン原子及び窒素原子を含む化合物の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは１～２０質量％、より好ましくは２～１５質量％、さらに好ましくは２．５～１３質量％、よりさらに好ましくは３～１１質量％、よりさらに好ましくは３～８質量％、特に好ましくは３～５質量％である。
　また、保護膜形成用樹脂組成物中における（Ｄ１）リン原子及び窒素原子を含む化合物の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分のうち無機充填材及び着色剤を除く成分の総量（１００質量％）に対して、好ましくは５～７０質量％、より好ましくは７～６０質量％、さらに好ましくは８～５０質量％、よりさらに好ましくは９～４０質量％、よりさらに好ましくは１４～３５質量％、特に好ましくは１９～３０質量％である。
　（Ｄ１）リン原子及び窒素原子を含む化合物の含有量が上記下限値以上であると、保護膜の難燃性がより良好になる傾向にある。また、（Ｄ１）リン原子及び窒素原子を含む化合物の含有量が上記上限値以下であると、保護膜形成用フィルムの凝集力及び保護膜の接着性がより良好になる傾向にある。 The content of (D1) the compound containing a phosphorus atom and a nitrogen atom in the protective film-forming resin composition is not particularly limited, but is preferably based on the solid content (100 mass%) of the protective film-forming resin composition. Is 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 2.5 to 13% by mass, even more preferably 3 to 11% by mass, even more preferably 3 to 8% by mass, particularly preferably It is 3 to 5% by mass.
In addition, the content of (D1) the compound containing a phosphorus atom and a nitrogen atom in the protective film-forming resin composition is not particularly limited. With respect to the total amount (100% by mass) of the components excluding the Even more preferably 14 to 35% by mass, particularly preferably 19 to 30% by mass.
(D1) When the content of the compound containing a phosphorus atom and a nitrogen atom is at least the above lower limit, the flame retardancy of the protective film tends to be better. Further, when the content of (D1) the compound containing a phosphorus atom and a nitrogen atom is equal to or less than the above upper limit, the cohesive force of the protective film-forming film and the adhesiveness of the protective film tend to be better.
　保護膜形成用樹脂組成物中における（Ｄ１）リン原子及び窒素原子を含む化合物の含有量に対する（Ｃ）無機充填材の含有量の比〔（Ｃ）成分／（Ｄ１）成分〕は、特に限定されないが、質量基準で、好ましくは２～４０、より好ましくは３～３５、さらに好ましくは４～３０、特に好ましくは５～２５である。
　含有量の比〔（Ｃ）成分／（Ｄ１）成分〕が上記範囲であると、保護膜の難燃性、接着性、低熱膨張性及び低吸湿性のバランスがより良好になる傾向にある。 The ratio of the content of the (C) inorganic filler to the content of the compound containing (D1) a phosphorus atom and a nitrogen atom in the protective film-forming resin composition [(C) component/(D1) component] is particularly limited. However, it is preferably 2 to 40, more preferably 3 to 35, even more preferably 4 to 30, and particularly preferably 5 to 25, based on mass.
When the content ratio [component (C)/component (D1)] is within the above range, the protective film tends to have a better balance of flame retardancy, adhesiveness, low thermal expansion and low hygroscopicity.
　保護膜形成用樹脂組成物中における（Ｄ）難燃剤の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは１～２０質量％、より好ましくは２～１５質量％、さらに好ましくは２．５～１３質量％、よりさらに好ましくは３～１１質量％であり、よりさらに好ましくは３～８質量％であり、特に好ましくは３～５質量％である。
　また、保護膜形成用樹脂組成物中における（Ｄ）難燃剤の含有量は、特に限定されないが、保護膜形成用樹脂組成物の固形分のうち無機充填材及び着色剤を除く成分の総量（１００質量％）に対して、好ましくは５～７０質量％、より好ましくは７～６０質量％、さらに好ましくは８～５０質量％、よりさらに好ましくは９～４０質量％であり、よりさらに好ましくは１４～３５質量％であり、特に好ましくは１９～３０質量％である。
　（Ｄ）難燃剤の含有量が上記下限値以上であると、保護膜の難燃性がより良好になる傾向にある。また、（Ｄ）難燃剤の含有量が上記上限値以下であると、保護膜の接着性がより良好になる傾向にある。 The content of the (D) flame retardant in the protective film-forming resin composition is not particularly limited, but is preferably 1 to 20% by mass based on the solid content (100% by mass) of the protective film-forming resin composition. , More preferably 2 to 15% by mass, still more preferably 2.5 to 13% by mass, still more preferably 3 to 11% by mass, still more preferably 3 to 8% by mass, particularly preferably 3 to 5% by mass.
In addition, the content of the (D) flame retardant in the protective film-forming resin composition is not particularly limited, but the total amount of the components excluding the inorganic filler and the colorant among the solids of the protective film-forming resin composition ( 100% by mass), preferably 5 to 70% by mass, more preferably 7 to 60% by mass, even more preferably 8 to 50% by mass, even more preferably 9 to 40% by mass, and even more preferably 14 to 35% by mass, particularly preferably 19 to 30% by mass.
(D) When the content of the flame retardant is at least the above lower limit, the flame retardancy of the protective film tends to be better. Moreover, when the content of the flame retardant (D) is equal to or less than the above upper limit, the adhesiveness of the protective film tends to be better.
　上記（Ｄ１）成分以外の（Ｄ）難燃剤としては、例えば、塩素原子を含有する塩素系難燃剤、臭素原子を含有する臭素系難燃剤等のハロゲン系化合物；赤リン、リン酸エステル、リン酸金属塩等のリン原子を含む化合物；トリアジン環を有する化合物、イソシアヌレート環を有する化合物等の窒素原子を含む化合物；水酸化アルミニウム、水酸化マグネシウム、アンチモン系化合物等の無機系難燃剤；等が挙げられる。 Examples of (D) flame retardants other than the component (D1) include halogen-based compounds such as chlorine-based flame retardants containing chlorine atoms and brominated flame-retardants containing bromine atoms; Phosphorus atom-containing compounds such as acid metal salts; Nitrogen atom-containing compounds such as triazine ring-containing compounds and isocyanurate ring-containing compounds; Inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and antimony compounds; are mentioned.
＜（Ｅ）硬化促進剤＞
　保護膜形成用樹脂組成物は、（Ｅ）硬化促進剤を含有していてもよい。
　保護膜形成用樹脂組成物が（Ｅ）硬化促進剤を含有することによって、本実施形態の保護膜形成用フィルムは、硬化性がより良好になる傾向にある。
　（Ｅ）硬化促進剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(E) Curing accelerator>
The protective film-forming resin composition may contain (E) a curing accelerator.
When the protective film-forming resin composition contains (E) the curing accelerator, the protective film-forming film of the present embodiment tends to have better curability.
(E) The curing accelerator may be used alone or in combination of two or more.
　（Ｅ）硬化促進剤としては、例えば、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）フェノール等の第３級アミン；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等のイミダゾール類；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等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等のテトラフェニルボロン塩；等が挙げられる。これらの中でも、イミダゾール類が好ましく、２－フェニル－４，５－ジヒドロキシメチルイミダゾールがより好ましい。 (E) Curing accelerators include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like organic phosphines; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and the like. Among these, imidazoles are preferred, and 2-phenyl-4,5-dihydroxymethylimidazole is more preferred.
　保護膜形成用樹脂組成物が（Ｅ）硬化促進剤を含有する場合、保護膜形成用樹脂組成物中における（Ｅ）硬化促進剤の含有量は、特に限定されないが、（Ｂ）熱硬化性樹脂１００質量部に対して、好ましくは０．０１～１０質量部、より好ましくは０．１～５質量部、さらに好ましくは１～３質量部である。
　（Ｅ）硬化促進剤の含有量が上記下限値以上であると、保護膜形成用フィルムの硬化性がより良好になる傾向にある。また、（Ｅ）硬化促進剤の含有量が上記上限値以下であると、硬化物の均質性がより良好になる傾向にある。 When the protective film-forming resin composition contains (E) a curing accelerator, the content of (E) the curing accelerator in the protective film-forming resin composition is not particularly limited, but (B) thermosetting It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 1 to 3 parts by mass, based on 100 parts by mass of the resin.
(E) When the content of the curing accelerator is at least the above lower limit, the curability of the protective film-forming film tends to be better. Further, when the content of (E) the curing accelerator is equal to or less than the above upper limit, the homogeneity of the cured product tends to be better.
＜（Ｆ）着色剤＞
　保護膜形成用樹脂組成物は、（Ｆ）着色剤を含有していてもよい。
　保護膜形成用樹脂組成物が（Ｆ）着色剤を含有することによって、本実施形態の保護膜形成用フィルムから形成される保護膜に、レーザー印字性、遮光性、意匠性等を付与することができる。
　（Ｆ）着色剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(F) Colorant>
The protective film-forming resin composition may contain (F) a colorant.
The resin composition for forming a protective film contains (F) a coloring agent, so that the protective film formed from the film for forming a protective film of the present embodiment is endowed with laser printability, light shielding properties, design properties, and the like. can be done.
(F) Colorants may be used alone or in combination of two or more.
　（Ｆ）着色剤としては、公知のものが挙げられ、例えば、無機系顔料、有機系顔料、有機系染料等が挙げられる。
　無機系顔料としては、例えば、カーボンブラック、コバルト系色素、鉄系色素、クロム系色素、チタン系色素、バナジウム系色素、ジルコニウム系色素、モリブデン系色素、ルテニウム系色素、白金系色素、ＩＴＯ（インジウムスズオキサイド）系色素、ＡＴＯ（アンチモンスズオキサイド）系色素等が挙げられる。
　有機系顔料及び有機系染料としては、例えば、アミニウム系色素、シアニン系色素、メロシアニン系色素、クロコニウム系色素、スクアリウム系色素、アズレニウム系色素、ポリメチン系色素、ナフトキノン系色素、ピリリウム系色素、フタロシアニン系色素、ナフタロシアニン系色素、ナフトラクタム系色素、アゾ系色素、縮合アゾ系色素、インジゴ系色素、ペリノン系色素、ペリレン系色素、ジオキサジン系色素、キナクリドン系色素、イソインドリノン系色素、キノフタロン系色素、ピロール系色素、チオインジゴ系色素、金属錯体系色素（金属錯塩染料）、ジチオール金属錯体系色素、インドールフェノール系色素、トリアリルメタン系色素、アントラキノン系色素、ナフトール系色素、アゾメチン系色素、ベンズイミダゾロン系色素、ピランスロン系色素、スレン系色素等が挙げられる。 (F) Colorants include known ones, and examples thereof include inorganic pigments, organic pigments, organic dyes, and the like.
Examples of inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
Examples of organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine dyes. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazolones dyes, pyranthrone dyes, threne dyes, and the like.
　保護膜形成用樹脂組成物が（Ｆ）着色剤を含有する場合、保護膜形成用樹脂組成物中における（Ｆ）着色剤の含有量は、特に限定されないが、適度な着色効果を得るという観点から、保護膜形成用樹脂組成物の固形分（１００質量％）に対して、好ましくは０．０１～１０質量％、より好ましくは０．０５～７．５質量％、さらに好ましくは０．１～５質量％、特に好ましくは１～３質量％である。 When the protective film-forming resin composition contains (F) a coloring agent, the content of the (F) coloring agent in the protective film-forming resin composition is not particularly limited, but from the viewpoint of obtaining an appropriate coloring effect. Therefore, the solid content (100% by mass) of the resin composition for forming a protective film is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, and still more preferably 0.1 to 5% by weight, particularly preferably 1 to 3% by weight.
＜（Ｇ）エポキシ樹脂硬化剤＞
　保護膜形成用樹脂組成物は、（Ｂ）熱硬化性樹脂としてエポキシ樹脂を含有する場合に、さらに、（Ｇ）エポキシ樹脂硬化剤を含有していてもよい。
　保護膜形成用樹脂組成物が（Ｇ）エポキシ樹脂硬化剤を含有することによって、本実施形態の保護膜形成用フィルムは、硬化性がより良好になる傾向にある。
　（Ｇ）エポキシ樹脂硬化剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(G) Epoxy resin curing agent>
When the protective film-forming resin composition contains (B) an epoxy resin as the thermosetting resin, it may further contain (G) an epoxy resin curing agent.
When the protective film-forming resin composition contains (G) the epoxy resin curing agent, the protective film-forming film of the present embodiment tends to have better curability.
(G) The epoxy resin curing agent may be used alone or in combination of two or more.
　（Ｇ）エポキシ樹脂硬化剤としては、例えば、エポキシ基と反応し得る官能基を１分子中に２個以上有する化合物が挙げられる。
　エポキシ基と反応し得る官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシ基、酸基が無水物化された基等が挙げられる。これらの中でも、フェノール性水酸基、アミノ基、酸基が無水物化された基が好ましく、フェノール性水酸基、アミノ基がより好ましい。 (G) The epoxy resin curing agent includes, for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule.
Examples of the functional group capable of reacting with an epoxy group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an anhydride group of an acid group. Among these, a phenolic hydroxyl group, an amino group, and an anhydride-modified acid group are preferable, and a phenolic hydroxyl group and an amino group are more preferable.
　フェノール性水酸基を有する（Ｇ）エポキシ樹脂硬化剤としては、例えば、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型フェノール樹脂、アラルキル型フェノール樹脂等のフェノール系硬化剤が挙げられる。
　アミノ基を有する（Ｇ）エポキシ樹脂硬化剤としては、例えば、ジシアンジアミド等のアミン系硬化剤が挙げられる。 Examples of the (G) epoxy resin curing agent having a phenolic hydroxyl group include phenolic curing agents such as biphenol, novolac type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin.
Examples of the (G) epoxy resin curing agent having an amino group include amine-based curing agents such as dicyandiamide.
　（Ｇ）エポキシ樹脂硬化剤のうち、例えば、ビフェノール、ジシアンジアミド等の非樹脂成分の分子量は、特に限定されないが、好ましくは６０～５００、より好ましくは７０～２００、さらに好ましくは８０～１２０である。 Among (G) epoxy resin curing agents, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, more preferably 70 to 200, and still more preferably 80 to 120. .
　保護膜形成用樹脂組成物が（Ｇ）エポキシ樹脂硬化剤を含有する場合、保護膜形成用樹脂組成物中における（Ｇ）エポキシ樹脂硬化剤の含有量は、特に限定されないが、保護膜形成用フィルムの硬化性をより良好にするという観点から、エポキシ樹脂１００質量部に対して、好ましくは０．１～２００質量部、より好ましくは０．５～１００質量部、さらに好ましくは０．７～５０質量部、特に好ましくは１～１０質量部である。 When the protective film-forming resin composition contains (G) epoxy resin curing agent, the content of (G) epoxy resin curing agent in the protective film-forming resin composition is not particularly limited. From the viewpoint of improving the curability of the film, it is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and still more preferably 0.7 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. 50 parts by weight, particularly preferably 1 to 10 parts by weight.
＜（Ｈ）架橋剤＞
　（Ａ）熱可塑性樹脂が官能基を有する場合、保護膜形成用樹脂組成物は、（Ｈ）架橋剤を含有していてもよい。（Ｈ）架橋剤によって官能基を有する（Ａ）熱可塑性樹脂を架橋させることによって、保護膜形成用フィルムの初期接着力及び凝集力を調整することができる。
　（Ｈ）架橋剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(H) Crosslinking agent>
(A) When the thermoplastic resin has a functional group, the protective film-forming resin composition may contain (H) a cross-linking agent. By cross-linking the (A) thermoplastic resin having a functional group with the (H) cross-linking agent, the initial adhesive strength and cohesive strength of the protective film-forming film can be adjusted.
(H) The crosslinking agent may be used alone or in combination of two or more.
　（Ｈ）架橋剤としては、例えば、有機多価イソシアネート化合物、有機多価イミン化合物、金属キレート系架橋剤（金属キレート構造を有する架橋剤）、アジリジン系架橋剤（アジリジニル基を有する架橋剤）等が挙げられる。 Examples of the (H) cross-linking agent include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. is mentioned.
　有機多価イソシアネート化合物としては、例えば、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及び脂環族多価イソシアネート化合物（以下、これら化合物をまとめて「芳香族多価イソシアネート化合物等」と略記することがある）；上記芳香族多価イソシアネート化合物等の三量体、イソシアヌレート体及びアダクト体；上記芳香族多価イソシアネート化合物等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が挙げられる。
　なお、上記「アダクト体」とは、上記の芳香族多価イソシアネート化合物等と、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油等の低分子活性水素含有化合物との反応物を意味する。その具体例としては、後述するトリメチロールプロパンのトリレンジイソシアネート付加物等が挙げられる。 Examples of organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds (hereinafter, these compounds are collectively abbreviated as "aromatic polyisocyanate compounds, etc." trimers, isocyanurates and adducts of the above aromatic polyvalent isocyanate compounds; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds and the like with polyol compounds, etc. are mentioned.
In addition, the above-mentioned "adduct" means a reaction product of the above aromatic polyvalent isocyanate compound and the like with a low-molecular-weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. means. Specific examples thereof include a tolylene diisocyanate adduct of trimethylolpropane, which will be described later.
　有機多価イソシアネート化合物としては、例えば、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－キシリ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；トリメチロールプロパン等のポリオールのすべて又は一部の水酸基に、トリレンジイソシアネート、ヘキサメチレンジイソシアネート及びキシリレンジイソシアネートからなる群から選択される１種以上が付加した化合物；リジンジイソシアネート等が挙げられる。 Examples of organic polyvalent isocyanate compounds include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane-4,4′-diisocyanate 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; Compounds in which one or more selected from the group consisting of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of hydroxyl groups; lysine diisocyanate and the like.
　有機多価イミン化合物としては、例えば、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、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が挙げられる。 Examples of organic polyvalent imine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane- Tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene melamine and the like.
　以上の選択肢の中でも、（Ｈ）架橋剤としては、有機多価イソシアネート化合物が好ましく、トリメチロールプロパン等のポリオールのすべて又は一部の水酸基に、トリレンジイソシアネート、ヘキサメチレンジイソシアネート及びキシリレンジイソシアネートからなる群から選択される１種以上が付加した化合物がより好ましく、トリメチロールプロパンのトリレンジイソシアネート付加物がさらに好ましい。 Among the above options, the (H) cross-linking agent is preferably an organic polyvalent isocyanate compound, and consists of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate in all or part of the hydroxyl groups of a polyol such as trimethylolpropane. A compound to which one or more selected from the group is added is more preferred, and a tolylene diisocyanate adduct of trimethylolpropane is even more preferred.
　（Ｈ）架橋剤として有機多価イソシアネート化合物を用いる場合、（Ａ）熱可塑性樹脂は、ヒドロキシ基を有することが好ましい。（Ｈ）架橋剤がイソシアネート基を有し、（Ａ）熱可塑性樹脂がヒドロキシ基を有する場合、（Ｈ）架橋剤と（Ａ）熱可塑性樹脂との反応によって、保護膜形成用フィルムに架橋構造を簡便に導入することができる。 (H) When an organic polyvalent isocyanate compound is used as the cross-linking agent, (A) the thermoplastic resin preferably has a hydroxy group. When the (H) cross-linking agent has an isocyanate group and the (A) thermoplastic resin has a hydroxy group, the reaction between the (H) cross-linking agent and the (A) thermoplastic resin results in a cross-linked structure in the film for forming a protective film. can be easily introduced.
　保護膜形成用樹脂組成物が（Ｈ）架橋剤を含有する場合、保護膜形成用樹脂組成物中における（Ｈ）架橋剤の含有量は、特に限定されないが、保護膜形成用フィルムの初期接着力及び凝集力をより良好にするという観点から、官能基を有する（Ａ）熱可塑性樹脂１００質量部に対して、好ましくは０．０１～２０質量部、より好ましくは０．１～１０質量部、さらに好ましくは０．５～５質量部である。 When the protective film-forming resin composition contains (H) a cross-linking agent, the content of the (H) cross-linking agent in the protective film-forming resin composition is not particularly limited, but initial adhesion of the protective film-forming film From the viewpoint of improving the force and cohesive force, it is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the (A) thermoplastic resin having a functional group. , more preferably 0.5 to 5 parts by mass.
＜（Ｉ）カップリング剤＞
　保護膜形成用樹脂組成物は、（Ｉ）カップリング剤を含有していてもよい。
　保護膜形成用樹脂組成物が（Ｉ）カップリング剤を含有することによって、（Ｃ）無機充填材の分散性が向上すると共に、保護膜の接着性、耐水性等が向上する傾向にある。
　（Ｉ）カップリング剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 <(I) Coupling agent>
The protective film-forming resin composition may contain (I) a coupling agent.
When the protective film-forming resin composition contains (I) the coupling agent, the dispersibility of the (C) inorganic filler tends to improve, and the adhesiveness, water resistance, etc. of the protective film tend to improve.
(I) Coupling agents may be used alone or in combination of two or more.
　（Ｉ）カップリング剤としては、例えば、シランカップリング剤、チタネートカップリング剤等が挙げられる。これらの中でも、シランカップリング剤が好ましい。
　（Ｉ）カップリング剤としては、例えば、官能基を有する（Ａ）熱可塑性樹脂、（Ｂ）熱硬化性樹脂等と、反応し得る官能基を有するものが好ましい。当該官能基としては、例えば、グリシジル基、アミノ基、メルカプト基、ビニル基、（メタ）アクリロイル基、ヒドロキシ基、カルボキシ基、イミダゾール基等が挙げられる。これらの中でも、グリシジル基を有するものが好ましい。 (I) Coupling agents include, for example, silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred.
As the (I) coupling agent, for example, one having a functional group capable of reacting with (A) a thermoplastic resin or (B) a thermosetting resin having a functional group is preferable. Examples of the functional group include glycidyl group, amino group, mercapto group, vinyl group, (meth)acryloyl group, hydroxy group, carboxy group, imidazole group and the like. Among these, those having a glycidyl group are preferable.
　（Ｉ）カップリング剤としては、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジメトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、２－（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、３－メタクリロイルオキシプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルメチルジエトキシシラン、３－アニリノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－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、これらの１種又は２種以上の部分加水分解縮合物等が挙げられる。これらの中でも、３－グリシジルオキシプロピルトリメトキシシランが好ましい。 (I) Coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-amino Ethylamino)propylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl ) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, and partially hydrolyzed condensates of one or more of these. Among these, 3-glycidyloxypropyltrimethoxysilane is preferred.
　保護膜形成用樹脂組成物が（Ｉ）カップリング剤を含有する場合、保護膜形成用樹脂組成物中における（Ｉ）カップリング剤の含有量は、特に限定されないが、（Ａ）熱可塑性樹脂及び（Ｂ）熱硬化性樹脂の総量１００質量部に対して、好ましくは０．００１～１０質量部、より好ましくは０．００５～１質量部、さらに好ましくは０．０１～０．１質量部である。
　（Ｉ）カップリング剤の含有量が上記下限値以上であると、（Ｃ）無機充填材の分散性、保護膜の接着性、耐水性等がより良好になる傾向にある。また、（Ｉ）カップリング剤の含有量が上記上限値以下であると、アウトガスの発生がより抑制される傾向にある。 When the protective film-forming resin composition contains (I) a coupling agent, the content of (I) the coupling agent in the protective film-forming resin composition is not particularly limited, but (A) the thermoplastic resin And (B) with respect to 100 parts by mass of the total amount of the thermosetting resin, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, still more preferably 0.01 to 0.1 parts by mass is.
When the content of (I) the coupling agent is at least the above lower limit, the dispersibility of the (C) inorganic filler, the adhesiveness of the protective film, the water resistance, etc. tend to be better. Further, when the content of (I) the coupling agent is equal to or less than the above upper limit, outgassing tends to be further suppressed.
＜溶媒＞
　保護膜形成用樹脂組成物は、フィルムの形成を容易にするという観点から、溶媒を含有していてもよい。
　溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。 <Solvent>
From the viewpoint of facilitating film formation, the protective film-forming resin composition may contain a solvent.
A solvent may be used individually by 1 type, and may use 2 or more types together.
　溶媒としては、例えば、トルエン、キシレン等の炭化水素；メタノール、エタノール、２－プロパノール、２－メチルプロパン－１－オール、１－ブタノール等のアルコール；酢酸エチル等のエステル；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン等のエーテル；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド（アミド結合を有する化合物）等が挙げられる。これらの中でも、トルエン、酢酸エチル、メチルエチルケトンが好ましい。 Examples of solvents include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, 2-methylpropan-1-ol and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone; Among these, toluene, ethyl acetate, and methyl ethyl ketone are preferred.
＜その他の成分＞
　保護膜形成用樹脂組成物は、上記各成分以外のその他の成分を含有していてもよく、含有していなくてもよい。
　その他の成分としては、例えば、上記各成分以外の樹脂成分、可塑剤、帯電防止剤、酸化防止剤、ゲッタリング剤等が挙げられる。
　その他の成分は、各々について、１種を単独で用いてもよく、２種以上を併用してもよい。
　保護膜形成用樹脂組成物中におけるその他の成分の含有量は、特に限定されず、目的に応じて適宜選択すればよい。 <Other ingredients>
The protective film-forming resin composition may or may not contain components other than the components described above.
Other components include, for example, resin components other than the above components, plasticizers, antistatic agents, antioxidants, gettering agents, and the like.
For each of the other components, one type may be used alone, or two or more types may be used in combination.
The content of other components in the protective film-forming resin composition is not particularly limited, and may be appropriately selected according to the purpose.
＜保護膜形成用樹脂組成物の製造方法＞
　保護膜形成用樹脂組成物は、これを構成するための各成分を配合することによって製造することができる。
　各成分を配合する際における添加順序は特に限定されず、２種以上の成分を同時に添加してもよいし、逐次的に添加してもよい。
　溶媒を用いる場合には、溶媒以外のいずれかの成分は、溶媒で希釈して用いてもよいし、溶媒で希釈せずに他の成分と混合してもよい。
　各成分を混合する方法は特に限定されず、例えば、撹拌子、撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法；等の公知の方法から適宜選択すればよい。
　各成分を添加及び混合する際における温度及び時間は特に限定されず、使用する成分に応じて適宜調整すればよい。 <Method for producing protective film-forming resin composition>
The protective film-forming resin composition can be produced by blending the constituent components.
The order of addition in blending each component is not particularly limited, and two or more components may be added simultaneously or sequentially.
When using a solvent, any component other than the solvent may be used after being diluted with the solvent, or may be mixed with other components without being diluted with the solvent.
The method of mixing each component is not particularly limited, and for example, a method of mixing by rotating a stirrer, a stirring blade, etc.; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves; can be selected as appropriate.
The temperature and time for adding and mixing each component are not particularly limited, and may be appropriately adjusted according to the components used.
〔保護膜形成用フィルムの厚さ及び形状〕
　本実施形態の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１～１００μｍ、より好ましくは３～７５μｍ、さらに好ましくは５～５０μｍである。
　保護膜形成用フィルムの厚さが上記下限値以上であると、保護膜の保護機能がより良好になる傾向にある。また、保護膜形成用フィルムの厚さが上記上限値以下であると、経済性に優れると共に、保護膜の割断等の加工が容易になる傾向にある。 [Thickness and shape of film for forming protective film]
The thickness of the protective film-forming film of the present embodiment is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 75 μm, still more preferably 5 to 50 μm.
When the thickness of the protective film-forming film is at least the above lower limit, the protective function of the protective film tends to be better. Moreover, when the thickness of the film for forming a protective film is equal to or less than the above upper limit value, the economical efficiency tends to be excellent, and processing such as cutting of the protective film tends to be facilitated.
　本実施形態の保護膜形成用フィルムの形状は、特に限定されないが、円形の半導体ウエハに貼付するという観点からは、平面視で円形であってもよい。保護膜形成用フィルムの形状が平面視で円形である場合、その直径は、例えば、２００ｍｍ（８インチウエハ用）、３００ｍｍ（１２インチウエハ用）等である。 The shape of the protective film-forming film of the present embodiment is not particularly limited, but from the viewpoint of being attached to a circular semiconductor wafer, it may be circular in plan view. When the protective film-forming film has a circular shape in plan view, its diameter is, for example, 200 mm (for 8-inch wafer), 300 mm (for 12-inch wafer), and the like.
〔保護膜形成用フィルムの使用方法〕
　本実施形態の保護膜形成用フィルムは、保護対象物に押圧することによって保護対象物に貼付することができる。押圧する際には、必要に応じて、保護膜形成用フィルムを加熱してもよい。 [How to use protective film forming film]
The protective film-forming film of the present embodiment can be attached to an object to be protected by pressing it against the object to be protected. When pressing, the film for forming a protective film may be heated, if necessary.
　本実施形態の保護膜形成用フィルムを貼付する保護対象物としては、例えば、半導体ウエハ、半導体チップ等が挙げられる。保護膜形成用フィルムを半導体ウエハに貼付する場合、例えば、保護膜形成用フィルムを半導体ウエハの裏面に貼付及び硬化させることによって保護膜付き半導体ウエハを形成し、その後、該保護膜付き半導体ウエハを個片化することによって、裏面に保護膜を有する保護膜付き半導体チップを得ることができる。
　半導体ウエハとしては、例えば、シリコンウエハ；ガリウム砒素、炭化ケイ素、サファイア、タンタル酸リチウム、ニオブ酸リチウム、窒化ガリウム、インジウム燐等のウエハ；ガラスウエハ；等が挙げられる。
　半導体チップとしては、上記半導体ウエハを個片化したものが挙げられる。 Examples of objects to be protected to which the protective film forming film of the present embodiment is attached include semiconductor wafers and semiconductor chips. When a protective film-forming film is attached to a semiconductor wafer, for example, a semiconductor wafer with a protective film is formed by applying and curing the protective film-forming film to the back surface of the semiconductor wafer, and then the semiconductor wafer with a protective film is attached. By singulating, a semiconductor chip with a protective film having a protective film on the back surface can be obtained.
Examples of semiconductor wafers include silicon wafers; wafers of gallium arsenide, silicon carbide, sapphire, lithium tantalate, lithium niobate, gallium nitride, indium phosphide, etc.; glass wafers;
Examples of semiconductor chips include those obtained by singulating the above semiconductor wafer.
　本実施形態の保護膜形成用フィルムを貼付する半導体ウエハ又は半導体チップは、裏面研削後のものであることが好ましい。
　裏面研削後の半導体ウエハ又は半導体チップの厚さは、特に限定されないが、好ましくは５～１５０μｍ、より好ましくは７～１００μｍ、さらに好ましくは１０～４５μｍである。 The semiconductor wafer or semiconductor chip to which the film for forming a protective film of the present embodiment is attached is preferably one after back grinding.
The thickness of the semiconductor wafer or semiconductor chip after back grinding is not particularly limited, but is preferably 5 to 150 μm, more preferably 7 to 100 μm, still more preferably 10 to 45 μm.
＜保護膜形成用フィルムの硬化条件＞
　保護膜形成用フィルムを保護対象物に貼付した後の硬化条件は特に限定されず、保護膜形成用フィルムの種類に応じて、適宜決定すればよい。例えば、保護膜形成用フィルムを熱硬化させる際の加熱温度は、例えば、１００～２００℃であってもよく、１１０～１８０℃であってもよく、１２０～１７０℃であってもよい。また、保護膜形成用フィルムを熱硬化させる際の加熱時間は、例えば、０．５～５時間であってもよく、０．７～４時間であってもよく、１～３時間であってもよい。
　また、エネルギー線硬化性を有する保護膜形成用フィルムに対して紫外線を照射して硬化させる場合、紫外線の照度は、例えば、３０～５００ｍＷ／ｃｍ２であってもよく、４０～４２０ｍＷ／ｃｍ２であってもよく、５０～３４０ｍＷ／ｃｍ２であってもよい。また、紫外線の光量は、例えば、１００～２，０００ｍＪ／ｃｍ２であってもよく、１２５～１，０００ｍＪ／ｃｍ２であってもよく、１５０～５００ｍＪ／ｃｍ２であってもよい。 <Curing Conditions for Protective Film Forming Film>
The curing conditions after the protective film-forming film is attached to the object to be protected are not particularly limited, and may be appropriately determined according to the type of the protective film-forming film. For example, the heating temperature for thermosetting the protective film-forming film may be, for example, 100 to 200°C, 110 to 180°C, or 120 to 170°C. The heating time for thermosetting the protective film-forming film may be, for example, 0.5 to 5 hours, 0.7 to 4 hours, or 1 to 3 hours. good too.
In addition, when the film for forming a protective film having energy ray curability is cured by irradiating it with ultraviolet rays, the illuminance of the ultraviolet rays may be, for example, 30 to 500 mW/cm 2 , and 40 to 420 mW/cm 2 . or 50 to 340 mW/cm 2 . Also, the amount of ultraviolet light may be, for example, 100 to 2,000 mJ/cm 2 , 125 to 1,000 mJ/cm 2 , or 150 to 500 mJ/cm 2 .
　本実施形態の保護膜形成用フィルムを保護対象物に貼付する時期及び硬化させる時期は特に限定されず、本実施形態の保護膜形成用フィルムを適用するプロセスに応じて適宜決定すればよい。
　例えば、半導体ウエハを裏面研削してから個片化することによって半導体チップを製造するプロセスにおいては、半導体ウエハの裏面研削後から、個片化後の半導体チップを基板に実装するまでのいずれかの時期に、保護膜形成用フィルムを半導体ウエハ又は半導体チップに貼付し、硬化させて保護膜を形成すればよい。
　但し、半導体ウエハを個片化する際における破損等を抑制するという観点からは、半導体ウエハの裏面研削後、個片化前の時期に、半導体ウエハの裏面に保護膜形成用フィルムを貼付し、硬化させることによって、保護膜付き半導体ウエハを形成することが好ましい。
　保護膜付き半導体ウエハの個片化方法としては、例えば、ブレードダイシング法、レーザーダイシング法、ステルスダイシング（登録商標）法等の公知の個片化方法を適用することができる。
　保護膜付き半導体ウエハを個片化することによって、保護膜付き半導体チップが得られる。 The timing of attaching the protective film-forming film of the present embodiment to an object to be protected and the timing of curing are not particularly limited, and may be appropriately determined according to the process for applying the protective film-forming film of the present embodiment.
For example, in the process of manufacturing semiconductor chips by grinding the backside of a semiconductor wafer and then singulating it, any process from grinding the backside of the semiconductor wafer to mounting the singulated semiconductor chips on a substrate may be performed. At this time, the film for forming a protective film may be attached to a semiconductor wafer or a semiconductor chip and cured to form a protective film.
However, from the viewpoint of suppressing breakage or the like when the semiconductor wafer is singulated, after the backside of the semiconductor wafer is ground and before singulation, a film for forming a protective film is attached to the back surface of the semiconductor wafer, Preferably, a semiconductor wafer with a protective film is formed by curing.
Known singulation methods such as a blade dicing method, a laser dicing method, and a stealth dicing (registered trademark) method can be applied as a method for singulating the semiconductor wafer with a protective film.
A semiconductor chip with a protective film is obtained by singulating the semiconductor wafer with a protective film.
〔保護膜形成用フィルムの製造方法〕
　保護膜形成用フィルムは、例えば、保護膜形成用樹脂組成物をフィルム状に製膜することによって製造することができる。具体的には、例えば、保護膜形成用樹脂組成物を、剥離フィルム等の支持シート上に塗工し、必要に応じて乾燥することによって、支持シート上に保護膜形成用フィルムを形成することができる。 [Method for producing protective film-forming film]
The protective film-forming film can be produced, for example, by forming a protective film-forming resin composition into a film. Specifically, for example, the protective film-forming resin composition is applied onto a support sheet such as a release film, and dried as necessary to form a protective film-forming film on the support sheet. can be done.
［第一態様の保護膜形成用複合シート］
　本実施形態の第一態様の保護膜形成用複合シートは、本実施形態の保護膜形成用フィルムが、２枚の剥離フィルムに挟持された構成を有する。
　なお、本明細書において「剥離フィルム」とは、剥がれる機能を有するフィルムを意味し、保護対象物に貼付する前の保護膜形成用フィルムを保護するために、保護膜形成用フィルムの表面に貼り付けられるものである。
　第一態様の保護膜形成用複合シートが有する保護膜形成用フィルムの好適な態様は上記した通りである。 [Composite sheet for forming a protective film of the first embodiment]
The protective film-forming composite sheet of the first aspect of the present embodiment has a structure in which the protective film-forming film of the present embodiment is sandwiched between two release films.
In the present specification, the term “peeling film” means a film having a function to be peeled off, and in order to protect the film for forming a protective film before being attached to an object to be protected, it is attached to the surface of the film for forming a protective film. It can be attached.
Preferred aspects of the protective film-forming film included in the protective film-forming composite sheet of the first aspect are as described above.
＜第一態様の保護膜形成用複合シートの構成＞
　図１は、第一態様の保護膜形成用複合シートの一例を模式的に示す断面図である。なお、以下の説明で用いる図は、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率等が実際と同じであるとは限らない。 <Structure of Composite Sheet for Forming Protective Film of First Aspect>
FIG. 1 is a cross-sectional view schematically showing an example of the protective film-forming composite sheet of the first embodiment. It should be noted that the drawings used in the following description may show the essential parts in an enlarged manner for convenience, and the dimensional ratios and the like of the respective constituent elements are not necessarily the same as the actual ones.
　図１に示す保護膜形成用複合シート１は、保護膜形成用フィルム１０の一方の表面１０ａ上に第１剥離フィルム１１１を有し、他方の表面１０ｂ上に第２剥離フィルム１１２を有する。
　このような構成を有する保護膜形成用複合シートは、例えば、ロール状として保管するのに好適である。
　第１剥離フィルム１１１及び第２剥離フィルム１１２は、互いに同じものであってもよいし、異なるものであってもよい。例えば、第１剥離フィルム１１１及び第２剥離フィルム１１２は、保護膜形成用フィルム１０から剥離させるときに必要な剥離力が互いに異なるものとしてもよい。 The protective film-forming composite sheet 1 shown in FIG. 1 has a first release film 111 on one surface 10a of the protective film-forming film 10 and a second release film 112 on the other surface 10b.
A composite sheet for forming a protective film having such a structure is suitable for storage as a roll, for example.
The first release film 111 and the second release film 112 may be the same or different. For example, the first peeling film 111 and the second peeling film 112 may have different peeling forces required when peeling them from the protective film forming film 10 .
＜剥離フィルム＞
　保護膜形成用複合シートに使用できる剥離フィルムとしては、例えば、剥離フィルム用の基材上に剥離剤を塗布したものが挙げられる。
　剥離フィルム用の基材としては、例えば、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の透明フィルム；これらの架橋フィルム；これらを着色したフィルム；不透明フィルム；上質紙、グラシン紙、クラフト紙等の紙類；等が挙げられる。これらは、単層で用いてもよく、２層以上を積層して用いてもよい。 <Release film>
Examples of the release film that can be used in the protective film-forming composite sheet include a release film base material coated with a release agent.
Base materials for release films include, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, poly Butylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylate copolymer film, polystyrene film, polycarbonate film, transparent films such as polyimide films and fluororesin films; crosslinked films thereof; films obtained by coloring these films; opaque films; These may be used as a single layer or as a laminate of two or more layers.
　剥離剤としては、例えば、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー；長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂；等が挙げられる。剥離剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins; long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins; The release agent may be used alone or in combination of two or more.
　剥離フィルムの厚さは、特に限定されないが、好ましくは１０～５００μｍ、より好ましくは１５～３００μｍ、さらに好ましくは２０～１００μｍである。
　剥離フィルムの厚さが上記下限値以上であると、保護膜形成用複合シートの耐変形性がより良好になる傾向にある。また、剥離フィルムの厚さが上記上限値以下であると、適度な柔軟性が得られ、保護膜形成用複合シートの取り扱い性がより良好になる傾向にある。 Although the thickness of the release film is not particularly limited, it is preferably 10 to 500 μm, more preferably 15 to 300 μm, still more preferably 20 to 100 μm.
When the thickness of the release film is at least the above lower limit, the deformation resistance of the protective film-forming composite sheet tends to be better. Moreover, when the thickness of the release film is equal to or less than the above upper limit value, appropriate flexibility is obtained, and the handleability of the protective film-forming composite sheet tends to be better.
＜第一態様の保護膜形成用複合シートの製造方法＞
　第一態様の保護膜形成用複合シートは、上記した〔保護膜形成用フィルムの製造方法〕に準拠して製造することができる。具体的には、例えば、保護膜形成用樹脂組成物を塗工する対象を、剥離フィルムの剥離処理面として、剥離フィルム上に保護膜形成用フィルムを形成した後、該保護膜形成用フィルムの露出面に対して、別の剥離フィルムの剥離処理面を貼付することによって、第一態様の保護膜形成用複合シートを製造することができる。 <Method for producing protective film-forming composite sheet of first embodiment>
The protective film-forming composite sheet of the first aspect can be produced according to the above-described [Production method of protective film-forming film]. Specifically, for example, the object to be coated with the protective film-forming resin composition is the release-treated surface of the release film, and after forming the protective film-forming film on the release film, the protective film-forming film is applied. By attaching the release-treated surface of another release film to the exposed surface, the protective film-forming composite sheet of the first aspect can be produced.
［第二態様の保護膜形成用複合シート］
　本実施形態の第二態様の保護膜形成用複合シートは、基材と、粘着剤層と、本実施形態の保護膜形成用フィルムと、をこの順で有する、保護膜形成用複合シートである。
　第二態様の保護膜形成用複合シートが有する保護膜形成用フィルムの好適な態様は上記した通りである。 [Composite sheet for forming a protective film of the second embodiment]
The protective film-forming composite sheet of the second aspect of the present embodiment is a protective film-forming composite sheet having a substrate, an adhesive layer, and the protective film-forming film of the present embodiment in this order. .
Preferred aspects of the protective film-forming film included in the protective film-forming composite sheet of the second embodiment are as described above.
　第二態様の保護膜形成用複合シートは、保護膜形成用フィルムに加え、基材及び粘着剤層を有する。そのため、例えば、第二態様の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及び硬化させて保護膜を形成した場合、粘着剤層を介して基材によって支持された保護膜付き半導体ウエハが得られる。粘着剤層を介して基材によって支持された保護膜付き半導体ウエハは、例えば、基材側の表面を固定して個片化することが可能である。すなわち、第二態様の保護膜形成用複合シートは、保護膜形成用フィルムと、基材及び粘着剤層を有するダイシングシートと、が一体化されたものとして使用することができる。 The protective film-forming composite sheet of the second aspect has a substrate and an adhesive layer in addition to the protective film-forming film. Therefore, for example, when the film for forming a protective film of the composite sheet for forming a protective film of the second embodiment is adhered to a semiconductor wafer and cured to form a protective film, the protective film is supported by the substrate via the pressure-sensitive adhesive layer. A semiconductor wafer is obtained. A semiconductor wafer with a protective film supported by a substrate via an adhesive layer can be singulated by fixing the surface on the substrate side, for example. That is, the protective film-forming composite sheet of the second aspect can be used as one in which a protective film-forming film and a dicing sheet having a substrate and an adhesive layer are integrated.
＜第二態様の保護膜形成用複合シートの構成＞
　第二態様の保護膜形成用複合シートは、基材、粘着剤層及び保護膜形成用フィルムのみからなるものであってもよいが、基材、粘着剤層及び保護膜形成用フィルム以外のその他の構成部材を有していてもよい。その他の構成部材としては、例えば、保護膜形成用フィルムの粘着剤層とは反対側の面に積層される剥離フィルム等が挙げられる。
　第二態様の保護膜形成用複合シートが有していてもよい剥離フィルムの好適な態様は上記した通りである。 <Structure of Composite Sheet for Forming Protective Film of Second Aspect>
The protective film-forming composite sheet of the second aspect may consist of only the base material, the adhesive layer and the protective film-forming film, but other than the base material, the pressure-sensitive adhesive layer and the protective film-forming film You may have a component of. Other constituent members include, for example, a release film laminated on the surface of the protective film-forming film opposite to the pressure-sensitive adhesive layer.
Preferred aspects of the release film that the protective film-forming composite sheet of the second aspect may have are as described above.
　図２及び図３は、第二態様の保護膜形成用複合シートの例を模式的に示す断面図である。
　なお、各図において、既に説明済みの図に示すものと同じ構成要素には、その説明済みの図の場合と同じ符号を付し、その詳細な説明は省略する。 2 and 3 are cross-sectional views schematically showing examples of the protective film-forming composite sheet of the second embodiment.
In each figure, the same constituent elements as those shown in already explained figures are denoted by the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.
　図２に示す保護膜形成用複合シート１Ａは、基材１２上に粘着剤層１３を有し、粘着剤層１３上に保護膜形成用フィルム１０を有している。保護膜形成用複合シート１Ａは、さらに保護膜形成用フィルム１０の表面１０ａ（上面）と、粘着剤層１３の表面１３ａ（上面）とに、剥離フィルム１１が積層されている。保護膜形成用複合シート１Ａは、剥離フィルム１１が取り除かれた状態で、保護膜形成用フィルム１０の表面１０ａのうち、中央側の一部の領域に半導体ウエハ（図示略）の裏面が貼付され、さらに、保護膜形成用フィルム１０の周縁部近傍の領域が、リングフレーム等の治具に貼付されて、使用される。 The protective film-forming composite sheet 1A shown in FIG. In the protective film-forming composite sheet 1A, a release film 11 is further laminated on the surface 10a (upper surface) of the protective film-forming film 10 and the surface 13a (upper surface) of the pressure-sensitive adhesive layer 13 . In the protective film-forming composite sheet 1A, the back surface of a semiconductor wafer (not shown) is attached to a central part of the front surface 10a of the protective film-forming film 10 with the release film 11 removed. Furthermore, the area near the peripheral edge of the protective film forming film 10 is used by being attached to a jig such as a ring frame.
　図３に示す保護膜形成用複合シート１Ｂは、粘着剤層１３の表面１３ａの一部、すなわち、周縁部近傍の領域に治具用接着剤層１４が積層され、保護膜形成用フィルム１０の表面１０ａ（上面）と、治具用接着剤層１４の表面１４ａ（上面）とに、剥離フィルム１１が積層されていること以外は、図２に示す保護膜形成用複合シート１Ａと同じものである。
　治具用接着剤層１４は、例えば、接着剤成分を含有する単層構造のものであってもよいし、芯材となるシートの両面に接着剤成分を含有する層が積層された複数層構造のものであってもよい。
　保護膜形成用複合シート１Ｂは、剥離フィルム１１が取り除かれた状態で、保護膜形成用フィルム１０の表面１０ａに半導体ウエハ（図示略）の裏面が貼付され、さらに、治具用接着剤層１４の表面１４ａのうち上面が、リングフレーム等の治具に貼付されて、使用される。 In the protective film-forming composite sheet 1B shown in FIG. It is the same as the protective film forming composite sheet 1A shown in FIG. be.
The jig adhesive layer 14 may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material. It may be structural.
In the protective film forming composite sheet 1B, the back surface of a semiconductor wafer (not shown) is adhered to the front surface 10a of the protective film forming film 10 in a state in which the release film 11 is removed, and an adhesive layer 14 for a jig is attached. The upper surface of the surface 14a of is attached to a jig such as a ring frame for use.
　本実施形態の第二態様の保護膜形成用複合シートは、図２及び図３に示すものに限定されず、本実施形態における効果を損なわない範囲内において、図２及び図３に示すものの一部の構成が変更又は削除されたもの、これまでに説明したものにさらに他の構成が追加されたものであってもよい。 The protective film-forming composite sheet of the second aspect of the present embodiment is not limited to those shown in FIGS. The configuration of the parts may be changed or deleted, or other configurations may be added to those described above.
＜基材＞
　基材の構成材料としては、例えば、各種樹脂が挙げられる。
　基材を構成する樹脂としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のポリエチレン；ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン；エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体、エチレン－ノルボルネン共重合体等のエチレン系共重合体（モノマーとしてエチレンを用いて得られた共重合体）；ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂（モノマーとして塩化ビニルを用いて得られた樹脂）；ポリスチレン；ポリシクロオレフィン；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン－２，６－ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル；２種以上のポリエステルの共重合体；ポリ（メタ）アクリル酸エステル；ポリウレタン；ポリウレタンアクリレート；ポリイミド；ポリアミド；ポリカーボネート；フッ素樹脂；ポリアセタール；変性ポリフェニレンオキシド；ポリフェニレンスルフィド；ポリスルホン；ポリエーテルケトン；これらの樹脂の１種又は２種以上が架橋した架橋樹脂；これらの樹脂の１種又は２種以上を用いたアイオノマー等の変性樹脂等が挙げられる。基材を構成する樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。
　これらの中でも、耐熱性の観点から、ポリプロピレン、ポリブチレンテレフタレートが好ましい。 <Base material>
Examples of constituent materials of the base material include various resins.
Examples of the resin constituting the base material include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin, and the like. Polyolefins other than polyethylene; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (Copolymer obtained using ethylene as a monomer); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (Resins obtained using vinyl chloride as a monomer); Polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylic ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Crosslinked resins obtained by crosslinking two or more of these resins; and modified resins such as ionomers using one or more of these resins. One of the resins constituting the substrate may be used alone, or two or more of them may be used in combination.
Among these, polypropylene and polybutylene terephthalate are preferable from the viewpoint of heat resistance.
　基材は、上記した樹脂以外にも、例えば、充填材、着色剤、帯電防止剤、酸化防止剤、有機滑剤、触媒、軟化剤（可塑剤）等の公知の各種添加剤を含有していてもよい。 In addition to the resins described above, the substrate contains various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers). good too.
　基材は、粘着剤層等の他の層との密着性を向上させるために、表面処理を施されたものであってもよい。
　表面処理の方法としては、例えば、サンドブラスト処理、溶剤処理等による凹凸化処理；コロナ放電処理、電子線照射処理、プラズマ処理、オゾン・紫外線照射処理、火炎処理、クロム酸処理、熱風処理等の酸化処理；プライマー処理；等が挙げられる。これらの中でも、保護膜形成用複合シートをブレードダイシングに適用する場合におけるブレードの摩擦による基材の断片の発生が抑制されるという観点から、電子線照射処理を施されたものが好ましい。 The base material may be subjected to a surface treatment in order to improve adhesion with other layers such as an adhesive layer.
Examples of surface treatment methods include sandblasting, unevenness treatment by solvent treatment, etc.; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and other oxidation. treatment; primer treatment; and the like. Among these, those subjected to electron beam irradiation treatment are preferable from the viewpoint of suppressing the generation of fragments of the base material due to blade friction when the composite sheet for forming a protective film is applied to blade dicing.
　基材は、１層のみからなるものであってもよく、２層以上の複数層からなるものであってもよい。基材が複数層からなる場合、複数層を構成する各層は、互いに同一であってもよく、異なっていてもよい。
　さらに、基材は、例えば、帯電防止コート層、保護膜形成用複合シートを重ね合わせて保存する際に、基材が他のシートに接着すること、基材が吸着テーブルに接着することを防止するための層等を有するものであってもよい。 The substrate may be composed of only one layer, or may be composed of multiple layers of two or more layers. When the substrate is composed of multiple layers, each layer constituting the multiple layers may be the same as or different from each other.
Furthermore, the base material prevents the base material from adhering to other sheets and the base material from adhering to the adsorption table when the antistatic coating layer and the composite sheet for forming a protective film are stacked and stored, for example. It may have a layer or the like for doing.
　基材の厚さは、特に限定されないが、好ましくは４０～３００μｍ、より好ましくは５０～２００μｍ、さらに好ましくは６０～１５０μｍである。
　基材の厚さが上記範囲であると、保護膜形成用複合シートの可撓性及び貼付性がより良好になる傾向にある。 Although the thickness of the substrate is not particularly limited, it is preferably 40 to 300 μm, more preferably 50 to 200 μm, still more preferably 60 to 150 μm.
When the thickness of the substrate is within the above range, the composite sheet for protective film formation tends to have better flexibility and sticking properties.
＜粘着剤層＞
　粘着剤層は、基材と保護膜形成用フィルムとの間に設けられる、粘着性を有する層である。
　粘着剤層は、１層のみからなるものであってもよく、２層以上の複数層からなるものであってもよい。粘着剤層が複数層からなる場合、複数層を構成する各層は、互いに同一であってもよく、異なっていてもよい。 <Adhesive layer>
The adhesive layer is a layer having adhesiveness provided between the substrate and the film for forming a protective film.
The pressure-sensitive adhesive layer may consist of only one layer, or may consist of multiple layers of two or more layers. When the pressure-sensitive adhesive layer consists of multiple layers, each layer constituting the multiple layers may be the same or different.
　粘着剤層を構成する粘着性樹脂としては、例えば、アクリル樹脂、ウレタン樹脂、ゴム系樹脂、シリコーン樹脂、エポキシ樹脂、ポリビニルエーテル樹脂、ポリカーボネート樹脂、エステル系樹脂等の粘着性樹脂が挙げられる。これらの粘着性樹脂が、２種以上の構成単位を有する共重合体である場合、当該共重合体の形態は、特に限定されず、ブロック共重合体、ランダム共重合体及びグラフト共重合体のいずれであってもよい。
　これらの中でも、優れた粘着力を発現させるという観点から、アクリル樹脂が好ましい。 Examples of adhesive resins constituting the adhesive layer include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether resins, polycarbonate resins, and ester resins. When these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and block copolymers, random copolymers and graft copolymers Either can be used.
Among these, acrylic resins are preferable from the viewpoint of exhibiting excellent adhesive strength.
　なお、本実施形態において、「粘着性樹脂」とは、粘着性を有する樹脂と、接着性を有する樹脂と、の両方を含む概念であり、例えば、樹脂自体が粘着性を有するものだけでなく、添加剤等の他の成分との併用によって粘着性を示す樹脂；熱、水等のトリガーの存在によって接着性を示す樹脂；等も含む。 In the present embodiment, the "adhesive resin" is a concept that includes both a resin having adhesiveness and a resin having adhesiveness. , resins that exhibit adhesiveness when used in combination with other components such as additives; resins that exhibit adhesiveness in the presence of triggers such as heat and water; and the like.
　粘着剤層の厚さは、特に限定されないが、好ましくは３～３０μｍ、より好ましくは４～２０μｍ、さらに好ましくは５～１７μｍである。
　粘着剤層の厚さが上記下限値以上であると、タック及び粘着力がより良好になる傾向にある。また、粘着剤層の厚さが上記上限値以下であると、保護膜形成用複合シートをブレードダイシングに適用する場合におけるブレードダイシング適性及びピックアップ適性がより良好になる傾向にある。 Although the thickness of the pressure-sensitive adhesive layer is not particularly limited, it is preferably 3 to 30 μm, more preferably 4 to 20 μm, still more preferably 5 to 17 μm.
When the thickness of the pressure-sensitive adhesive layer is at least the above lower limit, the tack and adhesive strength tend to be better. Further, when the thickness of the pressure-sensitive adhesive layer is equal to or less than the above upper limit, there is a tendency that blade dicing aptitude and pick-up aptitude when applying the composite sheet for forming a protective film to blade dicing become better.
　粘着剤層は、エネルギー線硬化性粘着剤を用いて形成されたものでもよいし、非エネルギー線硬化性粘着剤を用いて形成されたものでもよい。なお、非エネルギー線硬化性粘着剤には、熱硬化性粘着剤及び非硬化性粘着剤が包含される。 The adhesive layer may be formed using an energy ray-curable adhesive or may be formed using a non-energy ray-curable adhesive. The non-energy ray-curable adhesive includes thermosetting adhesives and non-curable adhesives.
＜第二態様の保護膜形成用複合シートの製造方法＞
　第二態様の保護膜形成用複合シートは、保護膜形成用複合シートを構成する各層を、対応する位置関係となるように順次積層することで製造できる。各層は、上記した〔保護膜形成用フィルムの製造方法〕に準拠して形成することができる。
　具体的には、例えば、基材に積層された粘着剤層の表面に保護膜形成用樹脂組成物を塗工して、粘着剤層上に保護膜形成用フィルムを形成してもよいし、予め剥離フィルムの剥離処理面上に保護膜形成用フィルムを形成しておき、該保護膜形成用フィルムの露出面を基材に積層された粘着剤層の表面と貼り合わせて、保護膜形成用フィルムを粘着剤層上に積層してもよい。
　基材に粘着剤層を積層する場合も同様に、粘着剤層を形成するため組成物を基材の表面に塗工してもよいし、剥離フィルムの剥離処理面上に形成した粘着剤層の露出面を、基材の表面と貼り合わせてから、剥離フィルムを除去してもよい。第二態様の保護膜形成用複合シートが、中間層等の任意の層を有する場合も、上記の方法に準じて必要な位置に当該任意の層を設ければよい。 <Method for producing composite sheet for forming protective film according to second embodiment>
The protective film-forming composite sheet of the second aspect can be produced by sequentially laminating each layer constituting the protective film-forming composite sheet so as to have a corresponding positional relationship. Each layer can be formed in conformity with the above-described [Production method of film for forming protective film].
Specifically, for example, a protective film-forming resin composition may be applied to the surface of the pressure-sensitive adhesive layer laminated on the substrate to form a protective film-forming film on the pressure-sensitive adhesive layer, A film for forming a protective film is formed in advance on the release-treated surface of the release film, and the exposed surface of the film for forming a protective film is attached to the surface of the adhesive layer laminated on the substrate to form a protective film. A film may be laminated onto the adhesive layer.
Similarly, in the case of laminating an adhesive layer on a substrate, the composition may be applied to the surface of the substrate to form the adhesive layer, or the adhesive layer formed on the release-treated surface of the release film. The release film may be removed after the exposed surface of is attached to the surface of the substrate. When the protective film-forming composite sheet of the second embodiment has arbitrary layers such as an intermediate layer, the arbitrary layers may be provided at required positions according to the above method.
［保護膜付き半導体チップ］
　本実施形態の保護膜付き半導体チップは、本実施形態の保護膜形成用フィルムの硬化物である保護膜を有する、保護膜付き半導体チップである。
　本実施形態の保護膜付き半導体チップが有する保護膜の形成に用いられる保護膜形成用フィルム及び該保護膜形成用フィルムから形成される保護膜、並びに半導体チップの好適な態様についての説明は、上記した通りである。
　半導体チップの平面視における大きさは、特に限定されないが、好ましくは６００ｍｍ２未満、より好ましくは４００ｍｍ２未満、さらに好ましくは３００ｍｍ２未満である。なお、平面視とは厚さ方向に見ることをいう。
　半導体チップの平面視における形状は、方形であってもよく、矩形等の細長形状であってもよい。
　本実施形態の保護膜付き半導体チップは、本実施形態の保護膜形成用フィルムの使用方法において説明した方法によって製造することができる。 [Semiconductor chip with protective film]
The protective film-attached semiconductor chip of the present embodiment is a protective film-attached semiconductor chip having a protective film that is a cured product of the protective film-forming film of the present embodiment.
The protective film-forming film used for forming the protective film of the semiconductor chip with a protective film according to the present embodiment, the protective film formed from the protective film-forming film, and the preferred aspects of the semiconductor chip are described above. As I said.
Although the size of the semiconductor chip in plan view is not particularly limited, it is preferably less than 600 mm 2 , more preferably less than 400 mm 2 , and still more preferably less than 300 mm 2 . In addition, planar view means viewing in a thickness direction.
The shape of the semiconductor chip in plan view may be a square or an elongated shape such as a rectangle.
The semiconductor chip with a protective film of this embodiment can be manufactured by the method described in the method of using the film for forming a protective film of this embodiment.
［半導体装置］
　本実施形態の半導体装置は、本実施形態の保護膜付き半導体チップを有する、半導体装置である。
　本実施形態の半導体装置としては、例えば、本実施形態の保護膜付き半導体チップを、回路を有する基板にフリップチップ接続してなる半導体パッケージ等が挙げられる。 [Semiconductor device]
The semiconductor device of this embodiment is a semiconductor device having the semiconductor chip with the protective film of this embodiment.
Examples of the semiconductor device of this embodiment include a semiconductor package formed by flip-chip connecting the semiconductor chip with a protective film of this embodiment to a substrate having a circuit.
　本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.
［質量平均分子量（Ｍｗ）］
　ゲル浸透クロマトグラフ装置（東ソー株式会社製、製品名「ＨＬＣ－８３２０ＧＰＣ」）を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
（測定条件）
・カラム：「ＴＳＫ　ｇｕａｒｄ　ｃｏｌｕｍｎ　ＳｕｐｅｒＨ－Ｈ」「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＭ－Ｈ」「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨＭ－Ｈ」「ＴＳＫ　ｇｅｌ　ＳｕｐｅｒＨ２０００」（いずれも東ソー株式会社製）を順次連結したもの
・カラム温度：４０℃
・展開溶媒：テトラヒドロフラン
・流速：１．０ｍＬ／ｍｉｎ [Mass average molecular weight (Mw)]
Using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name “HLC-8320GPC”), measurement was performed under the following conditions, and the values measured in terms of standard polystyrene were used.
(Measurement condition)
・ Column: “TSK guard column SuperH-H”, “TSK gel SuperHM-H”, “TSK gel SuperHM-H”, “TSK gel SuperH2000” (both manufactured by Tosoh Corporation) are sequentially connected ・Column temperature: 40 ° C.
・Developing solvent: tetrahydrofuran ・Flow rate: 1.0 mL/min
［各層の厚さ］
　株式会社テクロック製の定圧厚さ測定器（型番：「ＰＧ－０２Ｊ」、標準規格：ＪＩＳＫ６７８３、Ｚ１７０２、Ｚ１７０９に準拠）を用いて、２３℃にて、任意の５箇所において厚さを測定し、測定値の平均値を算出した。 [Thickness of each layer]
Using a constant pressure thickness measuring instrument manufactured by Teclock Co., Ltd. (model number: "PG-02J", standard specifications: compliant with JISK6783, Z1702, Z1709), the thickness is measured at any five points at 23 ° C., An average value of the measured values was calculated.
［貯蔵弾性率Ｅ’の測定方法］
　各例で得られた両面剥離フィルム付き保護膜形成用フィルムから剥離シートを剥がし、保護膜形成用フィルムを厚さ２００μｍになるように複数層積層した。得られた保護膜形成用フィルムの積層体から、平面視で３０ｍｍ×４ｍｍの矩形（厚さ：２００μｍ）を裁断し、これを貯蔵弾性率Ｅ’の測定試料とした。該測定試料を測定対象として、動的粘弾性測定装置（株式会社オリエンテック製、商品名「Ｒｈｅｏｖｉｂｒｏｎ　ＤＤＶ－ＩＩ－ＥＰ１」）を用いて、測定モード：引張モード、周波数：１１Ｈｚ、測定温度範囲：－２０～１５０℃、昇温速度：３℃／ｍｉｎの条件で貯蔵弾性率Ｅ’を測定した。測定時はサンプルの長辺の両端から５ｍｍまでを固定治具で固定し、固定治具間距離２０ｍｍにて測定を行った。
　測定によって得られた２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値及び該最小値を示す温度、２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最大値及び該最大値を示す温度、８０℃における貯蔵弾性率Ｅ’（８０）と１３０℃における貯蔵弾性率Ｅ’（１３０）との比〔Ｅ’（８０）／Ｅ’（１３０）〕を表１に示す。なお、貯蔵弾性率Ｅ’（８０）及び貯蔵弾性率Ｅ’（１３０）の値を特定する際、８０．０℃丁度又は１３０．０℃丁度における貯蔵弾性率Ｅ’の値が存在しない場合は、上記〔貯蔵弾性率Ｅ’（８０）及び貯蔵弾性率Ｅ’（１３０）の特定方法〕に記載の方法に従って、各々の値を特定した。 [Method for measuring storage modulus E']
The release sheet was peeled off from the film for forming a protective film with a double-sided release film obtained in each example, and a plurality of films for forming a protective film were laminated so as to have a thickness of 200 μm. A rectangle (thickness: 200 μm) of 30 mm×4 mm in plan view was cut from the laminate of the protective film-forming film thus obtained, and this was used as a measurement sample for the storage elastic modulus E′. Using the measurement sample as a measurement object, a dynamic viscoelasticity measurement device (manufactured by Orientec Co., Ltd., trade name "Rheovibron DDV-II-EP1") was used, measurement mode: tensile mode, frequency: 11 Hz, measurement temperature range: The storage elastic modulus E' was measured under conditions of -20 to 150°C and a heating rate of 3°C/min. At the time of measurement, the sample was fixed by fixing jigs up to 5 mm from both ends of the long side, and the measurement was performed with a distance between the fixing jigs of 20 mm.
The minimum value of the storage elastic modulus E 'in the temperature range of 23 to 150 ° C. obtained by measurement and the temperature indicating the minimum value, the maximum value of the storage elastic modulus E 'in the temperature range of 23 to 150 ° C. and the maximum value Table 1 shows the ratio [E'(80)/E'(130)] of the storage modulus E'(80) at 80.degree. C. and the storage modulus E'(130) at 130.degree. When specifying the values of storage elastic modulus E' (80) and storage elastic modulus E' (130), if there is no value of storage elastic modulus E' at exactly 80.0 ° C. or 130.0 ° C. Each value was specified according to the method described in [Method for specifying storage elastic modulus E′(80) and storage elastic modulus E′(130)] above.
［銅箔ピール強度の測定方法］
　各例で得られた両面剥離フィルム付き保護膜形成用フィルムから軽剥離フィルムを剥離し、表出した保護膜形成用フィルムの表面を、シリコンウエハ片（２，０００番研磨面を有する厚さ３５０μｍのシリコンウエハ）の研磨面に７０℃に加熱したロールラミネーターを用いて貼付した。次いで、貼付した保護膜形成用フィルムのシリコンウエハとは反対側の表面から重剥離フィルムを剥離し、表出した表面保護膜形成用フィルムの表面に、長辺５０ｍｍ×短辺１０ｍｍ×厚さ１５０μｍの銅箔を、７０℃に加熱したロールラミネーターを用いて貼付した。このとき、銅箔の長辺の一方の端部１０ｍｍは保護膜形成用フィルムに貼付しない未貼付部として残した。次に、１４０℃で２時間加熱することによって保護膜形成用フィルムを熱硬化させ、シリコンウエハ、保護膜形成用フィルムの硬化物である保護膜及び銅箔が、これらの厚さ方向に積層された積層体を形成し、これを銅箔ピール強度の測定試料とした。
　上記で得られた測定試料を、万能引張試験機（株式会社島津製作所製、商品名「ＡＧ－ＸＰｌｕｓ」）に取り付け、上記銅箔の未貼付部を掴み具で把持し、該銅箔を、引き剥がし速度５０ｍｍ／分の条件で９０°方向に引き剥がすことによって銅箔ピール強度を取得した。 [Method for measuring copper foil peel strength]
The light release film was peeled off from the protective film forming film with a double-sided release film obtained in each example, and the exposed surface of the protective film forming film was treated with a piece of silicon wafer (thickness 350 μm having a No. 2,000 polished surface). (silicon wafer) using a roll laminator heated to 70°C. Next, the heavy release film was peeled off from the surface of the attached protective film forming film opposite to the silicon wafer, and a film of 50 mm long side × 10 mm short side × 150 µm thick was applied to the exposed surface of the film for forming a surface protective film. was applied using a roll laminator heated to 70°C. At this time, 10 mm of one end of the long side of the copper foil was left as an unattached portion where the film for forming a protective film was not attached. Next, the film for forming a protective film is thermally cured by heating at 140° C. for 2 hours, and a silicon wafer, a protective film which is a cured product of the film for forming a protective film, and a copper foil are laminated in their thickness direction. A laminated body was formed, and this was used as a measurement sample for the copper foil peel strength.
The measurement sample obtained above is attached to a universal tensile tester (manufactured by Shimadzu Corporation, trade name "AG-XPlus"), the unattached portion of the copper foil is gripped with a grip, and the copper foil is The peel strength of the copper foil was obtained by peeling it off in the 90° direction at a peeling speed of 50 mm/min.
［難燃性の評価方法］
　各例で得られた両面剥離フィルム付き保護膜形成用フィルムを、１４０℃で２時間加熱することによって保護膜形成用フィルムを熱硬化させ、保護膜形成用フィルムの硬化物である保護膜を形成し、長辺２００ｍｍ×短辺５０ｍｍの大きさに裁断し、該保護膜の両面の剥離フィルムを剥離した。
　得られた保護膜を、温度２３℃、相対湿度５０％の環境下で４８時間保管した後、短辺方向を直径１２．７ｍｍの円筒状の棒に巻き、長辺方向の一方の端部から１２５ｍｍの位置に標線を設け、一方の端部と上記標線との間の部分（７５ｍｍの部分）をテープで留めて円筒状の保護膜を作製した後、棒を引き抜いた。
　次いで、円筒状の保護膜を、上記テープで留めた側の端部を上側にして、該上側の端部から空気が抜けないように、該端部を押し潰して偏平に閉合させた状態でクランプに垂直に取り付け、米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）のＵＬ９４ＶＴＭ試験（薄手材料垂直燃焼試験）に準拠して、接炎試験を行った。具体的には、円筒状の保護膜の下端から１０ｍｍの位置にバーナーの筒を設置し、円筒状の保護膜の下端の中央において２０ｍｍの青色炎による３秒間の１回目の接炎試験を行い、炎が消えた場合はすぐに同じ条件で２回目の接炎試験を行い、以下の基準にて評価した。
　Ａ：１回目及び２回目の接炎試験において炎が標線（１２５ｍｍ）を超えなかった。
　Ｆ：１回目又は２回目の接炎試験において炎が標線（１２５ｍｍ）を超えた。 [Method for evaluating flame retardancy]
The film for forming a protective film with a double-sided release film obtained in each example is heated at 140° C. for 2 hours to thermally cure the film for forming a protective film to form a protective film that is a cured product of the film for forming a protective film. Then, it was cut into a size of 200 mm long side×50 mm short side, and the release films on both sides of the protective film were peeled off.
The resulting protective film was stored for 48 hours in an environment of a temperature of 23° C. and a relative humidity of 50%. A marked line was provided at a position of 125 mm, and a portion (75 mm portion) between one end and the marked line was taped to prepare a cylindrical protective film, after which the bar was pulled out.
Next, the cylindrical protective film is placed with the taped end facing upward, and the end is crushed and closed flat so that air does not escape from the upper end. Attached vertically to the clamp, UL94 VTM test (thin material vertical burning test) of UL94 test (combustion test of plastic materials for equipment parts) stipulated by Underwriters Laboratories (UL) in the United States, flame contact test did Specifically, a burner cylinder was installed at a position 10 mm from the lower end of the cylindrical protective film, and the first flame contact test was performed for 3 seconds with a 20 mm blue flame at the center of the lower end of the cylindrical protective film. When the flame was extinguished, a second flame contact test was immediately conducted under the same conditions and evaluated according to the following criteria.
A: The flame did not exceed the marked line (125 mm) in the first and second flame contact tests.
F: The flame exceeded the marked line (125 mm) in the first or second flame contact test.
［保護膜形成用フィルムの製造］
実施例１～６、比較例１～３
（保護膜形成用樹脂組成物の製造）
　表１に示す各成分を、表１に記載の配合組成に従って、メチルエチルケトン、トルエン及び酢酸エチルの混合溶媒に溶解又は分散させた後、２３℃で撹拌することによって、固形分濃度６２質量％の保護膜形成用樹脂組成物を得た。 [Production of film for forming protective film]
Examples 1-6, Comparative Examples 1-3
(Production of protective film-forming resin composition)
Each component shown in Table 1 is dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate according to the formulation shown in Table 1, and then stirred at 23 ° C. to protect the solid content concentration of 62% by mass. A film-forming resin composition was obtained.
（保護膜形成用フィルムの作製）
　重剥離フィルム（リンテック株式会社製、商品名「ＳＰ－ＰＥＴ５０２１５０」、厚さ５０μｍのポリエチレンテレフタレート製フィルムの片面をシリコーン樹脂で剥離処理したもの）の剥離処理面に、上記で得られた保護膜形成用樹脂組成物をナイフコーターを用いて塗工し、１００℃で２分間乾燥させて、重剥離フィルム上に厚さ２５μｍの保護膜形成用フィルムを形成した。その後、保護膜形成用フィルムに、軽剥離フィルム（リンテック株式会社製、商品名「ＳＰ－ＰＥＴ３８１１３０」、厚さ３８μｍのポリエチレンテレフタレート製フィルムの片面をシリコーン樹脂で剥離処理したもの）の剥離処理面を貼り合わせて、保護膜形成用フィルムが２枚の剥離フィルムに挟持された構成を有する両面剥離フィルム付き保護膜形成用フィルムを製造した。
　各例で得られた保護膜形成用フィルムを、上記に示す方法によって評価した。結果を表１に示す。 (Preparation of protective film forming film)
The protective film obtained above is formed on the release-treated surface of a heavy release film (manufactured by Lintec Corporation, trade name "SP-PET502150", a polyethylene terephthalate film having a thickness of 50 μm and one side of which is release-treated with a silicone resin). was applied using a knife coater and dried at 100° C. for 2 minutes to form a 25 μm-thick protective film-forming film on the heavy release film. After that, the release-treated surface of a light release film (manufactured by Lintec Co., Ltd., trade name "SP-PET381130", a polyethylene terephthalate film with a thickness of 38 μm and one side of which is release-treated with a silicone resin) is attached to the protective film-forming film. A film for forming a protective film with a double-sided release film having a configuration in which the film for forming a protective film was sandwiched between two release films was produced by laminating them together.
The protective film-forming film obtained in each example was evaluated by the methods described above. Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、表１に示す各成分の詳細は、以下の通りである。
＜（Ａ）熱可塑性樹脂＞
　メチルアクリレート８５質量部及び２－ヒドロキシエチルアクリレート１５質量部を共重合してなるアクリル樹脂（質量平均分子量（Ｍｗ）：３７万、ガラス転移温度：６℃） The details of each component shown in Table 1 are as follows.
<(A) Thermoplastic resin>
Acrylic resin obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (mass average molecular weight (Mw): 370,000, glass transition temperature: 6°C)
＜（Ｂ）熱硬化性樹脂＞
　（Ｂ）－１：ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ株式会社製、商品名「エピクロンＨＰ－７２００ＨＨ」、エポキシ当量２５５～２６０ｇ／ｅｑ）
　（Ｂ）－２：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製、商品名「ｊＥＲ１０５５」、エポキシ当量８００～９００ｇ／ｅｑ）
　（Ｂ）－３：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製、商品名「ｊＥＲ８２８」、エポキシ当量１８４～１９４ｇ／ｅｑ） <(B) Thermosetting resin>
(B)-1: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name “Epiclon HP-7200HH”, epoxy equivalent 255 to 260 g/eq)
(B)-2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “jER1055”, epoxy equivalent 800 to 900 g/eq)
(B)-3: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name “jER828”, epoxy equivalent 184 to 194 g/eq)
＜（Ｃ）無機充填材＞
　球状シリカ（株式会社アドマテックス製、商品名「ＳＣ２０５０ＭＡ」、平均粒子径（Ｄ５０）０．５μｍ） <(C) Inorganic filler>
Spherical silica (manufactured by Admatechs Co., Ltd., trade name “SC2050MA”, average particle size (D 50 ) 0.5 μm)
＜（Ｄ）難燃剤＞
　ヘキサフェノキシシクロトリホスファゼン（下記式（Ｄ－２）で表される化合物であり、（Ｄ１）成分に相当する。） <(D) Flame Retardant>
Hexaphenoxycyclotriphosphazene (a compound represented by the following formula (D-2) and corresponding to the component (D1))
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
＜（Ｅ）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 <(E) Curing accelerator>
2-phenyl-4,5-dihydroxymethylimidazole
＜（Ｆ）着色剤＞
　カーボンブラック <(F) Colorant>
Carbon black
＜（Ｇ）エポキシ樹脂硬化剤＞
　ジシアンジアミド型潜在性硬化剤（株式会社ＡＤＥＫＡ製、商品名「アデカハードナーＥＨ－３６３６ＡＳ」、活性水素当量２１ｇ／ｅｑ） <(G) Epoxy resin curing agent>
Dicyandiamide type latent curing agent (manufactured by ADEKA Co., Ltd., trade name “ADEKA HARDNER EH-3636AS”, active hydrogen equivalent 21 g/eq)
＜（Ｈ）架橋剤＞
　トリメチロールプロパンのトリレンジイソシアネート付加物 <(H) Crosslinking agent>
tolylene diisocyanate adduct of trimethylolpropane
＜（Ｉ）カップリング剤＞
　３－グリシジルオキシプロピルトリメトキシシラン <(I) Coupling agent>
3-glycidyloxypropyltrimethoxysilane
　表１より、実施例１～６の保護膜形成用フィルムから形成された保護膜は、難燃性と接着性とを両立していることが分かる。一方、比較例１～３の保護膜形成用フィルムから形成された保護膜は、難燃性及び接着性のいずれかに劣っていた。 From Table 1, it can be seen that the protective films formed from the protective film-forming films of Examples 1 to 6 have both flame retardancy and adhesiveness. On the other hand, the protective films formed from the protective film-forming films of Comparative Examples 1 to 3 were inferior in either flame retardancy or adhesiveness.
　１、１Ａ、１Ｂ　保護膜形成用複合シート
　１０　保護膜形成用フィルム
　１０ａ、１０ｂ　保護膜形成用フィルムの剥離フィルム側の表面
　１１　剥離フィルム、
　１１１　第１剥離フィルム
　１１２　第２剥離フィルム
　１２　基材
　１３　粘着剤層
　１３ａ　粘着剤層の保護膜形成用フィルム側の表面
　１４　治具用接着剤層
　１４ａ　治具用接着剤層の剥離フィルム側の表面
  Reference Signs List 1, 1A, 1B protective film-forming composite sheet 10 protective film-forming film 10a, 10b release film side surface of protective film-forming film 11 release film,
REFERENCE SIGNS LIST 111 First release film 112 Second release film 12 Base material 13 Adhesive layer 13a Protective film forming film side surface of adhesive layer 14 Jig adhesive layer 14a Peeling film side surface of jig adhesive layer

Claims (14)

  1. 　硬化性を有する保護膜形成用フィルムであり、
    　２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が１．０ＭＰａ以上、かつ、８０℃における貯蔵弾性率Ｅ’（８０）と１３０℃における貯蔵弾性率Ｅ’（１３０）との比［Ｅ’（８０）／Ｅ’（１３０）］が１．２５以上であり、
    　前記保護膜形成用フィルムの硬化物の銅箔ピール強度が３．０Ｎ／１０ｍｍ以上であり、
    　下記の要件（１）を満たす、保護膜形成用フィルム。
    要件（１）：保護膜形成用フィルムを硬化させて得られた保護膜を、長辺２００ｍｍ×短辺５０ｍｍの大きさに裁断し、温度２３℃、相対湿度５０％の環境下で４８時間保管した後、短辺方向を直径１２．７ｍｍの円筒状の棒に巻き、長辺方向の一方の端部から１２５ｍｍの位置に標線を設け、もう一方の端部と上記標線との間の部分（７５ｍｍの部分）をテープで留めて円筒状の保護膜を作製した後、棒を引き抜く。該円筒状の保護膜を、前記テープで留めた側の端部を上側にして、該上側の端部から空気が抜けないように該端部を閉じた状態でクランプに垂直に取付け、米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）のＵＬ９４ＶＴＭ試験（薄手材料垂直燃焼試験）に準拠して、前記円筒状の保護膜の下端から１０ｍｍの位置にバーナーの筒を設置し、前記円筒状の保護膜の下端の中央において２０ｍｍの青色炎による３秒間の１回目の接炎試験を行い、炎が消えた場合は同じ条件で２回目の接炎試験を行い、１回目及び２回目の接炎試験において炎が前記標線を超えない。     A film for forming a protective film having curability,
    The minimum value of the storage elastic modulus E′ in the temperature range of 23 to 150° C. is 1.0 MPa or more, and the ratio of the storage elastic modulus E′ (80) at 80° C. to the storage elastic modulus E′ (130) at 130° C. [E'(80)/E'(130)] is 1.25 or more,
    The cured product of the protective film-forming film has a copper foil peel strength of 3.0 N/10 mm or more,
    A protective film-forming film that satisfies the following requirement (1).
    Requirement (1): Cut the protective film obtained by curing the protective film-forming film into a size of 200 mm long side × 50 mm short side, and store it for 48 hours in an environment with a temperature of 23 ° C. and a relative humidity of 50%. After that, the short side direction is wound around a cylindrical rod with a diameter of 12.7 mm, a marked line is provided at a position 125 mm from one end in the long side direction, and the other end and the marked line Tape a section (75 mm section) to create a cylindrical protective membrane, then pull out the rod. Mount the cylindrical protective membrane vertically on the clamp with the taped end up and the end closed to prevent air from escaping from the upper end; In accordance with the UL94 VTM test (thin material vertical burning test) of the UL94 test (combustion test of plastic materials for parts of equipment) specified by Writers Laboratories (UL), 10 mm from the lower end of the cylindrical protective film A burner cylinder is installed at the position, and the first flame contact test is performed for 3 seconds with a 20 mm blue flame at the center of the lower end of the cylindrical protective film. A flame test is performed and the flame does not exceed the above marked line in the first and second flame contact tests.
  2. 　前記２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値が、１００ＭＰａ以下である、請求項１に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1, wherein the minimum value of the storage elastic modulus E' in the temperature range of 23 to 150°C is 100 MPa or less.
  3. 　前記２３～１５０℃の温度範囲における貯蔵弾性率Ｅ’の最小値を示す温度が、９０～１４８℃である、請求項１又は２に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, wherein the temperature showing the minimum value of storage elastic modulus E' in the temperature range of 23 to 150°C is 90 to 148°C.
  4. 　前記貯蔵弾性率Ｅ’の比［Ｅ’（８０）／Ｅ’（１３０）］が、３．００以下である、請求項１又は２に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, wherein the ratio [E'(80)/E'(130)] of the storage elastic modulus E' is 3.00 or less.
  5. 　前記保護膜形成用フィルムが熱硬化性を有する、請求項１又は２に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film has thermosetting properties.
  6. 　前記保護膜形成用フィルムが、（Ａ）熱可塑性樹脂と、（Ｂ）熱硬化性樹脂と、を含有する樹脂組成物を用いて形成された、請求項１又は２に記載の保護膜形成用フィルム。 3. The protective film forming film according to claim 1 or 2, wherein the protective film forming film is formed using a resin composition containing (A) a thermoplastic resin and (B) a thermosetting resin. film.
  7. 　前記（Ａ）熱可塑性樹脂が、アクリル樹脂である、請求項６に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 6, wherein (A) the thermoplastic resin is an acrylic resin.
  8. 　前記（Ｂ）熱硬化性樹脂が、エポキシ樹脂である、請求項６に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 6, wherein the thermosetting resin (B) is an epoxy resin.
  9. 　厚さが、１～１００μｍである、請求項１又は２に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, which has a thickness of 1 to 100 μm.
  10. 　半導体ウエハの裏面に貼付され、保護膜付き半導体チップの製造に用いられる、請求項１又は２に記載の保護膜形成用フィルム。 The film for forming a protective film according to claim 1 or 2, which is attached to the back surface of a semiconductor wafer and used for manufacturing a semiconductor chip with a protective film.
  11. 　請求項１又は２に記載の保護膜形成用フィルムが、２枚の剥離フィルムに挟持された構成を有する、保護膜形成用複合シート。 A composite sheet for forming a protective film, wherein the film for forming a protective film according to claim 1 or 2 is sandwiched between two release films.
  12. 　基材と、粘着剤層と、請求項１又は２に記載の保護膜形成用フィルムと、をこの順で有する、保護膜形成用複合シート。 A protective film-forming composite sheet comprising a substrate, an adhesive layer, and the protective film-forming film according to claim 1 or 2 in this order.
  13. 　請求項１又は２に記載の保護膜形成用フィルムの硬化物である保護膜を有する、保護膜付き半導体チップ。 A semiconductor chip with a protective film, which has a protective film that is a cured product of the film for forming a protective film according to claim 1 or 2.
  14. 　請求項１３に記載の保護膜付き半導体チップを有する、半導体装置。
          A semiconductor device comprising the semiconductor chip with a protective film according to claim 13 .
PCT/JP2023/005403 2022-02-18 2023-02-16 Film for forming protective coating, composite sheet for forming protective coating, protective coating-equipped semiconductor chip, and semiconductor device WO2023157907A1 (en)

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PCT/JP2023/005401 WO2023157905A1 (en) 2022-02-18 2023-02-16 Film for forming protective membrane, composite sheet for forming protective membrane, semiconductor chip and semiconductor device equipped with protective membrane

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021001338A (en) * 2020-08-24 2021-01-07 信越化学工業株式会社 Resin composition and resin film
WO2021020542A1 (en) * 2019-08-01 2021-02-04 株式会社カネカ Thermosetting resin composition, thermosetting resin film, thermoset film, multilayer body, printed wiring board and method for producing same
JP2021014478A (en) * 2019-07-10 2021-02-12 東レ株式会社 Thermoplastic polyester resin composition and molded article
WO2021153414A1 (en) * 2020-01-31 2021-08-05 東レ株式会社 Thermoplastic polyester resin composition and molded article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021014478A (en) * 2019-07-10 2021-02-12 東レ株式会社 Thermoplastic polyester resin composition and molded article
WO2021020542A1 (en) * 2019-08-01 2021-02-04 株式会社カネカ Thermosetting resin composition, thermosetting resin film, thermoset film, multilayer body, printed wiring board and method for producing same
WO2021153414A1 (en) * 2020-01-31 2021-08-05 東レ株式会社 Thermoplastic polyester resin composition and molded article
JP2021001338A (en) * 2020-08-24 2021-01-07 信越化学工業株式会社 Resin composition and resin film

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