WO2020137947A1 - Film-like adhesive, laminate sheet, composite sheet, and manufacturing method for laminate - Google Patents

Film-like adhesive, laminate sheet, composite sheet, and manufacturing method for laminate Download PDF

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Publication number
WO2020137947A1
WO2020137947A1 PCT/JP2019/050300 JP2019050300W WO2020137947A1 WO 2020137947 A1 WO2020137947 A1 WO 2020137947A1 JP 2019050300 W JP2019050300 W JP 2019050300W WO 2020137947 A1 WO2020137947 A1 WO 2020137947A1
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Prior art keywords
adhesive
film
film adhesive
resin
group
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PCT/JP2019/050300
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French (fr)
Japanese (ja)
Inventor
陽輔 佐藤
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201980079178.0A priority Critical patent/CN113165349A/en
Priority to JP2020563241A priority patent/JP7497299B2/en
Priority to KR1020217015508A priority patent/KR20210110571A/en
Publication of WO2020137947A1 publication Critical patent/WO2020137947A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/38Layered products comprising a layer of synthetic resin comprising epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515Three-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/29Compounds containing one or more carbon-to-nitrogen double bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/50Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52Mounting semiconductor bodies in containers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144Devices controlled by radiation
    • H01L27/146Imager structures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to a film adhesive, a laminated sheet, a composite sheet, and a method for producing a laminated body.
  • the present application claims priority based on Japanese Patent Application No. 2018-246839 filed on December 28, 2018 in Japan, and the content thereof is incorporated herein.
  • film adhesives are used depending on the purpose at the time of manufacturing or processing various parts constituting electronic devices. For example, when mounting the semiconductor chip on the circuit forming surface of the substrate, a film adhesive is pasted on the back surface of the semiconductor chip, and the semiconductor chip is attached to the circuit forming surface of the substrate via this film adhesive. Adhere (die bonding). When protecting the circuit forming surface of a chip such as a sensor, the circuit forming surface is covered with a light transmissive cover via a light-transmissive film adhesive.
  • the film adhesive contains a resin component in order to exhibit adhesiveness, and in some cases, contains a thermosetting component in order to impart thermosetting property, but these components are Some are unstable to heat. That is, the conventional film-like adhesive is easily discolored by heating.
  • a film-like adhesive having a light-transmitting property for example, a die-bonding film for die-bonding a semiconductor chip and having a light transmittance of 80% or more at a wavelength of 1065 nm is disclosed (see Patent Document 1).
  • Patent Document 1 does not disclose physical properties after heating, such as the color of the die bond film after heating.
  • the present invention uses a film-like adhesive that has optical transparency before and after heating and is suppressed from being colored after heating, a laminated sheet and a composite sheet using the film-like adhesive, and the film-like adhesive. It is an object of the present invention to provide a method for manufacturing a laminated body having such a structure.
  • the present invention is a film adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover, wherein at least one surface of the film adhesive contains a substantially aromatic compound. No, provide a film adhesive.
  • the linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive before heating at 260° C. is 90% or more, and the film adhesive is heated at 260° C. for 10 minutes.
  • the linear adhesiveness of light having a wavelength of 400 to 800 nm may be 85% or more, and the thickness of the adhesive film may be 10 to 40 ⁇ m.
  • the film adhesive of the present invention preferably contains an aliphatic epoxy compound.
  • the film adhesive of the present invention may contain an aliphatic phosphite ester as an antioxidant.
  • the film adhesive contains an acrylic resin and an aliphatic polyisocyanate crosslinking agent, and the acrylic resin is a functional group capable of binding to the crosslinking agent. It may have a group.
  • the present invention provides a laminated sheet comprising the film adhesive and a resin film provided on one surface of the film adhesive.
  • the present invention comprises the film adhesive and a dicing sheet provided on one surface of the film adhesive, wherein the dicing sheet is a base material and one surface of the base material. And a pressure-sensitive adhesive layer provided on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer being disposed between the substrate and the film adhesive.
  • the present invention the one surface of the film adhesive, the circuit forming surface of the chip is attached, the other surface of the film adhesive, by attaching a light-transmitting cover, the chip, the Provided is a method for producing a laminate, which comprises obtaining a laminate in which a film adhesive and the light-transmitting cover are laminated in this order.
  • the film-like adhesive of the present invention has optical transparency before and after heating, and coloration after heating is suppressed.
  • the film adhesive can be provided to a component to which the film adhesive is applied.
  • the method for producing a laminated body of the present invention it is possible to produce a laminated body including a chip, a film adhesive, and a light-transmitting cover, which are laminated in this order.
  • FIG. 6 is a cross-sectional view for schematically explaining an example of a method of using the composite sheet according to the embodiment of the present invention.
  • 3 is a result of FT-IR measurement of a film adhesive in Examples and Comparative Examples.
  • a film-shaped adhesive according to an embodiment of the present invention is a film-shaped adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover, At least one side of which is substantially free of aromatic compounds.
  • the film-like adhesive satisfying these conditions is suppressed from turbidity and coloration before and after heating at 260° C. or the like, and has a wavelength of 400 to 800 nm (in the present specification, “light (400 to 800 nm )” may be abbreviated)).
  • the film-like adhesive of the present embodiment can be used for adhering an object when manufacturing or processing various parts constituting an electronic device.
  • the circuit forming surface of a chip such as a sensor can be covered with a light transmissive cover (protective cover) via the film adhesive.
  • the film adhesive can be used as a film for adhering the cover to the circuit forming surface of the chip.
  • the film adhesive has high light transmittance before and after heating, and coloring is suppressed.Therefore, the visual presence present on the circuit formation surface of the chip is exceeded through the light transparent cover and the film adhesive. Information can be viewed with stability and high accuracy.
  • a fingerprint sensor is an example of a sensor to be covered by the light-transmitting cover (protective cover). However, this is an example of a sensor.
  • circuit forming surface the surface of the substrate and the chip on which the circuit is formed.
  • circuit forming surface the surface of the substrate and the chip on which the circuit is formed.
  • the mere description of “chip” does not mean only a semiconductor chip, but includes chips other than the semiconductor chip.
  • the film adhesive of the present embodiment preferably has thermosetting properties and preferably pressure-sensitive adhesive properties.
  • a film adhesive having both thermosetting property and pressure-sensitive adhesive property can be attached by lightly pressing to various adherends in the uncured state.
  • the film adhesive may be one that can be attached to various adherends by heating and softening. When cured, the film adhesive finally becomes a cured product having high impact resistance, and this cured product can retain sufficient adhesive properties even under severe conditions of high temperature and high humidity.
  • the linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment before heating at 260° C. (in this specification, may be abbreviated as “pre-heating linear transmittance”) is It is preferably 90% or more, more preferably 91.5% or more, further preferably 93% or more, and particularly preferably 94.5% or more. Since the linear transmittance before heating is equal to or higher than the lower limit value, the film adhesive before heating has a property that an image can be correctly recognized when the image is viewed through the film adhesive (in the present specification. , It is sometimes abbreviated as "image recognition property").
  • the upper limit of the linear transmittance of light (400 to 800 nm) before heating is not particularly limited and may be 100%.
  • the film adhesive having a linear transmittance before heating of 99.8% or less is easier to manufacture.
  • the above-mentioned linear transmittance of light (400 to 800 nm) before heating can be appropriately adjusted within a range that is set by arbitrarily combining any of the above lower limit value and upper limit value.
  • the linear transmittance before heating is preferably 90 to 99.8%, more preferably 91.5 to 99.8%, and 93 to 99.8%. It is more preferable, and it is particularly preferable that it is 94.5 to 99.8%.
  • Linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment after heating at 260° C. for 10 minutes may be abbreviated as “linear transmittance after heating” in this specification). Is preferably 85% or more, and may be any of 87.5% or more, 90% or more, and 94% or more, for example. When the linear transmittance after heating is at least the lower limit value, the film adhesive after heating has high image recognizability.
  • the upper limit of the linear transmittance of light (400 to 800 nm) after heating It is not particularly limited and may be 100%.
  • the film adhesive having a linear transmittance of 99.8% or less after heating is easier to manufacture.
  • the linear transmittance of light (400 to 800 nm) after heating can be appropriately adjusted within a range set by arbitrarily combining any one of the above lower limit value and upper limit value.
  • the linear transmittance after heating is preferably 85 to 99.8%, for example, 87.5 to 99.8%, 90 to 99.8%, and 94 to 99.%. It may be either 8%. However, these are examples of the linear transmittance after heating.
  • the linear transmittance before heating and the linear transmittance after heating of light (400 to 800 nm) can be measured by a known method using a spectrophotometer.
  • the heating condition of the film adhesive of 260° C. for 10 minutes when defining the linear transmittance after heating is set in consideration of the conditions in the heating process such as the solder reflow process.
  • the shear strength of the film adhesive of the present embodiment is not particularly limited, but is preferably 20 N/2 mm ⁇ or more, for example, 50 N/2 mm ⁇ or more, 60 N/2 mm ⁇ or more, 70 N/2 mm ⁇ or more, and It may be either 78 N/2 mm ⁇ or more.
  • the shear strength of the film adhesive is equal to or more than the lower limit value, the adhesive strength to the pasting target becomes stronger.
  • the unit “N/2 mm ⁇ ” has the same meaning as “N/(2 mm ⁇ 2 mm)”.
  • the upper limit of the shear strength of the film adhesive is also not particularly limited.
  • a film adhesive having a shear strength of 300 N/2 mm ⁇ or less is easier to manufacture.
  • the shear strength of the film adhesive can be appropriately adjusted within a range set by any combination of the above lower limit and upper limit.
  • the shear strength is preferably 20 to 300 N/2 mm ⁇ , for example, 50 to 300 N/2 mm ⁇ , 60 to 300 N/2 mm ⁇ , 70 to 300 N/2 mm ⁇ , and 78 to It may be either 300 N/2 mm ⁇ .
  • these are examples of the shear strength.
  • the shear strength of the film adhesive in the present embodiment is measured by the method described below. (Measuring method of shear strength of film adhesive) Using a film-like adhesive having a size of 2 mm ⁇ 2 mm and a thickness of 20 ⁇ m, a copper plate having a size of 30 mm ⁇ 30 mm and a thickness of 300 ⁇ m, and a silicon chip, the film-like adhesive of A test piece is prepared in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate. On at least one side surface of this test piece, the side surfaces of the film adhesive and the silicon chip are aligned.
  • the film adhesive it is preferable that at least one surface thereof is substantially free of an aromatic compound and both surfaces are substantially free of an aromatic compound.
  • the single-layered film-like adhesive usually has no unevenness in the composition therein and has a high compositional uniformity. Therefore, there is no significant difference in the type and content of the components on both sides of the single-layer film adhesive, or even if they are observed, the effect brought by them is negligible. It is slight.
  • the single-layer film adhesive if at least one surface thereof does not substantially contain an aromatic compound, the entire film adhesive and the other surface also contain substantially an aromatic compound. You can judge that it is not.
  • the film adhesive contains substantially no aromatic compound
  • the film adhesive contains no aromatic compound or contains no aromatic compound. Even if it is, it means that the effect brought by it is negligibly negligible, and the film-like adhesive exhibits the same properties as in the case where the adhesive does not contain an aromatic compound.
  • the fact that the surface of the film adhesive does not substantially contain an aromatic compound means that the surface of the film adhesive has a Fourier transform red.
  • FT-IR Freier Transform Infrared Spectroscopy, sometimes abbreviated as “FT-IR” in this specification
  • the main functional group specified in the wave number range of 3050 to 2990 cm ⁇ 1 is only the aromatic cyclic group.
  • the film adhesive may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers are the same as each other. However, they may be different, and the combination of these plural layers is not particularly limited.
  • the thickness of the film adhesive is preferably 10 to 40 ⁇ m, and may be any of 10 to 35 ⁇ m, 10 to 30 ⁇ m, and 10 to 25 ⁇ m, or 13 to 40 ⁇ m and 16 to 40 ⁇ m. , And 19 to 40 ⁇ m, or 13 to 35 ⁇ m, 16 to 30 ⁇ m, and 19 to 25 ⁇ m.
  • the thickness of the film adhesive is not less than the above lower limit, the adhesive force of the film adhesive with respect to the object to be bonded becomes stronger.
  • the thickness of the film adhesive is equal to or less than the above upper limit, the linear transmittance of light (for example, light (400 to 800 nm)) of the film adhesive increases regardless of whether or not the film adhesive is heated.
  • the "thickness of the film-like adhesive” means the thickness of the whole film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers means all the constituents of the film-like adhesive. Means the total thickness of the layers.
  • the film adhesive is preferably, for example, 90% or more of the linear transmittance of light (400 to 800 nm) before heating and 85% or more of the linear transmittance of light (400 to 800 nm) after heating. And the film adhesive has a thickness of 10 to 40 ⁇ m.
  • the above-mentioned physical properties of the film-like adhesive are, for example, It can be adjusted by adjusting the type and content of the components contained in the film adhesive.
  • the film adhesive is preferably, for example, one or two selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). The thing containing the above is mentioned.
  • the film adhesive is one or two selected from the group consisting of its constituent materials (for example, an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). It can be formed using an adhesive composition containing the above).
  • the film-shaped adhesive can be formed at a desired site by applying the adhesive composition to the surface on which the film-shaped adhesive is to be formed and drying it as necessary.
  • the ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film adhesive.
  • “normal temperature” means a temperature at which it is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.
  • the coating of the adhesive composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.
  • the drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains the solvent described below, it is preferable to heat-dry.
  • the solvent-containing adhesive composition is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.
  • the components contained in the film adhesive and the adhesive composition will be described in detail.
  • the acrylic resin (a) is a component that can be regarded as formed by a polymerization reaction of one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, and derivatives thereof. is there.
  • the “derivative” means one having a structure in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified.
  • the "group” includes not only an atomic group formed by combining a plurality of atoms but also one atom.
  • the acrylic resin (a) is a resin component for imparting film-forming properties and flexibility to the film-like adhesive and improving the adhesiveness (sticking property) to an object to be adhered such as the chip.
  • (meth)acrylic acid is a concept that includes both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth)acrylic acid.
  • the acrylic resin (a) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
  • the acrylic resin (a) examples include known acrylic polymers.
  • the weight average molecular weight (Mw) of the acrylic resin (a) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 15,000,000.
  • Mw weight average molecular weight of the acrylic resin (a)
  • the weight average molecular weight of the acrylic resin (a) is within such a range, it becomes easy to adjust the adhesive force between the film adhesive and the adherend within a preferable range.
  • the weight average molecular weight of the acrylic resin (a) is not less than the lower limit value, the shape stability of the film adhesive (stability during storage) is improved.
  • a "weight average molecular weight” is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.
  • the glass transition temperature (Tg) of the acrylic resin (a) is preferably ⁇ 60 to 70° C., more preferably ⁇ 30 to 50° C.
  • Tg of the acrylic resin (a) is at least the lower limit value, the adhesive force between the film adhesive and the adherend is suppressed, and for example, the film adhesive is provided at the time of pickup. It becomes easier to separate the chip from the dicing sheet described later.
  • Tg of the acrylic resin (a) is not more than the above upper limit value, the adhesive force between the film adhesive and the adherend is improved.
  • Examples of the (meth)acrylic acid ester that constitutes the acrylic resin (a) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate.
  • N-butyl (meth)acrylate N-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth) Decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl acrylate), (meth ) Penta
  • the acrylic resin (a) is, for example, one or two kinds selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. in addition to the (meth)acrylic acid ester. It may be a resin obtained by copolymerizing the above monomers.
  • the monomer constituting the acrylic resin (a) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof can be arbitrarily selected.
  • the acrylic resin (a) may have a functional group capable of binding to other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a carboxy group and an isocyanate group, in addition to the above-mentioned hydroxyl group.
  • These functional groups including the hydroxyl group of the acrylic resin (a) may be bonded to other compounds via a crosslinking agent (f) described later, or other compounds may be bonded without the crosslinking agent (f). May be directly combined with.
  • the acrylic resin (a) is bonded to another compound by the functional group, the reliability of the package obtained by using the film adhesive tends to be improved.
  • Preferred examples of the acrylic resin (a) include those having a functional group capable of binding to the crosslinking agent (f) described later.
  • the content ratio of a) is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, further preferably 20 to 65% by mass, for example, 30 to 55% by mass. It may be either mass% or 30 to 50 mass %. When the ratio is at least the lower limit value, the structure of the film adhesive will be more stable.
  • the ratio is less than or equal to the upper limit value, for example, it becomes easy to increase the amount of components other than the acrylic resin (a) such as the epoxy compound (b1) and the phosphorus-based antioxidant (z), The effect of using a component other than the acrylic resin (a) can be more easily obtained.
  • the epoxy compound (b1) may be either a resin component or a non-resin component.
  • the epoxy compound (b1) include known compounds, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and triazine type alicyclic epoxy compound can be mentioned.
  • an epoxy compound having an unsaturated hydrocarbon group may be used as the epoxy compound (b1).
  • the epoxy compound having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin (a) than the epoxy compound having no unsaturated hydrocarbon group. Therefore, by using the epoxy compound (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film adhesive is improved.
  • Examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include compounds having a structure in which a part of the epoxy groups of a polyfunctional epoxy compound is converted to a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition-reacting (meth)acrylic acid or its derivative with an epoxy group.
  • the epoxy compound (b1) having an unsaturated hydrocarbon group for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy compound can be mentioned.
  • the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth) Examples thereof include an acrylamide group, and an acryloyl group is preferable.
  • the number average molecular weight of the epoxy compound (b1) which is a resin component is not particularly limited, but the curability of the film adhesive, and the strength and heat resistance of the cured product of the film adhesive. From the viewpoint of the above, it is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
  • the epoxy equivalent of the epoxy compound (b1) is preferably 100 to 1000 g/eq, and more preferably 120 to 600 g/eq.
  • the epoxy compound (b1) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.
  • the epoxy compound (b1) is preferably an aliphatic compound. That is, the film adhesive preferably contains an aliphatic epoxy compound.
  • the "aliphatic compound” means a compound having an aliphatic group and not an aromatic group.
  • the “aliphatic group” includes a chain aliphatic group and an aliphatic cyclic group (alias: alicyclic group).
  • the “aromatic group” includes an aromatic hydrocarbon group and an aromatic heterocyclic group. Since the adhesive composition and the film adhesive contain an aliphatic compound as the epoxy compound (b1), the effect of suppressing coloration after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.
  • the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the epoxy compound (b1), heating the film adhesive (for example, heating at 260° C.)
  • the effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), the above coloring
  • the effect of suppressing is significantly increased.
  • the content of the epoxy compound (b1) is preferably 5 to 500 parts by mass relative to 100 parts by mass of the acrylic resin (a), for example, It may be any of 5 to 200 parts by mass, 5 to 150 parts by mass, 5 to 110 parts by mass, and 5 to 100 parts by mass, or 10 to 110 parts by mass, 25 to 110 parts by mass, and 40 to 110 parts by mass. It may be either part by mass.
  • the content of the epoxy compound (b1) is in such a range, it becomes easier to adjust the adhesive force between the film adhesive and the resin film or the dicing sheet described below.
  • phosphorus-based antioxidant (z) Since the film adhesive contains the phosphorus-based antioxidant (z), coloring before and after heating is further suppressed.
  • the phosphorus-based antioxidant (z) is not particularly limited as long as it has a phosphorus atom as its constituent atom and has an antioxidant action. Examples of the phosphorus-based antioxidant (z) include compounds in which the oxidation number of phosphorus is 3.
  • the phosphorus antioxidant (z) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily set. You can choose.
  • the phosphorus-based antioxidant (z) is preferably an aliphatic compound. Since the adhesive composition and the film adhesive contain an aliphatic compound as the phosphorus-based antioxidant (z), coloring of the film adhesive after heating (for example, heating at 260° C.) The inhibitory effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described inhibitory effect of coloring is significantly enhanced.
  • the phosphorus-based antioxidant (z) is preferably a phosphite ester because it stably exhibits an antioxidant action.
  • the phosphorus-based antioxidant (z) is more preferably an aliphatic phosphite ester, and further preferably an aliphatic phosphite trialkyl ester. That is, the film adhesive, as an antioxidant, preferably contains a phosphite ester, more preferably contains an aliphatic phosphite ester, an aliphatic phosphite trialkyl ester It is more preferable to contain.
  • Examples of the aliphatic trialkyl phosphite include triethyl phosphite ((C 2 H 5 O) 3 P), tris(2-ethylhexyl) phosphite ((CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 2 CH 3) CH 2 O) 3 P), tridecyl phosphite ((C 10 H 21 O) 3 P), trilauryl phosphite ((C 12 H 25 O) 3 P), tris (tridecyl) phosphite ((C 13 H 27 O) 3 P), tristearyl phosphite ((C 18 H 37 O) 3 P), bis(decyl)pentaerythritol diphosphite (C 10 H 21 OP(OCH 2 ) 2 C( CH 2 O) 2 POC 10 H 21), bis (tridecyl) pentaerythritol diphosphite (C 13 H 27 OP (OCH 2)
  • the ratio of the content of the phosphorus-based antioxidant (z) with respect to the total content of all components other than the solvent that is, phosphorus in the film-shaped adhesive with respect to the total mass of the film-shaped adhesive
  • the ratio of the content of the system antioxidant (z)) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.3 to 1.5% by mass. % Is more preferable, and it may be, for example, 0.3 to 1% by mass.
  • the ratio is at least the lower limit value, the effect of using the phosphorus-based antioxidant (z) can be more remarkably obtained.
  • the ratio is not more than the upper limit value, excessive use of the phosphorus-based antioxidant (z) is suppressed.
  • any one of these may be used in addition to the acrylic resin (a), the epoxy compound (b1), and the phosphorus antioxidant (z) in order to improve various physical properties. It may also contain other components that do not correspond to the above.
  • Other components contained in the film adhesive include, for example, phenol resin (b2), curing accelerator (c), filler (d), coupling agent (e), cross-linking agent (f), energy ray.
  • antioxidant (y) other than phosphorus-based antioxidant (z) in the present specification, abbreviated as “other antioxidant (y)
  • Thermoplastic resin (x) other than acrylic resin (a) in the present specification, may be abbreviated as “thermoplastic resin (x)"
  • general-purpose additive (i), etc. are listed.
  • phenol resin (b2) functions as a thermosetting agent for the epoxy compound (b1).
  • epoxy thermosetting resin (b) such an epoxy thermosetting resin may be referred to as "epoxy thermosetting resin (b)".
  • the phenol resin (b2) may be one having two or more phenolic hydroxyl groups in one molecule as a functional group capable of reacting with an epoxy group.
  • phenol resin (b2) examples include polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin and the like.
  • the phenol resin (b2) may have an unsaturated hydrocarbon group.
  • the other phenolic resin (b2) having an unsaturated hydrocarbon group include, for example, a compound having a structure in which a part of hydroxyl groups of the phenolic resin is replaced with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenolic resin. Examples thereof include compounds having a structure in which a group having an unsaturated hydrocarbon group is directly bonded.
  • the unsaturated hydrocarbon group in the phenol resin (b2) is the same as the unsaturated hydrocarbon group in the epoxy compound having an unsaturated hydrocarbon group described above.
  • the phenolic resin (b2) is preferably one having a high softening point or glass transition temperature because it is easy to adjust the adhesive force of the film adhesive.
  • the number average molecular weight of the phenol resin (b2) is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
  • the phenol resin (b2) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
  • the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent is not particularly limited, but is preferably 10% by mass or less, more preferably 7.5% by mass or less, and 5% by mass or less. Is more preferable.
  • the ratio is less than or equal to the upper limit value, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) becomes higher. That is, as one preferable example of the film adhesive containing the phenol resin (b2), the ratio of the content of the phenol resin (b2) to the total mass of the film adhesive in the film adhesive is The content is 10% by mass or less.
  • the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent that is, the film adhesive in the film adhesive
  • the lower limit value of the ratio of the content of the phenol resin (b2) to the total mass of is not particularly limited.
  • the above ratio is preferably 0.5% by mass or more from the viewpoint that the effect of using the phenol resin (b2) can be more remarkably obtained.
  • the ratio can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and any upper limit value.
  • the ratio is preferably 0.5 to 10% by mass, more preferably 0.5 to 7.5% by mass, and 0.5 to 5% by mass. Is more preferable.
  • the content of the phenol resin (b2) in the adhesive composition and the film adhesive is, for example, 3 to 30 with respect to 100 parts by mass of the epoxy compound (b1). It may be any one of 3 parts by mass, 3 to 25 parts by mass, and 3 to 20 parts by mass, or 5 to 30 parts by mass, 10 to 30 parts by mass, and 15 to 30 parts by mass. It may be 5 to 25 parts by mass or 10 to 20 parts by mass.
  • the curing accelerator (c) is a component for controlling the curing rate of the adhesive composition and the film adhesive.
  • Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.
  • organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, triphenylphosphine A tetraphenylboron salt such as tetraphenylborate; an inclusion compound having the above-mentioned imidazole as a guest compound, and the like.
  • the curing accelerator (c) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected. ..
  • the content of the curing accelerator (c) in the adhesive composition and the film adhesive is 100 parts by mass of the total content of the epoxy compound (b1) and the phenol resin (b2). On the other hand, it is preferably 0.01 to 7 parts by mass, and more preferably 0.1 to 4 parts by mass.
  • the content of the curing accelerator (c) is equal to or more than the lower limit value, the effect of using the curing accelerator (c) can be more remarkably obtained.
  • the content of the curing accelerator (c) is less than or equal to the upper limit value, for example, the highly polar curing accelerator (c) forms a film with the adherend in a film adhesive under high temperature and high humidity conditions.
  • the total content of the epoxy compound (b1) and the phenol resin (b2) means the content of the epoxy compound (b1).
  • the film adhesive contains the filler (d), the coefficient of thermal expansion thereof can be easily adjusted. By optimizing the coefficient of thermal expansion for the object to which the film adhesive is attached, the film adhesive The reliability of the package obtained by using the adhesive tape is further improved. In addition, by containing the filler (d) in the film adhesive, it is possible to reduce the moisture absorption rate of the cured product of the film adhesive or to improve the heat dissipation.
  • the filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
  • Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or a surface modified product thereof.
  • the average particle size of the filler (d) is not particularly limited, but is preferably 10 to 100 nm, more preferably 10 to 80 nm, and further preferably 10 to 60 nm.
  • the average particle diameter of the filler (d) is not more than the upper limit value, turbidity of the film adhesive is highly suppressed, and the straight line of the film adhesive before heating with light (400 to 800 nm) The transmittance and the linear transmittance after heating are improved, and as a result, the image recognizability of the film adhesive before and after heating becomes higher.
  • the average particle size of the filler (d) is not less than the lower limit value, the effect of using the filler (d) can be more remarkably obtained.
  • the “average particle diameter” means the value of the particle diameter (D 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. ..
  • the filler (d) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.
  • the ratio of the content of the filler (d) to the total content of all components other than the solvent is preferably 7.5 to 50% by mass, for example, 10 to 45% by mass or 10 to 40% by mass. Good.
  • the content of the filler (d) is in such a range, it becomes easier to adjust the thermal expansion coefficient.
  • the film adhesive has improved adhesiveness and adhesion to the adherend. Further, since the film adhesive contains the coupling agent (e), the cured product has improved water resistance without impairing heat resistance.
  • the coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.
  • the coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the acrylic resin (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. Is more preferable.
  • Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, and 2-glycidyloxymethyldiethoxysilane.
  • the coupling agent (e) is preferably an aliphatic compound. Since the adhesive composition and the film adhesive contain an aliphatic compound as the coupling agent (e), the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) Is further increased, and by containing only an aliphatic compound (in other words, not containing an aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.
  • aliphatic compound examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and the like.
  • 3-glycidyloxypropyltriethoxysilane 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethylmethyl Examples thereof include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane,
  • the coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
  • the content of the coupling agent (e) in the adhesive composition and the film adhesive is the total amount of the acrylic resin (a) and the epoxy thermosetting resin (b).
  • the content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
  • the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the film adhesive to the adherend is improved. The effect of using the coupling agent (e) can be more remarkably obtained.
  • the content of the coupling agent (e) is equal to or less than the upper limit value, the generation of outgas is further suppressed.
  • ⁇ Crosslinking agent (f)> When an acrylic resin (a) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group capable of binding to the above-mentioned other compounds is used, an adhesive composition
  • the material and the film-like adhesive may contain a cross-linking agent (f) for binding the functional group to another compound to cross-link it. By crosslinking with the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.
  • cross-linking agent (f) for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), etc. are listed.
  • organic polyvalent isocyanate compound for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound etc.” Abbreviated); trimers of the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds with polyol compounds Etc.
  • the "adduct” is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil or the like. Means a reaction product with a molecularly active hydrogen-containing compound.
  • the term "terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.
  • organic polyvalent isocyanate compound examples include, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; tri A compound in which one or more of tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of hydroxyl groups of a polyol such as methyl
  • organic polyvalent imine compound examples include N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
  • -Tri- ⁇ -aziridinyl propionate, N,N′-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine and the like can be mentioned.
  • the crosslinking agent (f) When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the acrylic resin (a).
  • a cross-linking structure can be easily formed on the film adhesive by the reaction between the cross-linking agent (f) and the acrylic resin (a). Can be introduced to.
  • the cross-linking agent (f) is preferably an aliphatic compound. Since the adhesive composition and the film adhesive contain an aliphatic compound as the cross-linking agent (f), an effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.
  • the cross-linking agent (f) is an aliphatic organic polyvalent isocyanate compound (aliphatic polyvalent isocyanate cross-linking agent) in that it has a particularly high effect of suppressing the above coloring and has excellent properties as a cross-linking agent. Is preferred.
  • aliphatic polyvalent isocyanate crosslinking agent examples include, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4′- Diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compound obtained by adding one or more of tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate to all or part of hydroxyl groups of polyols such as trimethylolpropane. Lysine diisocyanate and the like.
  • the cross-linking agent (f) When the film adhesive is focused on the acrylic resin (a) and the cross-linking agent (f), the cross-linking agent (f) has a particularly high effect of suppressing the above-mentioned coloring and has excellent properties. It is preferable to contain the aliphatic polyvalent isocyanate cross-linking agent and to contain, as the acrylic resin (a), a resin having a functional group capable of binding to the aliphatic polyvalent isocyanate cross-linking agent.
  • the cross-linking agent (f) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
  • the content of the cross-linking agent (f) in the adhesive composition and the film adhesive is 0.3 to 100 parts by mass with respect to 100 parts by mass of the acrylic resin (a).
  • the amount is preferably 12 parts by mass, more preferably 0.3 to 3.5 parts by mass, still more preferably 0.3 to 2 parts by mass.
  • the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) can be obtained more significantly. Further, when the content of the crosslinking agent (f) is not more than the upper limit value, excessive use of the crosslinking agent (f) is suppressed.
  • the adhesive composition and the film adhesive may contain an energy ray curable resin (g). Since the film adhesive contains the energy ray curable resin (g), its characteristics can be changed by irradiation with energy rays.
  • the “energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, electron beams and the like.
  • Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet ray source.
  • the electron beam can be emitted by an electron beam accelerator or the like.
  • “energy ray curable” means a property of being cured by irradiation with energy rays
  • “non-energy ray curable” means a property of not being cured by irradiation of energy rays. To do.
  • the energy ray-curable resin (g) is obtained by polymerizing (curing) an energy ray-curable compound.
  • the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferable.
  • the acrylate compound examples include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta( (Meth)acrylate containing a chain aliphatic skeleton such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; Cycloaliphatic skeleton-containing (meth)acrylate such as cyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; urethane (meth
  • the weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.
  • the energy ray curable resin (g) contained in the adhesive composition may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
  • the ratio of the content of the energy ray-curable resin (g) to the total weight of the adhesive composition in the adhesive composition is 1 to 95% by mass. Is more preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.
  • a photopolymerization initiator (h) is added in order to efficiently proceed the polymerization reaction of the energy ray-curable resin (g). It may be contained.
  • Examples of the photopolymerization initiator (h) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and other benzoin compounds; acetophenone; Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; ⁇ -ketol such as 1-hydroxycyclohexyl phenyl ketone Compound
  • the photopolymerization initiator (h) is preferably an aliphatic compound. Since the adhesive composition and the film adhesive contain an aliphatic compound as the photopolymerization initiator (h), suppression of coloring after heating the film adhesive (for example, heating at 260° C.) The effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.
  • the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and by containing only those having no such bond or group (in other words, not containing those having these bonds or groups), the above-described effect of suppressing coloration is remarkably high. Become.
  • the photopolymerization initiators (h) more specifically, as the aliphatic compound (aliphatic photopolymerization initiator), for example, an acylphosphine oxide compound; a sulfide compound such as tetramethylthiuram monosulfide; an azo Examples thereof include azo compounds such as bisisobutyronitrile; peroxide compounds; diketone compounds such as diacetyl; photosensitizers such as amines.
  • the photopolymerization initiator (h) that does not have one or more selected from the group consisting of include, for example, compounds other than azobisisobutyronitrile.
  • the photopolymerization initiator (h) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrarily selected. it can.
  • the content of the photopolymerization initiator (h) in the adhesive composition is 0.1 with respect to 100 parts by mass of the energy ray-curable resin (g). It is preferably from 20 to 20 parts by mass, more preferably from 1 to 10 parts by mass, particularly preferably from 2 to 5 parts by mass.
  • the adhesive composition and the film adhesive may contain the other antioxidant (y) as long as the effect of the present invention is not impaired.
  • the other antioxidant (y) is not particularly limited as long as it is an antioxidant other than the phosphorus-based antioxidant (z), and may be an organic compound or an inorganic compound.
  • the other antioxidant (y) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio may be arbitrarily set. You can choose.
  • the content of the other antioxidant (y) in the adhesive composition and the film adhesive is 100 parts by mass of the phosphorus-based antioxidant (z). On the other hand, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less.
  • the content of the other antioxidant (y) is not more than the upper limit value, the coloring of the film adhesive before and after heating is further suppressed.
  • the adhesive composition and the film adhesive preferably do not contain any other antioxidant (y).
  • the adhesive composition and the film adhesive may contain the thermoplastic resin (x) as long as the effects of the present invention are not impaired.
  • the thermoplastic resin (x) for example, at the time of pickup, it becomes easier to separate the chip provided with the film adhesive from a dicing sheet described later, or a film is formed on an uneven surface of an adherend.
  • the linear adhesive may easily follow, and the occurrence of voids and the like between the adherend and the film adhesive may be further suppressed.
  • thermoplastic resin (x) is not particularly limited as long as it is a thermoplastic resin other than the acrylic resin (a).
  • examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene and the like.
  • the weight average molecular weight of the thermoplastic resin (x) is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.
  • the glass transition temperature (Tg) of the thermoplastic resin (x) is preferably ⁇ 30 to 150° C., more preferably ⁇ 20 to 120° C.
  • thermoplastic resin (x) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
  • the content of the thermoplastic resin (x) is 10 parts by mass based on 100 parts by mass of the acrylic resin (a). It is preferably not more than 5 parts by mass, more preferably not more than 5 parts by mass, still more preferably not more than 1 part by mass.
  • the content of the thermoplastic resin (x) is equal to or less than the upper limit value, the effect of using the acrylic resin (a) can be more significantly obtained.
  • the adhesive composition and the film adhesive do not contain the thermoplastic resin (x).
  • the general-purpose additive (i) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited.
  • Examples of preferable general-purpose additives (I) include plasticizers, antistatic agents, colorants (dyes and pigments), gettering agents, and the like.
  • the general-purpose additive (i) is an organic compound
  • such general-purpose additive (i) is preferably an aliphatic compound. .. Since the adhesive composition and the film adhesive contain an aliphatic compound as an organic general-purpose additive, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is further improved. The effect of suppressing the above-mentioned coloring is significantly increased by containing only the aliphatic compound (in other words, not containing the aromatic compound).
  • the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and only the aliphatic compound having no such bond or group is contained (in other words, the aliphatic compound having these bond or group is not contained), the above-mentioned coloring The suppression effect is remarkably enhanced.
  • the general-purpose additive (i) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
  • the content of the general-purpose additive (i) in the adhesive composition and the film adhesive is not particularly limited and may be appropriately selected depending on the purpose.
  • the adhesive composition preferably further contains a solvent.
  • the adhesive composition containing a solvent has good handleability.
  • the solvent is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
  • the solvent contained in the adhesive composition may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
  • the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the adhesive composition can be mixed more uniformly.
  • the adhesive composition can be obtained by blending each component for constituting the adhesive composition.
  • the order of adding each component is not particularly limited, and two or more components may be added simultaneously.
  • a solvent it may be used by preliminarily diluting this compounding ingredient by mixing the solvent with any compounding ingredient other than the solvent, or diluting any compounding ingredient other than the solvent beforehand.
  • the solvent may be used as a mixture with these compounding ingredients.
  • the method of mixing the components at the time of blending is not particularly limited, and a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by adding ultrasonic waves It may be selected appropriately.
  • the temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.
  • FIG. 1 is a sectional view schematically showing a film adhesive according to one embodiment of the present invention. It should be noted that, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there may be a case where an essential part is enlarged, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.
  • the film adhesive 13 shown here is provided with a first release film 151 on one surface (sometimes referred to as “first surface” in the present specification) 13a thereof, and the first surface 13a is The second release film 152 is provided on the other surface (may be referred to as “second surface” in this specification) 13b on the opposite side.
  • reference numeral 109 is given to the laminated sheet configured by laminating the first release film 151, the film adhesive 13 and the second release film 152 in this order in this order in the thickness direction. ing.
  • Such a film-like adhesive 13 (laminated sheet 109) is suitable for storage as a roll, for example.
  • the film adhesive 13 has the above-mentioned light transmittance.
  • at least one of the first surface 13a and the second surface 13b of the film adhesive 13 does not substantially contain an aromatic compound.
  • the thickness of the film adhesive 13 is preferably 10 to 40 ⁇ m.
  • the film adhesive 13 can be formed using the above-mentioned adhesive composition.
  • Both the first release film 151 and the second release film 152 may be known ones.
  • the first release film 151 and the second release film 152 may be the same as each other, or different from each other, such as different release forces required when releasing from the film adhesive 13. Good.
  • one of the first peeling film 151 and the second peeling film 152 is removed, and the exposed surface thus formed becomes the sticking surface to the sticking target.
  • the sticking target for example, the chip and the like can be mentioned.
  • the chip the surface on which the film adhesive 13 is attached becomes the circuit forming surface.
  • the preferable film adhesive for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, At least one surface of the film adhesive is substantially free of aromatic compounds, Using the film adhesive having a size of 2 mm ⁇ 2 mm and a thickness of 20 ⁇ m, the copper plate having a size of 30 mm ⁇ 30 mm and a thickness of 300 ⁇ m, and a silicon chip, the film adhesive , A test piece in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate, and the side surfaces of the film adhesive and the silicon chip are aligned.
  • the other of the film adhesive A force is applied in a direction parallel to the surface at a speed of 200 ⁇ m/s, and the maximum value of the force applied until the film adhesive is broken is defined as the shear strength (N /2 mm ⁇ ), the shear strength is 20 N/2 mm ⁇ or more.
  • the preferable film adhesive for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, At least one surface of the film adhesive is substantially free of aromatic compounds,
  • the film adhesive contains a phosphorus-based antioxidant (z),
  • the phosphorus-based antioxidant (z) is an aliphatic compound, and is one selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Or the thing which does not have 2 or more types is mentioned.
  • the preferable film adhesive for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, At least one surface of the film adhesive is substantially free of aromatic compounds,
  • the film adhesive contains an epoxy compound (b1),
  • the epoxy compound (b1) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above.
  • the preferable film adhesive for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, At least one surface of the film adhesive is substantially free of aromatic compounds,
  • the film adhesive contains an acrylic resin (a) and a crosslinking agent (f),
  • the acrylic resin (a) has a functional group capable of binding to the crosslinking agent (f),
  • the cross-linking agent (f) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above are included.
  • the preferable film adhesive for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover, At least one surface of the film adhesive is substantially free of aromatic compounds,
  • the film adhesive contains a filler (d),
  • the filler (d) has an average particle diameter of 10 to 100 nm.
  • a laminated sheet according to an embodiment of the present invention is configured to include the film adhesive and a resin film provided on one surface of the film adhesive. ..
  • a composite sheet according to an embodiment of the present invention includes the film adhesive and a dicing sheet provided on one surface of the film adhesive, and the dicing sheet is a base material. And a pressure-sensitive adhesive layer provided on one surface of the base material, and the pressure-sensitive adhesive layer is disposed between the base material and the film adhesive.
  • the resin film may be provided only on one side, or on both sides (that is, the one side A resin film may be provided on the surface of (1) and on the other surface on the opposite side.
  • these resin films may be the same or different from each other, and the combination of these resin films is not particularly limited.
  • the resin film may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other.
  • the combination of these plural layers is not particularly limited.
  • the resin film may be a sheet containing only resin as a constituent material, or may be a sheet containing resin and other components as constituent materials and resin as a major constituent material.
  • Examples of the resin that is a constituent material of the resin film include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene.
  • polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene.
  • Polyolefin other than polyethylene such as norbornene resin; ethylene such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer -Based copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene; Polycycloolefins; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylic acid ester; polyurethane; polyurethane acrylate; polyimide
  • the resin also include polymer alloys such as a mixture of the polyester and other resins.
  • the polymer alloy of the polyester and the resin other than the polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
  • the resin for example, a crosslinked resin obtained by crosslinking one or two or more of the resins exemplified so far; modification of an ionomer or the like using one or more of the resins exemplified so far Resins are also included.
  • the resin film may be a release film or a base material described later.
  • the base material will be explained in detail separately.
  • the release film includes, for example, a multi-layered film including a resin layer and a release treatment layer provided on one surface of the resin layer.
  • the release film can be manufactured by subjecting one surface of the resin layer to a release treatment.
  • the resin layer can be prepared by molding or coating a resin composition containing a resin and drying it as necessary.
  • the resin that is a constituent material of the resin layer is the same as the resin that is a constituent material of the resin film.
  • the peeling treatment of the resin layer can be performed with various known peeling agents such as alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents.
  • the release agent is preferably an alkyd-based, silicone-based or fluorine-based release agent in terms of heat resistance.
  • the resin layer may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other, The combination of these plural layers is not particularly limited.
  • the laminated sheet 109 shown in FIG. 1 As a laminated sheet configured by providing the release film as a resin film on both surfaces of the film adhesive, for example, the laminated sheet 109 shown in FIG. 1 can be cited.
  • the laminated sheet 108 shown in FIG. 2 can be cited. 2 and subsequent figures, the same components as those shown in the already described figures are designated by the same reference numerals as those in the already described figures, and detailed description thereof will be omitted.
  • the laminated sheet 108 shown here is configured by including the resin film 19 on the first surface 13 a of the film adhesive 13.
  • the resin film 19 is as described above, and may be a release film (for example, the first release film 151 or the second release film 152 in FIG. 1) or a base material described later.
  • the thickness of the resin film can be arbitrarily set according to the purpose and is not particularly limited.
  • the thickness of the resin film may be, for example, 10 to 200 ⁇ m.
  • the laminated sheet of the present embodiment is not limited to the one shown in FIG. 2, and a configuration in which a part of the configuration shown in FIG. 2 is changed or deleted, or is described so far, within a range that does not impair the effects of the present invention.
  • Other configurations may be added to the above configuration. More specifically, it is as follows.
  • the laminated sheet of the present embodiment may have nothing on the second surface of the film adhesive, but the laminated sheet may be provided on the second surface of the film adhesive in a region near the peripheral portion.
  • a jig adhesive layer for fixing to a jig such as a ring frame may be provided.
  • the adhesive layer for a jig may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet as a core material. It may be one.
  • the surface area of the film-like adhesive and the resin film may be the same or almost the same when the laminated sheet is viewed from above the film-like adhesive side or the resin film side and viewed in a plan view.
  • the surface area of the film adhesive may be smaller than the surface area of the resin film, and a partial region of the resin film may be exposed. In that case, for example, at least the peripheral portion in the width direction of the resin film may be exposed without being covered with the film adhesive.
  • Such a laminated sheet may be provided with the jig adhesive layer on the exposed surface of the resin film.
  • FIG. 3 is a sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention.
  • the composite sheet 101 shown here includes a film adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film adhesive 13, and the dicing sheet 10 includes a base material 11 and The pressure-sensitive adhesive layer 12 provided on one surface (sometimes referred to as “first surface” in the present specification) 11a of the base material 11, and the pressure-sensitive adhesive layer 12 is a base material. 11 and the film adhesive 13 are arranged and configured.
  • the composite sheet 101 is configured by laminating the base material 11, the adhesive layer 12, and the film adhesive 13 in this order in the thickness direction thereof.
  • the surface 10 a of the dicing sheet 10 on the film adhesive 13 side (may be referred to as “first surface” in the present specification) is a surface opposite to the base material 11 side of the pressure-sensitive adhesive layer 12 (the book). In the specification, it may be referred to as a "first surface") 12a.
  • the composite sheet 101 further includes a release film 15 on the film adhesive 13.
  • the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the film adhesive 13 is laminated on the entire surface or almost all of the first surface 12a of the pressure-sensitive adhesive layer 12 to form a film.
  • the release film 15 is laminated on the entire surface or almost the entire surface of the first surface 13 a of the adhesive 13.
  • the dicing sheet 10 may be a known one.
  • the base material 11 and the pressure-sensitive adhesive layer 12 in the dicing sheet 10 will be sequentially described.
  • the base material 11 in the dicing sheet 10 has a sheet shape or a film shape, and examples of the constituent material thereof include various resins.
  • examples of the resin which is a constituent material of the dicing sheet 10 include the same resin as a constituent material of the resin film in the laminated sheet.
  • the resin constituting the base material may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.
  • the base material may be composed of one layer (single layer) or may be composed of two or more layers. When composed of a plurality of layers, the plurality of layers may be the same or different from each other. However, the combination of these plural layers is not particularly limited.
  • the thickness of the base material 11 is preferably 50 to 300 ⁇ m, more preferably 60 to 150 ⁇ m. When the thickness of the base material 11 is in such a range, the flexibility of the composite sheet 101 and the sticking property to the sticking target are further improved.
  • the “thickness of the base material” means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all layers constituting the base material. means.
  • the base material 11 has a high thickness accuracy, that is, a material in which the thickness variation is suppressed regardless of the part.
  • a highly accurate base material examples include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Are listed.
  • the base material 11 contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst and a softening agent (plasticizer) in addition to the main constituent materials such as the resin. May be
  • the base material 11 may be transparent or opaque, and may be colored depending on the purpose, or another layer may be vapor-deposited.
  • the base material 11 has a roughening treatment such as a sand blasting treatment or a solvent treatment, a corona discharge treatment, an electron beam treatment, or the like in order to improve the adhesion with other layers (here, the pressure-sensitive adhesive layer 12) provided thereon.
  • the surface may be subjected to irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, or the like.
  • the base material 11 may have a surface subjected to a primer treatment.
  • the base material 11 is an antistatic coating layer; a layer that prevents the base material 11 from adhering to another sheet and the base material 11 from adhering to the suction table when the composite sheets are stored in a stacked state. Etc. may be included.
  • the base material 11 can be manufactured by a known method.
  • the base material 11 containing a resin can be manufactured by molding a resin composition containing the resin.
  • the pressure-sensitive adhesive layer 12 in the dicing sheet 10 has a sheet shape or a film shape and contains a pressure-sensitive adhesive.
  • the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin, and acrylic resin is preferable. ..
  • adhesive resin includes both a resin having an adhesive property and a resin having an adhesive property.
  • the adhesive resin is not only the resin having adhesiveness itself, but also the resin that exhibits adhesiveness when used in combination with other components such as additives, and the adhesiveness due to the presence of a trigger such as heat or water. Resins and the like indicating are also included.
  • the pressure-sensitive adhesive layer 12 may be composed of one layer (single layer) or may be composed of two or more layers. When composed of a plurality of layers, these layers may be the same as each other. They may be different, and the combination of these plural layers is not particularly limited.
  • the thickness of the pressure-sensitive adhesive layer 12 is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
  • the "thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer, for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.
  • the adhesive layer 12 may be formed using an energy ray curable adhesive or may be formed using a non-energy ray curable adhesive. That is, the adhesive layer 12 may be either energy ray curable or non-energy ray curable.
  • the energy ray-curable pressure-sensitive adhesive layer 12 can easily adjust physical properties before and after curing. For example, by curing the energy ray-curable pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive force to the attachment target can be easily adjusted.
  • the pressure-sensitive adhesive layer 12 can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive composition can be applied to the surface on which the pressure-sensitive adhesive layer 12 is to be formed and, if necessary, dried to form the pressure-sensitive adhesive layer 12 at a desired site.
  • the content ratio of the components that do not vaporize at room temperature is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer 12.
  • the “normal temperature” means a temperature at which it is not cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.
  • the coating of the adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater.
  • a known method for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater.
  • Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.
  • the pressure-sensitive adhesive composition is applied on the base material 11 and dried as necessary to form the pressure-sensitive adhesive layer 12 on the base material 11. It may be laminated.
  • the pressure-sensitive adhesive layer 12 is provided on the base material 11, for example, the pressure-sensitive adhesive composition is applied on the release film and dried as necessary to form the pressure-sensitive adhesive layer 12 on the release film. Even if the pressure-sensitive adhesive layer 12 is laminated on the base material 11 by forming it and bonding the exposed surface of the pressure-sensitive adhesive layer 12 to one surface (here, the first surface 11 a) of the base material 11. Good. In this case, the release film may be removed at any timing during the manufacturing process or the use process of the composite sheet 101.
  • the energy ray-curable pressure-sensitive adhesive composition may be, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, referred to as “pressure-sensitive adhesive (I -1a)”) and an energy ray-curable compound; and an unsaturated group in the side chain of the adhesive resin (I-1a).
  • a pressure-sensitive adhesive composition (I-2) containing the introduced energy ray-curable pressure-sensitive adhesive resin (I-2a) hereinafter, may be abbreviated as “adhesive resin (I-2a)”
  • Examples thereof include an adhesive composition (I-3) containing an adhesive resin (I-2a) and an energy ray-curable compound.
  • the non-energy ray curable pressure sensitive adhesive composition is, for example, a pressure sensitive adhesive composition (I-4) containing the pressure sensitive adhesive resin (I-1a). Etc.
  • the film adhesive 13 has the above-mentioned light transmittance.
  • at least one of the first surface 13a and the second surface 13b of the film adhesive 13 does not substantially contain an aromatic compound.
  • the thickness of the film adhesive 13 is preferably 10 to 40 ⁇ m.
  • the film adhesive 13 can be formed using the above-mentioned adhesive composition.
  • the release film 15 is similar to the first release film 151 or the second release film 152 shown in FIG.
  • the release film (for example, the release film 15 shown in FIG. 3) has any configuration, and the composite sheet of the present embodiment includes the release film. It may or may not be provided.
  • the composite sheet 101 is used with an object (for example, a circuit forming surface of a chip) attached to the first surface 13a of the film adhesive 13 with the release film 15 removed.
  • an object for example, a circuit forming surface of a chip
  • the composite sheet of the present embodiment is not limited to the one shown in FIG. 3, and a part of the configuration shown in FIG. 3 has been changed or deleted, or has been described so far, as long as the effect of the present invention is not impaired.
  • Other configurations may be added to the above configuration. More specifically, it is as follows.
  • the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment may include a dicing sheet including only the base material. .. That is, the composite sheet comprises a base material and a film adhesive provided on one surface of the base material, and a pressure-sensitive adhesive layer is provided between the base material and the film adhesive. It may be configured without being arranged.
  • An example of such a composite sheet is the laminated sheet 108 shown in FIG. 2 in which the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3).
  • the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment includes an intermediate layer in addition to the base material and the pressure-sensitive adhesive layer.
  • a dicing sheet for example, a base material, a pressure-sensitive adhesive layer provided on one surface of the base material, and a surface of the pressure-sensitive adhesive layer opposite to the base material side are provided. And an intermediate layer.
  • an intermediate layer is arranged between the pressure-sensitive adhesive layer and the film adhesive in the composite sheet.
  • the composite sheet of the present embodiment may include only the release film on the first surface of the film adhesive, but in the first surface of the film adhesive, in the region near the peripheral edge, A jig adhesive layer for fixing the composite sheet to a jig such as a ring frame may be provided.
  • the jig adhesive layer in this case is the same as that described above.
  • the surface area of the film-like adhesive and the dicing sheet may be the same or almost the same when the composite sheet is viewed from above the film-like adhesive side or the dicing sheet side and viewed in a plane.
  • the surface area of the film adhesive may be smaller than the surface area of the dicing sheet, and a partial area of the dicing sheet (for example, the pressure-sensitive adhesive layer) may be exposed. In that case, for example, at least the peripheral portion in the width direction of the dicing sheet may be exposed without being covered with the film adhesive.
  • Such a composite sheet may include the jig adhesive layer on the exposed surface of the dicing sheet.
  • a substrate, a pressure-sensitive adhesive layer, an intermediate layer, a film adhesive, a jig adhesive layer and a release film have been shown as constituting the composite sheet, but the composite sheet of the present embodiment is Other layers that do not correspond to any of these may be provided.
  • the composite sheet includes the other layer, the arrangement position is not particularly limited.
  • the size and shape of each layer can be arbitrarily selected according to the purpose.
  • the film adhesive in the laminated sheet of the present embodiment can be used as a film for adhering the light-transmitting cover to the circuit forming surface of a chip such as a sensor. More specifically, by using the film adhesive, the chip, the film adhesive provided on the circuit forming surface of the chip, and the surface of the film adhesive opposite to the chip side. It is possible to manufacture a laminated body including the light-transmitting cover provided above.
  • the chip-side surface of the film adhesive and the light-transmissive cover-side surface do not substantially contain an aromatic compound, and both are substantially aromatic. It is preferably free of compounds.
  • FIG. 4 is a sectional view schematically showing an example of the laminated body.
  • the laminated body 801 shown here is the chip 8, the film adhesive 13 provided on the circuit forming surface 8a of the chip 8, and the surface of the film adhesive 13 opposite to the chip 8 side (first surface). And a light-transmitting cover 7 provided on 13a.
  • the surfaces of the chip 8 and the film adhesive 13 that face each other that is, the circuit forming surface 8a of the chip 8 and the surface (second surface) 13b of the film adhesive 13 on the chip 8 side are formed. , Are in direct contact.
  • the film adhesive 13 and the light transmissive cover 7 face each other, that is, the first surface 13a of the film adhesive 13 and the film adhesive 13 side of the light transmissive cover 7 (the book In the specification, it may be referred to as the "second surface") 7b, and is in direct contact.
  • the chip 8, the film adhesive 13, and the light transmissive cover 7 are laminated in this order in the thickness direction thereof, and the circuit forming surface 8a of the chip 8 is in the film form. It is arranged and configured on the adhesive 13 side.
  • the film adhesive 13 in the laminated body 801 is, for example, the laminated sheet 109 shown in FIG. 1 from which the first release film 151 and the second release film 152 are removed, or the laminated sheet 108 shown in FIG. The resin film 19 is removed.
  • the laminate 801 either one or both of the first surface 13a and the second surface 13b of the film adhesive 13 do not substantially contain an aromatic compound, and both do not substantially contain an aromatic compound. It is preferable.
  • Reference numeral 7a indicates a surface of the light transmissive cover 7 opposite to the second surface 7b (may be referred to as "first surface” in the present specification).
  • the light transmissive cover 7 protects the circuit forming surface 8a of the chip 8 and makes the outside of the second surface 7b side visible from the outside of the first surface 7a side.
  • the film adhesive 13 has the above-mentioned light transmittance. Therefore, in the laminated body 801, the visual information existing on the circuit forming surface 8a of the chip 8 through the light transmissive cover 7 and the film adhesive 13 (through the light transmissive cover 7 and the film adhesive 13). However, it is visible. Furthermore, as described above, the film adhesive 13 has high light transmittance before and after heating and is suppressed from being colored. Therefore, the laminated body 801 can visually recognize the visual information on the chip 8 stably and with high accuracy.
  • the laminated body 801 can be used as a fingerprint sensor module.
  • the laminated body using the film adhesive is not limited to that shown in FIG. 4, and a part of the configuration shown in FIG. 4 is changed or deleted within a range not impairing the effects of the present invention. Further, other configurations may be added to those described above.
  • one surface (second surface) of the film adhesive is attached to a circuit forming surface of the chip, and the other surface (first surface) of the film adhesive is optically transparent. It can be manufactured by laminating a flexible cover.
  • FIG. 5 is sectional drawing for demonstrating an example of the usage method of the composite sheet of this embodiment typically. Here, the case where the composite sheet 101 shown in FIG. 3 is used is shown.
  • the composite sheet 101 is used by removing the release film 15 and then attaching the first surface 13a of the film adhesive 13 to the circuit forming surface 8a of the chip 8.
  • the chip 8 After attaching the composite sheet 101 to the chip 8, for example, the chip 8 is diced into individual pieces, and the film adhesive 13 is cut along the outer periphery of the individual chips 8. At this time, the chip 8 can be divided into individual pieces and the film adhesive 13 can be cut by a known method. For example, these can be performed at the same time, or the chip 8 can be divided into individual pieces and then separated. The film adhesive 13 may be cut.
  • the individual chips 8 are separated from the dicing sheet 10 together with the cut film adhesive 13 and picked up.
  • the pressure-sensitive adhesive layer 12 is energy ray-curable, the pressure-sensitive adhesive layer 12 is cured with energy rays to reduce the adhesive strength to the film adhesive 13 and then picked up to make the pickup easier. It can be carried out.
  • the above-mentioned laminated body (for example, laminated body 801 shown in FIG. 4) can be manufactured by attaching a light-transmitting cover to the second surface of the film adhesive 13 after cutting and picking up.
  • the first surface and the second surface of the film adhesive are preferably substantially free of an aromatic compound, and both are preferably substantially free of an aromatic compound. ..
  • the film-like adhesive in the composite sheet is stuck to the chip, and after the chip is divided into pieces and the film-like adhesive is cut, a light-transmitting cover is attached to the cut film-like adhesive.
  • laminating is explained, the order of laminating the chip and the light-transmitting cover to the film adhesive may be reversed.
  • the light-transmitting cover is diced into individual pieces, and the film-like adhesive is cut, and if necessary, After curing the pressure-sensitive adhesive layer with energy rays, the light-transmitting cover after separation into pieces is separated from the dicing sheet together with the film adhesive after cutting and picked up, and then the film bonding after cutting and picking up
  • the laminated body (for example, the laminated body 801 shown in FIG. 4) can also be manufactured by bonding a chip to the first surface of the agent.
  • Acrylic resin (a)] (A)-1: An acrylic resin (weight average molecular weight 800,000, glass transition temperature 6° C.) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). (A)-2: An acrylic resin (weight average molecular weight 800,000, glass transition temperature 9° C.) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass).
  • a polyethylene terephthalate (PET) film has a release film (one side of which has been subjected to a release treatment by silicone treatment) (SP-PET381031 manufactured by Lintec Co., Ltd., thickness: 38 ⁇ m), and the above-mentioned release treatment is applied to the release-treated surface.
  • the adhesive composition is applied and dried by heating at 100° C. for 2 minutes to form a film adhesive having a thickness of 20 ⁇ m, and the release film and the film adhesive are laminated in the thickness direction thereof.
  • a structured adhesive sheet was obtained.
  • a dicing blade (“NBC-ZH2050-SE27HECC manufactured by DISCO”) was used to perform dicing at a blade rotation speed of 30,000 rpm and a cutting speed of 40 mm/s.
  • a plurality of 2 mm ⁇ 2 mm silicon chips (hereinafter sometimes referred to as “silicon chip group”) were obtained, and the dicing sheet is formed by laminating a base material and an adhesive layer, and Occasionally, the dicing blade was used to cut into a region having a depth of 20 ⁇ m in the dicing sheet.
  • the adhesive sheet obtained above was attached to the silicon chip group obtained above while being heated to 60° C. with the film-like adhesive therein. At this time, the adhesive sheet was attached to the surface (exposed surface) opposite to the side to which the dicing sheet was attached, of the silicon chips in the silicon chip group. Then, the adhesive sheet after the attachment was cut along the outer periphery of the silicon chip. As described above, the dicing sheet, the silicon chip, and the adhesive sheet were laminated in this order in the thickness direction to obtain a laminate having a size of 2 mm ⁇ 2 mm.
  • the release film was removed from the film adhesive in this laminate, and the exposed surface of the newly formed film adhesive was measured with a manual die bonder to have a size of 30 mm ⁇ 30 mm and a thickness of 300 ⁇ m. It was attached to the surface of a copper plate.
  • the film adhesive was applied by applying a force of 2.45 N (250 gf) to the copper plate while heating it to 125°C. Further, the bonded pieces were heated at 175° C. for 5 hours to obtain a test piece.
  • the film adhesive obtained above was attached to one surface of a glass slide (thickness 0.9 mm) while heating at 40°C.
  • the film adhesive was not subjected to heat treatment immediately after its production and before this attachment. Then, of the film adhesive after sticking, the part protruding from the glass slide is cut, and the film adhesive of the same size and the glass slide are in a state where the positions of these peripheral portions are the same, A test piece (hereinafter referred to as a “pre-heating test piece”) configured by stacking in the thickness direction was obtained.
  • a straight line of light (400 to 800 nm) was prepared in advance using a spectrophotometer (“UV-3101PC” manufactured by Shimadzu Co.) before the preparation of the pre-heating test piece.
  • the transmittance (hereinafter, referred to as “reference linear transmittance”) was measured.
  • the linear transmittance of light (400 to 800 nm) was also measured for the pre-heated test piece obtained above by the same method.
  • the value obtained by subtracting the measured value of the reference linear transmittance at the same wavelength from the measured value of the linear transmittance of light (400 to 800 nm) at each wavelength of the test piece before heating is the film before heating. It was adopted as the linear transmittance of light (400 to 800 nm) of the linear adhesive (that is, the linear transmittance before heating).
  • Table 1 The results are shown in Table 1.
  • test piece after heating ⁇ Measurement of linear transmittance after heating with light (400 to 800 nm)> An electric furnace was used to heat the test piece after measuring the linear transmittance of the light (400 to 800 nm) before heating at 260° C. for 10 minutes. Then, the heated test piece was allowed to cool to the same temperature as room temperature. Then, the linear transmittance of light (400 to 800 nm) of the test piece after heating and cooling (hereinafter, referred to as “test piece after heating”) is measured by the same method as in the case of the test piece before heating. did.
  • a digital camera (“IXY650” manufactured by Canon Inc.) is placed in front of the ball of the left index finger, and the distance between the surface of the ball of the left index finger and the surface of the camera lens is adjusted to 50 mm.
  • Imaging data of the fingerprint of the left index finger (hereinafter referred to as “reference imaging data”) was acquired in macro mode. While maintaining the positional relationship between the left index finger and the digital camera, the pre-heating test piece was further arranged between the belly of the left index finger and the digital camera.
  • pre-heating transmission imaging data the imaging data of the fingerprint of the left index finger
  • the value obtained by subtracting the R value of the valley portion of the fingerprint acquired from the reference imaging data from the R value of the valley portion of the fingerprint acquired from the transmission imaging data before heating is obtained during the pre-heating evaluation. It was adopted as the R value of the valley part of the fingerprint.
  • the G value and B value of the valley portion of the fingerprint at the time of evaluation before heating were determined.
  • the absolute value of the difference between the R value of the mountain portion and the R value of the valley portion (hereinafter sometimes referred to as “absolute value ⁇ R”) is calculated, and the G value of the mountain portion and the valley portion are calculated.
  • the absolute value of the difference between the B value of the mountain portion and the B value of the valley portion (hereinafter, referred to as “absolute value ⁇ G”) is calculated. “Absolute value ⁇ B” may be described) was calculated.
  • the R value, G value, and B value of the fingerprint ridge portion during the pre-heating evaluation instead of the R value, G value, and The B value was obtained, and instead of the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation before heating, the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation after heating were obtained. Further, from these R value, G value and B value, instead of the absolute value ⁇ R, absolute value ⁇ G and absolute value ⁇ B at the time of evaluation before heating, the absolute value ⁇ R, absolute value ⁇ G and absolute value ⁇ B at the time of evaluation after heating are used. Was calculated. The results are shown in Table 1.
  • the film adhesives before and after heating at 260° C. all had high light transmittance, suppressed coloring, and had high fingerprint recognizability.
  • the linear adhesiveness of light (400 to 800 nm) of the film adhesive before heating at 260° C. was 95% or more (95 to 98%), and the film adhesive after heating at 260° C. was used.
  • the linear transmittance of light (400 to 800 nm) of the adhesive was 86% or more (86 to 95%).
  • the shear strength of the film adhesive was 48 N/2 mm ⁇ or more (48 to 80 N/2 mm ⁇ ), and the adhesive strength of the film adhesive was sufficiently strong.
  • the film adhesive contained a phosphorus-based antioxidant (z), and all components including the phosphorus-based antioxidant (z) were aromatic cyclic compounds. Since it did not have a group, it was speculated that coloring due to heating was suppressed.
  • in the wave number range of 3050 to 2990 cm ⁇ 1 there was no clear inflection point which could not be called noise in the curve showing the transmittance, and the measurement surface of the film-like adhesive was not observed. , which indicates the substantial absence of aromatic compounds, a result consistent with the use of each of the above components.
  • FIG. 6 does not show the results in Examples 3 to 4 in order to make the curve showing the transmittance easy to see, but the curves in Examples 3 to 4 also have the same shape as the curves in Examples 1 and 2. there were.
  • Comparative Examples 1 to 3 the film adhesives after heating at 260° C. had low light transmittance, coloring was not suppressed, and fingerprint recognition was low.
  • the linear transmittance of light (400 to 800 nm) of the film adhesive after heating at 260° C. was 16% or less.
  • Comparative Examples 1 and 3 although the film adhesive contained the phosphorus-based antioxidant (z), the epoxy compound (b1), the phenol resin (b2), and the cross-linking agent (f) were all aromatic. It was speculated that coloring due to heating was not suppressed because it had a group cyclic group. As is clear from FIG. 5, in Comparative Examples 1 and 3, in the wave number range of 3050 to 2990 cm ⁇ 1, a clear inflection point which is not noise can be observed in the curve showing the transmittance, and the film-like adhesion is observed. It is shown that an aromatic compound is present on the measurement surface of the agent. This result was consistent with the use of each of the above components.
  • the film adhesive before heating at 260° C. had high light transmittance and suppressed coloring, but did not contain any antioxidants including the phosphorus-based antioxidant (z). Moreover, since the epoxy compound (b1), the phenol resin (b2), and the cross-linking agent (f) each had an aromatic cyclic group, it was speculated that coloring due to heating was not suppressed. .. As is clear from FIG. 5, in Comparative Example 2, a clear inflection point was observed in the curve showing the transmittance in the wave number range of 3050 to 2990 cm ⁇ 1 , and the measurement surface of the film-like adhesive was observed. , Indicating the presence of aromatic compounds. This result was consistent with the use of each of the above components.
  • the present invention can be used as an adhesive at the time of manufacturing or processing various parts constituting an electronic device.

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Abstract

A film-like adhesive of this embodiment is for bonding a circuit formation surface of a chip to a light-transmissive cover. At least one surface of the film-like adhesive does not substantially include an aromatic compound.

Description

フィルム状接着剤、積層シート、複合シート、及び積層体の製造方法Film adhesive, laminated sheet, composite sheet, and method for producing laminated body
 本発明は、フィルム状接着剤、積層シート、複合シート、及び積層体の製造方法に関する。
 本願は、2018年12月28日に日本に出願された特願2018-246839号に基づき優先権を主張し、その内容をここに援用する。
The present invention relates to a film adhesive, a laminated sheet, a composite sheet, and a method for producing a laminated body.
The present application claims priority based on Japanese Patent Application No. 2018-246839 filed on December 28, 2018 in Japan, and the content thereof is incorporated herein.
 電子機器を構成する各種部品の製造又は加工時には、目的に応じて種々のフィルム状接着剤が使用される。
 例えば、半導体チップを基板の回路形成面に装着する場合には、半導体チップの裏面にフィルム状接着剤を貼付しておき、このフィルム状接着剤を介して、半導体チップを基板の回路形成面に接着(ダイボンディング)する。また、センサー等のチップの回路形成面を保護する場合には、光透過性を有するフィルム状接着剤を介して、前記回路形成面を光透過性カバーで被覆する。
Various film adhesives are used depending on the purpose at the time of manufacturing or processing various parts constituting electronic devices.
For example, when mounting the semiconductor chip on the circuit forming surface of the substrate, a film adhesive is pasted on the back surface of the semiconductor chip, and the semiconductor chip is attached to the circuit forming surface of the substrate via this film adhesive. Adhere (die bonding). When protecting the circuit forming surface of a chip such as a sensor, the circuit forming surface is covered with a light transmissive cover via a light-transmissive film adhesive.
 一方で、このようなフィルム状接着剤を備えた部品は、はんだリフロー工程等の加熱工程によって、高温下に晒されることがある。その場合、熱の影響による、フィルム状接着剤の変質が問題となることがある。例えば、光透過性を有するフィルム状接着剤が変色すると、このフィルム状接着剤を介した情報の読み取りが、困難になってしまう。フィルム状接着剤は、接着性を発現するために樹脂成分を含有しており、場合によっては、熱硬化性を付与するために、熱硬化性成分を含有しているが、これらの成分は、熱に対して不安定なものがある。すなわち、従来のフィルム状接着剤は、加熱によって変色し易い。 On the other hand, parts equipped with such a film adhesive may be exposed to high temperatures due to the heating process such as the solder reflow process. In that case, deterioration of the film adhesive due to the influence of heat may be a problem. For example, if the film adhesive having light transmittance changes color, it becomes difficult to read information through the film adhesive. The film adhesive contains a resin component in order to exhibit adhesiveness, and in some cases, contains a thermosetting component in order to impart thermosetting property, but these components are Some are unstable to heat. That is, the conventional film-like adhesive is easily discolored by heating.
 光透過性を有するフィルム状接着剤としては、例えば、半導体チップのダイボンディング用であり、波長1065nmにおける光線透過率が80%以上であるダイボンドフィルムが開示されている(特許文献1参照)。 As a film-like adhesive having a light-transmitting property, for example, a die-bonding film for die-bonding a semiconductor chip and having a light transmittance of 80% or more at a wavelength of 1065 nm is disclosed (see Patent Document 1).
日本国特許第6310748号公報Japanese Patent No. 6310748
 しかし、特許文献1には、ダイボンドフィルムの加熱後の色など、加熱後の物性については開示されていない。 However, Patent Document 1 does not disclose physical properties after heating, such as the color of the die bond film after heating.
 本発明は、加熱前後で光透過性を有し、加熱後の着色が抑制されるフィルム状接着剤と、前記フィルム状接着剤を用いた積層シート及び複合シートと、前記フィルム状接着剤を用いた積層体の製造方法を提供することを目的とする。 The present invention uses a film-like adhesive that has optical transparency before and after heating and is suppressed from being colored after heating, a laminated sheet and a composite sheet using the film-like adhesive, and the film-like adhesive. It is an object of the present invention to provide a method for manufacturing a laminated body having such a structure.
 本発明は、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まない、フィルム状接着剤を提供する。
 本発明のフィルム状接着剤においては、260℃で加熱する前の前記フィルム状接着剤の、波長が400~800nmである光の直線透過率が、90%以上であり、260℃で10分加熱した後の前記フィルム状接着剤の、波長が400~800nmである光の直線透過率が、85%以上であり、前記フィルム状接着剤の厚さが10~40μmであってもよい。
 本発明のフィルム状接着剤は、脂肪族系エポキシ化合物を含有することが好ましい。
The present invention is a film adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover, wherein at least one surface of the film adhesive contains a substantially aromatic compound. No, provide a film adhesive.
In the film adhesive of the present invention, the linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive before heating at 260° C. is 90% or more, and the film adhesive is heated at 260° C. for 10 minutes. The linear adhesiveness of light having a wavelength of 400 to 800 nm may be 85% or more, and the thickness of the adhesive film may be 10 to 40 μm.
The film adhesive of the present invention preferably contains an aliphatic epoxy compound.
 本発明のフィルム状接着剤は、酸化防止剤として、脂肪族系亜リン酸エステルを含有していてもよい。
 本発明のフィルム状接着剤においては、前記フィルム状接着剤が、アクリル系樹脂と、脂肪族多価イソシアネート系架橋剤と、を含有し、前記アクリル系樹脂が、前記架橋剤と結合可能な官能基を有していてもよい。
 本発明は、前記フィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられた樹脂フィルムと、を備えた、積層シートを提供する。
 本発明は、前記フィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられたダイシングシートと、を備えており、前記ダイシングシートが、基材と、前記基材の一方の面上に設けられた粘着剤層と、を備えており、前記粘着剤層が、前記基材と前記フィルム状接着剤との間に配置されている、複合シートを提供する。
 本発明は、前記フィルム状接着剤の一方の面に、チップの回路形成面を貼り合わせ、前記フィルム状接着剤の他方の面に、光透過性カバーを貼り合わせることにより、前記チップと、前記フィルム状接着剤と、前記光透過性カバーと、がこの順に積層されて構成された積層体を得る、積層体の製造方法を提供する。
The film adhesive of the present invention may contain an aliphatic phosphite ester as an antioxidant.
In the film adhesive of the present invention, the film adhesive contains an acrylic resin and an aliphatic polyisocyanate crosslinking agent, and the acrylic resin is a functional group capable of binding to the crosslinking agent. It may have a group.
The present invention provides a laminated sheet comprising the film adhesive and a resin film provided on one surface of the film adhesive.
The present invention comprises the film adhesive and a dicing sheet provided on one surface of the film adhesive, wherein the dicing sheet is a base material and one surface of the base material. And a pressure-sensitive adhesive layer provided on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer being disposed between the substrate and the film adhesive.
The present invention, the one surface of the film adhesive, the circuit forming surface of the chip is attached, the other surface of the film adhesive, by attaching a light-transmitting cover, the chip, the Provided is a method for producing a laminate, which comprises obtaining a laminate in which a film adhesive and the light-transmitting cover are laminated in this order.
 本発明のフィルム状接着剤は、その加熱前後で光透過性を有し、加熱後の着色が抑制される。
 本発明のフィルム状接着剤を備えた、本発明の積層シート又は複合シートを用いることにより、前記フィルム状接着剤を、その適用対象である部品に設けることができる。
 本発明の積層体の製造方法により、チップと、フィルム状接着剤と、光透過性カバーと、がこの順に積層されて構成された積層体を製造できる。
The film-like adhesive of the present invention has optical transparency before and after heating, and coloration after heating is suppressed.
By using the laminated sheet or the composite sheet of the present invention provided with the film adhesive of the present invention, the film adhesive can be provided to a component to which the film adhesive is applied.
According to the method for producing a laminated body of the present invention, it is possible to produce a laminated body including a chip, a film adhesive, and a light-transmitting cover, which are laminated in this order.
本発明の一実施形態に係るフィルム状接着剤及び積層シートの一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the film adhesive and laminated sheet which concern on one Embodiment of this invention. 本発明の一実施形態に係る積層シートの他の例を模式的に示す断面図である。It is sectional drawing which shows typically the other example of the laminated sheet which concerns on one Embodiment of this invention. 本発明の一実施形態に係る複合シートの一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the composite sheet which concerns on one Embodiment of this invention. 本発明の一実施形態に係るフィルム状接着剤を用いて製造された積層体の一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the laminated body manufactured using the film adhesive which concerns on one Embodiment of this invention. 本発明の一実施形態に係る複合シートの使用方法の一例を模式的に説明するための断面図である。FIG. 6 is a cross-sectional view for schematically explaining an example of a method of using the composite sheet according to the embodiment of the present invention. 実施例及び比較例における、フィルム状接着剤についての、FT-IRの測定結果である。3 is a result of FT-IR measurement of a film adhesive in Examples and Comparative Examples.
◇フィルム状接着剤
 本発明の一実施形態に係るフィルム状接着剤は、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まない。
 このような条件を満たすフィルム状接着剤は、その260℃等での加熱前後において、濁りと着色が抑制され、波長が400~800nmである光(本明細書においては、「光(400~800nm)」と略記することがある)の直線透過率が高い。
◇Film-shaped adhesive A film-shaped adhesive according to an embodiment of the present invention is a film-shaped adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover, At least one side of which is substantially free of aromatic compounds.
The film-like adhesive satisfying these conditions is suppressed from turbidity and coloration before and after heating at 260° C. or the like, and has a wavelength of 400 to 800 nm (in the present specification, “light (400 to 800 nm )” may be abbreviated)).
 本実施形態のフィルム状接着剤は、電子機器を構成する各種部品の製造又は加工時に、目的物の接着用に使用できる。
 例えば、センサー等のチップの回路形成面を、前記フィルム状接着剤を介して、光透過性カバー(保護カバー)で被覆できる。すなわち、前記フィルム状接着剤は、チップの回路形成面に対してカバーを接着するためのフィルムとして使用できる。
 その場合、フィルム状接着剤が上記のように、加熱前後で光透過性が高く、着色が抑制されるため、光透過性カバー及びフィルム状接着剤越しに、チップの回路形成面に存在する視覚情報を安定して高精度に視認可能である。
The film-like adhesive of the present embodiment can be used for adhering an object when manufacturing or processing various parts constituting an electronic device.
For example, the circuit forming surface of a chip such as a sensor can be covered with a light transmissive cover (protective cover) via the film adhesive. That is, the film adhesive can be used as a film for adhering the cover to the circuit forming surface of the chip.
In that case, as described above, the film adhesive has high light transmittance before and after heating, and coloring is suppressed.Therefore, the visual presence present on the circuit formation surface of the chip is exceeded through the light transparent cover and the film adhesive. Information can be viewed with stability and high accuracy.
 前記光透過性カバー(保護カバー)の被覆対象であるセンサーとしては、例えば、指紋センサーが挙げられる。ただし、これはセンサーの一例である。 A fingerprint sensor is an example of a sensor to be covered by the light-transmitting cover (protective cover). However, this is an example of a sensor.
 本明細書においては、基板及びチップの回路が形成されている面を「回路形成面」と称する。
 なお、本明細書において、単なる「チップ」との記載は、半導体チップのみを意味するものではなく、半導体チップ以外のチップも含む。
In this specification, the surface of the substrate and the chip on which the circuit is formed is referred to as a “circuit forming surface”.
In the present specification, the mere description of “chip” does not mean only a semiconductor chip, but includes chips other than the semiconductor chip.
 本実施形態のフィルム状接着剤は、熱硬化性を有することが好ましく、感圧接着性を有することが好ましい。例えば、熱硬化性及び感圧接着性をともに有するフィルム状接着剤は、未硬化状態では各種被着体に軽く押圧することで貼付できる。また、フィルム状接着剤は、加熱して軟化させることで各種被着体に貼付できるものであってもよい。フィルム状接着剤は、硬化によって最終的には耐衝撃性が高い硬化物となり、この硬化物は、厳しい高温・高湿度条件下においても十分な接着特性を保持し得る。 The film adhesive of the present embodiment preferably has thermosetting properties and preferably pressure-sensitive adhesive properties. For example, a film adhesive having both thermosetting property and pressure-sensitive adhesive property can be attached by lightly pressing to various adherends in the uncured state. Further, the film adhesive may be one that can be attached to various adherends by heating and softening. When cured, the film adhesive finally becomes a cured product having high impact resistance, and this cured product can retain sufficient adhesive properties even under severe conditions of high temperature and high humidity.
 260℃で加熱する前の本実施形態のフィルム状接着剤の、光(400~800nm)の直線透過率(本明細書においては、「加熱前直線透過率」と略記することがある)は、90%以上であることが好ましく、91.5%以上であることがより好ましく、93%以上であることがさらに好ましく、94.5%以上であることが特に好ましい。前記加熱前直線透過率が前記下限値以上であることで、加熱前の前記フィルム状接着剤は、このフィルム状接着剤越しに像を見たときに、像を正しく認識できる性質(本明細書においては、「像認識性」と略記することがある)が高い。 The linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment before heating at 260° C. (in this specification, may be abbreviated as “pre-heating linear transmittance”) is It is preferably 90% or more, more preferably 91.5% or more, further preferably 93% or more, and particularly preferably 94.5% or more. Since the linear transmittance before heating is equal to or higher than the lower limit value, the film adhesive before heating has a property that an image can be correctly recognized when the image is viewed through the film adhesive (in the present specification. , It is sometimes abbreviated as "image recognition property").
 光(400~800nm)の前記加熱前直線透過率の上限値は、特に限定されず、100%であってもよい。
 例えば、前記加熱前直線透過率が99.8%以下であるフィルム状接着剤は、その製造がより容易である。
The upper limit of the linear transmittance of light (400 to 800 nm) before heating is not particularly limited and may be 100%.
For example, the film adhesive having a linear transmittance before heating of 99.8% or less is easier to manufacture.
 光(400~800nm)の前記加熱前直線透過率は、上述のいずれかの下限値と、上限値と、を任意に組み合わせて設定される範囲内に、適宜調節できる。例えば、一実施形態において、前記加熱前直線透過率は、90~99.8%であることが好ましく、91.5~99.8%であることがより好ましく、93~99.8%であることがさらに好ましく、94.5~99.8%であることが特に好ましい。ただし、これらは、前記加熱前直線透過率の一例である。 The above-mentioned linear transmittance of light (400 to 800 nm) before heating can be appropriately adjusted within a range that is set by arbitrarily combining any of the above lower limit value and upper limit value. For example, in one embodiment, the linear transmittance before heating is preferably 90 to 99.8%, more preferably 91.5 to 99.8%, and 93 to 99.8%. It is more preferable, and it is particularly preferable that it is 94.5 to 99.8%. However, these are examples of the linear transmittance before heating.
 260℃で10分加熱した後の本実施形態のフィルム状接着剤の、光(400~800nm)の直線透過率(本明細書においては、「加熱後直線透過率」と略記することがある)は、85%以上であることが好ましく、例えば、87.5%以上、90%以上、及び94%以上のいずれかであってもよい。前記加熱後直線透過率が前記下限値以上であることで、加熱後の前記フィルム状接着剤は、その像認識性が高い。 Linear transmittance of light (400 to 800 nm) of the film adhesive of the present embodiment after heating at 260° C. for 10 minutes (may be abbreviated as “linear transmittance after heating” in this specification). Is preferably 85% or more, and may be any of 87.5% or more, 90% or more, and 94% or more, for example. When the linear transmittance after heating is at least the lower limit value, the film adhesive after heating has high image recognizability.
 光(400~800nm)の前記加熱後直線透過率の上限値は。特に限定されず、100%であってもよい。
 例えば、前記加熱後直線透過率が99.8%以下であるフィルム状接着剤は、その製造がより容易である。
What is the upper limit of the linear transmittance of light (400 to 800 nm) after heating. It is not particularly limited and may be 100%.
For example, the film adhesive having a linear transmittance of 99.8% or less after heating is easier to manufacture.
 光(400~800nm)の前記加熱後直線透過率は、上述のいずれかの下限値と、上限値と、を任意に組み合わせて設定される範囲内に、適宜調節できる。例えば、一実施形態において、前記加熱後直線透過率は、85~99.8%であることが好ましく、例えば、87.5~99.8%、90~99.8%、及び94~99.8%のいずれかであってもよい。ただし、これらは、前記加熱後直線透過率の一例である。 The linear transmittance of light (400 to 800 nm) after heating can be appropriately adjusted within a range set by arbitrarily combining any one of the above lower limit value and upper limit value. For example, in one embodiment, the linear transmittance after heating is preferably 85 to 99.8%, for example, 87.5 to 99.8%, 90 to 99.8%, and 94 to 99.%. It may be either 8%. However, these are examples of the linear transmittance after heating.
 光(400~800nm)の前記加熱前直線透過率及び加熱後直線透過率は、分光光度計を用いて、公知の方法で測定できる。 The linear transmittance before heating and the linear transmittance after heating of light (400 to 800 nm) can be measured by a known method using a spectrophotometer.
 前記加熱後直線透過率を規定するときの、260℃、10分という前記フィルム状接着剤の加熱条件は、はんだリフロー工程等の加熱工程での条件を考慮して、設定されている。 The heating condition of the film adhesive of 260° C. for 10 minutes when defining the linear transmittance after heating is set in consideration of the conditions in the heating process such as the solder reflow process.
 本実施形態のフィルム状接着剤のせん断強度は、特に限定されないが、20N/2mm□以上であることが好ましく、例えば、50N/2mm□以上、60N/2mm□以上、70N/2mm□以上、及び78N/2mm□以上のいずれかであってもよい。フィルム状接着剤のせん断強度が前記下限値以上であることで、その貼付対象物に対する接着力が、より強くなる。
 なお、本明細書において、単位「N/2mm□」は「N/(2mm×2mm)」と同義である。
The shear strength of the film adhesive of the present embodiment is not particularly limited, but is preferably 20 N/2 mm□ or more, for example, 50 N/2 mm□ or more, 60 N/2 mm□ or more, 70 N/2 mm□ or more, and It may be either 78 N/2 mm□ or more. When the shear strength of the film adhesive is equal to or more than the lower limit value, the adhesive strength to the pasting target becomes stronger.
In the present specification, the unit “N/2 mm□” has the same meaning as “N/(2 mm×2 mm)”.
 前記フィルム状接着剤のせん断強度の上限値も、特に限定されない。
 例えば、せん断強度が300N/2mm□以下であるフィルム状接着剤は、その製造がより容易である。
The upper limit of the shear strength of the film adhesive is also not particularly limited.
For example, a film adhesive having a shear strength of 300 N/2 mm□ or less is easier to manufacture.
 前記フィルム状接着剤のせん断強度は、上述のいずれかの下限値と、上限値と、を任意に組み合わせて設定される範囲内に、適宜調節できる。例えば、一実施形態において、前記せん断強度は、20~300N/2mm□であることが好ましく、例えば、50~300N/2mm□、60~300N/2mm□、70~300N/2mm□、及び78~300N/2mm□のいずれかであってもよい。ただし、これらは、前記せん断強度の一例である。 The shear strength of the film adhesive can be appropriately adjusted within a range set by any combination of the above lower limit and upper limit. For example, in one embodiment, the shear strength is preferably 20 to 300 N/2 mm□, for example, 50 to 300 N/2 mm□, 60 to 300 N/2 mm□, 70 to 300 N/2 mm□, and 78 to It may be either 300 N/2 mm□. However, these are examples of the shear strength.
 本実施形態における、前記フィルム状接着剤のせん断強度は、以下に示す方法で測定されたものである。
(フィルム状接着剤のせん断強度の測定方法)
 大きさが2mm×2mmで、厚さが20μmであるフィルム状接着剤と、大きさが30mm×30mmで、厚さが300μmである銅板と、シリコンチップとを用い、前記フィルム状接着剤の、一方の面全面が前記シリコンチップの表面に貼付され、他方の面全面が前記銅板の表面に貼付されて構成された試験片を作製する。この試験片のうち、少なくとも一の側面においては、前記フィルム状接着剤と前記シリコンチップとの側面の位置合わせを行う。
 23℃の温度条件下で、前記試験片中の、前記位置合わせを行った側面において、前記フィルム状接着剤と前記シリコンチップの両方に対して、前記フィルム状接着剤の前記他方の面に対して平行な方向に、200μm/sの速度で力を加え、前記フィルム状接着剤が破壊されるまでに加えられていた力の最大値を、前記フィルム状接着剤のせん断強度(N/2mm□)として採用する。
The shear strength of the film adhesive in the present embodiment is measured by the method described below.
(Measuring method of shear strength of film adhesive)
Using a film-like adhesive having a size of 2 mm×2 mm and a thickness of 20 μm, a copper plate having a size of 30 mm×30 mm and a thickness of 300 μm, and a silicon chip, the film-like adhesive of A test piece is prepared in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate. On at least one side surface of this test piece, the side surfaces of the film adhesive and the silicon chip are aligned.
Under the temperature condition of 23° C., in the side surface where the alignment is performed in the test piece, for both the film adhesive and the silicon chip, for the other surface of the film adhesive. In a direction parallel to each other at a speed of 200 μm/s, and the maximum value of the force applied until the film adhesive is broken is defined as the shear strength (N/2 mm□ of the film adhesive. ) Is adopted as.
 前記フィルム状接着剤において、その少なくとも一方の面は、実質的に芳香族化合物を含まず、両方の面が実質的に芳香族化合物を含まないことが好ましい。
 単層の前記フィルム状接着剤は、通常、その中の組成に偏りが見られず、組成の均一性が高い。したがって、単層のフィルム状接着剤の両面において、含有成分の種類及び含有量には、有意な差が認められないか、認められたとしても、それによりもたらされる効果は、無視し得る程度に軽微である。
 単層の前記フィルム状接着剤において、その少なくとも一方の面が、実質的に芳香族化合物を含んでいなければ、フィルム状接着剤全体、及び他方の面も、実質的に芳香族化合物を含んでいないと判断できる。
In the film adhesive, it is preferable that at least one surface thereof is substantially free of an aromatic compound and both surfaces are substantially free of an aromatic compound.
The single-layered film-like adhesive usually has no unevenness in the composition therein and has a high compositional uniformity. Therefore, there is no significant difference in the type and content of the components on both sides of the single-layer film adhesive, or even if they are observed, the effect brought by them is negligible. It is slight.
In the single-layer film adhesive, if at least one surface thereof does not substantially contain an aromatic compound, the entire film adhesive and the other surface also contain substantially an aromatic compound. You can judge that it is not.
 本明細書において、フィルム状接着剤の部位によらず、「フィルム状接着剤が実質的に芳香族化合物を含まない」とは、フィルム状接着剤が芳香族化合物を全く含まないか、又は含んでいたとしても、それによりもたらされる効果が、無視し得る程度に軽微であり、フィルム状接着剤が芳香族化合物を含まない場合と同様の特性を示すことを意味する。 In the present specification, “regardless of the site of the film adhesive, “the film adhesive contains substantially no aromatic compound” means that the film adhesive contains no aromatic compound or contains no aromatic compound. Even if it is, it means that the effect brought by it is negligibly negligible, and the film-like adhesive exhibits the same properties as in the case where the adhesive does not contain an aromatic compound.
 本実施形態において、フィルム状接着剤の面(すなわち、前記一方の面又は両方の面)が実質的に芳香族化合物を含まないことは、フィルム状接着剤の対象となる面について、フーリエ変換赤外分光法(Fourier Transform Infrared Spectroscopy、本明細書においては、「FT-IR」と略記することがある)で分析を行ったとき、波数3050~2990cm-1の範囲で、透過率を示す曲線において、変曲点が存在しないことにより、確認できる。波数3050~2990cm-1の範囲で特定される主な官能基は、芳香族環式基のみであり、この波数域で、透過率を示す曲線において変曲点が存在しなければ、分析対象面に芳香族環式基は存在せず、芳香族化合物が含まれないと判断できる。ここで「変曲点が存在しない」とは、透過率を示す曲線において、ノイズ以外にピークが存在しないことと同義である。 In the present embodiment, the fact that the surface of the film adhesive (that is, the one surface or both surfaces) does not substantially contain an aromatic compound means that the surface of the film adhesive has a Fourier transform red. In a curve showing transmittance in a wave number range of 3050 to 2990 cm −1 when analyzed by an external spectroscopy (Fourier Transform Infrared Spectroscopy, sometimes abbreviated as “FT-IR” in this specification) , Can be confirmed by the absence of an inflection point. The main functional group specified in the wave number range of 3050 to 2990 cm −1 is only the aromatic cyclic group. In this wave number region, if there is no inflection point in the curve showing the transmittance, the surface to be analyzed is Since there is no aromatic cyclic group, it can be judged that the aromatic compound is not included. Here, “there is no inflection point” is synonymous with that there is no peak other than noise in the curve showing the transmittance.
 前記フィルム状接着剤は1層(単層)からなるものであってもよいし、2層以上の複数層からなるものであってもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The film adhesive may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers are the same as each other. However, they may be different, and the combination of these plural layers is not particularly limited.
 なお、本明細書においては、フィルム状接着剤の場合に限らず、「複数層が互いに同一でも異なっていてもよい」とは、「すべての層が同一であってもよいし、すべての層が異なっていてもよいし、一部の層のみが同一であってもよい」ことを意味し、さらに「複数層が互いに異なる」とは、「各層の構成材料及び厚さの少なくとも一方が互いに異なる」ことを意味する。 In addition, in the present specification, not only in the case of the film-like adhesive, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers may be the same”. May be different, or only a part of the layers may be the same", and "a plurality of layers are different from each other" means that "at least one of the constituent material and the thickness of each layer is mutually different". Means "different".
 前記フィルム状接着剤の厚さは、10~40μmであることが好ましく、例えば、10~35μm、10~30μm、及び10~25μmのいずれかであってもよいし、13~40μm、16~40μm、及び19~40μmのいずれかであってもよいし、13~35μm、16~30μm、及び19~25μmのいずれかであってもよい。フィルム状接着剤の厚さが前記下限値以上であることで、フィルム状接着剤の接着対象物に対する接着力がより強くなる。フィルム状接着剤の厚さが前記上限値以下であることで、加熱の有無によらず、フィルム状接着剤の光(例えば、光(400~800nm))の直線透過率が高くなる。
 ここで、「フィルム状接着剤の厚さ」とは、フィルム状接着剤全体の厚さを意味し、例えば、複数層からなるフィルム状接着剤の厚さとは、フィルム状接着剤を構成するすべての層の合計の厚さを意味する。
The thickness of the film adhesive is preferably 10 to 40 μm, and may be any of 10 to 35 μm, 10 to 30 μm, and 10 to 25 μm, or 13 to 40 μm and 16 to 40 μm. , And 19 to 40 μm, or 13 to 35 μm, 16 to 30 μm, and 19 to 25 μm. When the thickness of the film adhesive is not less than the above lower limit, the adhesive force of the film adhesive with respect to the object to be bonded becomes stronger. When the thickness of the film adhesive is equal to or less than the above upper limit, the linear transmittance of light (for example, light (400 to 800 nm)) of the film adhesive increases regardless of whether or not the film adhesive is heated.
Here, the "thickness of the film-like adhesive" means the thickness of the whole film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers means all the constituents of the film-like adhesive. Means the total thickness of the layers.
 前記フィルム状接着剤で好ましいものとしては、例えば、光(400~800nm)の前記加熱前直線透過率が90%以上であり、光(400~800nm)の前記加熱後直線透過率が85%以上であり、前記フィルム状接着剤の厚さが10~40μmである、ものが挙げられる。 The film adhesive is preferably, for example, 90% or more of the linear transmittance of light (400 to 800 nm) before heating and 85% or more of the linear transmittance of light (400 to 800 nm) after heating. And the film adhesive has a thickness of 10 to 40 μm.
 前記フィルム状接着剤の上述の各物性(光(400~800nm)の前記加熱前直線透過率、光(400~800nm)の前記加熱後直線透過率、せん断強度、FT-IR特性)は、例えば、フィルム状接着剤の含有成分の種類及び含有量を調節することで、調節できる。 The above-mentioned physical properties of the film-like adhesive (the linear transmittance of light (400 to 800 nm) before heating, the linear transmittance of light (400 to 800 nm) after heating, shear strength, and FT-IR characteristics) are, for example, It can be adjusted by adjusting the type and content of the components contained in the film adhesive.
 前記フィルム状接着剤で好ましいものとしては、例えば、アクリル系樹脂(a)と、エポキシ化合物(b1)と、リン系酸化防止剤(z)と、からなる群から選択される1種又は2種以上を含有するものが挙げられる。 The film adhesive is preferably, for example, one or two selected from the group consisting of an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). The thing containing the above is mentioned.
<<接着剤組成物>>
 前記フィルム状接着剤は、その構成材料(例えば、アクリル系樹脂(a)と、エポキシ化合物(b1)と、リン系酸化防止剤(z)と、からなる群から選択される1種又は2種以上)を含有する接着剤組成物を用いて形成できる。例えば、フィルム状接着剤の形成対象面に接着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位にフィルム状接着剤を形成できる。
 接着剤組成物中の、常温で気化しない成分同士の含有量の比率は、通常、フィルム状接着剤の前記成分同士の含有量の比率と同じとなる。なお、本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、すなわち平常の温度を意味し、例えば、15~25℃の温度等が挙げられる。
<< adhesive composition >>
The film adhesive is one or two selected from the group consisting of its constituent materials (for example, an acrylic resin (a), an epoxy compound (b1), and a phosphorus antioxidant (z). It can be formed using an adhesive composition containing the above). For example, the film-shaped adhesive can be formed at a desired site by applying the adhesive composition to the surface on which the film-shaped adhesive is to be formed and drying it as necessary.
The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film adhesive. In addition, in the present specification, “normal temperature” means a temperature at which it is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.
 接着剤組成物の塗工は、公知の方法で行えばよく、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーター等の各種コーターを用いる方法が挙げられる。 The coating of the adhesive composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.
 接着剤組成物の乾燥条件は、特に限定されないが、接着剤組成物は、後述する溶媒を含有している場合、加熱乾燥させることが好ましい。溶媒を含有する接着剤組成物は、例えば、70~130℃で10秒~5分の条件で乾燥させることが好ましい。
 以下、フィルム状接着剤及び接着剤組成物の含有成分について、詳細に説明する。
The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains the solvent described below, it is preferable to heat-dry. The solvent-containing adhesive composition is preferably dried, for example, at 70 to 130° C. for 10 seconds to 5 minutes.
Hereinafter, the components contained in the film adhesive and the adhesive composition will be described in detail.
<アクリル系樹脂(a)>
 アクリル系樹脂(a)は、(メタ)アクリル酸、(メタ)アクリル酸エステル、及びこれらの誘導体からなる群から選択される1種又は2種以上が、重合反応して形成されたとみなせる成分である。
 なお、本明細書において「誘導体」とは、特に断りのない限り、元の化合物の1個以上の基がそれ以外の基(置換基)で置換された構造を有するものを意味する。ここで、「基」とは、複数個の原子が結合して構成された原子団だけでなく、1個の原子も包含するものとする。
 アクリル系樹脂(a)は、フィルム状接着剤に造膜性や可撓性等を付与すると共に、前記チップ等の接着対象への接着性(貼付性)を向上させるための樹脂成分である。
<Acrylic resin (a)>
The acrylic resin (a) is a component that can be regarded as formed by a polymerization reaction of one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, and derivatives thereof. is there.
In the present specification, the “derivative” means one having a structure in which one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified. Here, the "group" includes not only an atomic group formed by combining a plurality of atoms but also one atom.
The acrylic resin (a) is a resin component for imparting film-forming properties and flexibility to the film-like adhesive and improving the adhesiveness (sticking property) to an object to be adhered such as the chip.
 本明細書において、「(メタ)アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の両方を包含する概念とする。(メタ)アクリル酸と類似の用語についても同様である。 In this specification, “(meth)acrylic acid” is a concept that includes both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth)acrylic acid.
 接着剤組成物及びフィルム状接着剤が含有するアクリル系樹脂(a)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The acrylic resin (a) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
 アクリル系樹脂(a)としては、公知のアクリル重合体が挙げられる。
 アクリル系樹脂(a)の重量平均分子量(Mw)は、10000~2000000であることが好ましく、100000~1500000であることがより好ましい。アクリル系樹脂(a)の重量平均分子量がこのような範囲内であることで、フィルム状接着剤と被着体との間の接着力を好ましい範囲に調節することが容易となる。
 一方、アクリル系樹脂(a)の重量平均分子量が前記下限値以上であることで、フィルム状接着剤の形状安定性(保管時の経時安定性)が向上する。また、アクリル系樹脂(a)の重量平均分子量が前記上限値以下であることで、被着体の凹凸面へフィルム状接着剤が追従し易くなり、被着体とフィルム状接着剤との間でボイド等の発生がより抑制される。
 なお、本明細書において、「重量平均分子量」とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値である。
Examples of the acrylic resin (a) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin (a) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 15,000,000. When the weight average molecular weight of the acrylic resin (a) is within such a range, it becomes easy to adjust the adhesive force between the film adhesive and the adherend within a preferable range.
On the other hand, when the weight average molecular weight of the acrylic resin (a) is not less than the lower limit value, the shape stability of the film adhesive (stability during storage) is improved. Further, when the weight average molecular weight of the acrylic resin (a) is not more than the upper limit value, the film-like adhesive easily follows the uneven surface of the adherend, so that the adhesive between the adherend and the film-like adhesive becomes Therefore, the generation of voids is further suppressed.
In addition, in this specification, a "weight average molecular weight" is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.
 アクリル系樹脂(a)のガラス転移温度(Tg)は、-60~70℃であることが好ましく、-30~50℃であることがより好ましい。アクリル系樹脂(a)のTgが前記下限値以上であることで、フィルム状接着剤と被着体との間の接着力が抑制されて、例えば、ピックアップ時において、フィルム状接着剤を備えた前記チップの、後述するダイシングシートからの引き離しがより容易となる。アクリル系樹脂(a)のTgが前記上限値以下であることで、フィルム状接着剤と被着体との間の接着力が向上する。 The glass transition temperature (Tg) of the acrylic resin (a) is preferably −60 to 70° C., more preferably −30 to 50° C. When the Tg of the acrylic resin (a) is at least the lower limit value, the adhesive force between the film adhesive and the adherend is suppressed, and for example, the film adhesive is provided at the time of pickup. It becomes easier to separate the chip from the dicing sheet described later. When the Tg of the acrylic resin (a) is not more than the above upper limit value, the adhesive force between the film adhesive and the adherend is improved.
 アクリル系樹脂(a)を構成する前記(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル((メタ)アクリル酸ラウリル)、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル((メタ)アクリル酸ミリスチル)、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル((メタ)アクリル酸パルミチル)、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル((メタ)アクリル酸ステアリル)等の、アルキルエステルを構成するアルキル基が、炭素数が1~18の鎖状構造である(メタ)アクリル酸アルキルエステル;
 (メタ)アクリル酸イソボルニル、(メタ)アクリル酸ジシクロペンタニル等の(メタ)アクリル酸シクロアルキルエステル;
 (メタ)アクリル酸ベンジル等の(メタ)アクリル酸アラルキルエステル;
 (メタ)アクリル酸ジシクロペンテニルエステル等の(メタ)アクリル酸シクロアルケニルエステル;
 (メタ)アクリル酸ジシクロペンテニルオキシエチルエステル等の(メタ)アクリル酸シクロアルケニルオキシアルキルエステル;
 (メタ)アクリル酸イミド;
 (メタ)アクリル酸グリシジル等のグリシジル基含有(メタ)アクリル酸エステル;
 (メタ)アクリル酸ヒドロキシメチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシブチル等の水酸基含有(メタ)アクリル酸エステル;
 (メタ)アクリル酸N-メチルアミノエチル等の置換アミノ基含有(メタ)アクリル酸エステル等が挙げられる。ここで、「置換アミノ基」とは、アミノ基の1個又は2個の水素原子が水素原子以外の基で置換された構造を有する基を意味する。
Examples of the (meth)acrylic acid ester that constitutes the acrylic resin (a) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth) Decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl acrylate), (meth ) Pentadecyl acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. A (meth)acrylic acid alkyl ester whose group has a chain structure having 1 to 18 carbon atoms;
(Meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylic acid and dicyclopentanyl (meth)acrylic acid;
Aralkyl esters of (meth)acrylic acid such as benzyl (meth)acrylate;
(Meth)acrylic acid cycloalkenyl ester such as (meth)acrylic acid dicyclopentenyl ester;
(Meth)acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl ester;
(Meth)acrylic acid imide;
Glycidyl group-containing (meth)acrylic acid ester such as glycidyl (meth)acrylate;
Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate;
Examples include substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylic acid. Here, the “substituted amino group” means a group having a structure in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.
 アクリル系樹脂(a)は、例えば、前記(メタ)アクリル酸エステル以外に、(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、スチレン及びN-メチロールアクリルアミド等から選択される1種又は2種以上のモノマーが共重合して得られた樹脂であってもよい。 The acrylic resin (a) is, for example, one or two kinds selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. in addition to the (meth)acrylic acid ester. It may be a resin obtained by copolymerizing the above monomers.
 アクリル系樹脂(a)を構成するモノマーは、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The monomer constituting the acrylic resin (a) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof can be arbitrarily selected.
 アクリル系樹脂(a)は、上述の水酸基以外に、ビニル基、(メタ)アクリロイル基、アミノ基、カルボキシ基、イソシアネート基等の他の化合物と結合可能な官能基を有していてもよい。アクリル系樹脂(a)の水酸基をはじめとするこれら官能基は、後述する架橋剤(f)を介して他の化合物と結合してもよいし、架橋剤(f)を介さずに他の化合物と直接結合していてもよい。アクリル系樹脂(a)が前記官能基により他の化合物と結合することで、フィルム状接着剤を用いて得られたパッケージの信頼性が向上する傾向がある。 The acrylic resin (a) may have a functional group capable of binding to other compounds such as a vinyl group, a (meth)acryloyl group, an amino group, a carboxy group and an isocyanate group, in addition to the above-mentioned hydroxyl group. These functional groups including the hydroxyl group of the acrylic resin (a) may be bonded to other compounds via a crosslinking agent (f) described later, or other compounds may be bonded without the crosslinking agent (f). May be directly combined with. When the acrylic resin (a) is bonded to another compound by the functional group, the reliability of the package obtained by using the film adhesive tends to be improved.
 アクリル系樹脂(a)で好ましいものとしては、例えば、後述する架橋剤(f)と結合可能な官能基を有するものが挙げられる。 Preferred examples of the acrylic resin (a) include those having a functional group capable of binding to the crosslinking agent (f) described later.
 接着剤組成物において、溶媒以外の全ての成分の総含有量に対するアクリル系樹脂(a)の含有量の割合(すなわち、フィルム状接着剤における、フィルム状接着剤の総質量に対する、アクリル系樹脂(a)の含有量の割合)は、10~90質量%であることが好ましく、15~70質量%であることがより好ましく、20~65質量%であることがさらに好ましく、例えば、30~55質量%、及び30~50質量%のいずれかであってもよい。前記割合が前記下限値以上であることで、フィルム状接着剤の構造がより安定化する。前記割合が前記上限値以下であることで、例えば、エポキシ化合物(b1)及びリン系酸化防止剤(z)等の、アクリル系樹脂(a)以外の成分の使用量を増やすことが容易となり、アクリル系樹脂(a)以外の成分を用いたことによる効果が、より容易に得られる。 In the adhesive composition, the ratio of the content of the acrylic resin (a) to the total content of all components other than the solvent (that is, in the film adhesive, based on the total mass of the film adhesive, the acrylic resin ( The content ratio of a) is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, further preferably 20 to 65% by mass, for example, 30 to 55% by mass. It may be either mass% or 30 to 50 mass %. When the ratio is at least the lower limit value, the structure of the film adhesive will be more stable. When the ratio is less than or equal to the upper limit value, for example, it becomes easy to increase the amount of components other than the acrylic resin (a) such as the epoxy compound (b1) and the phosphorus-based antioxidant (z), The effect of using a component other than the acrylic resin (a) can be more easily obtained.
<エポキシ化合物(b1)>
 エポキシ化合物(b1)は、樹脂成分及び非樹脂成分のいずれであってもよい。
 エポキシ化合物(b1)としては、公知のものが挙げられ、例えば、多官能系エポキシ樹脂、ビフェニル化合物、ビスフェノールAジグリシジルエーテル及びその水添物、オルソクレゾールノボラックエポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェニレン骨格型エポキシ樹脂、トリアジン型脂環式エポキシ化合物等、2官能以上のエポキシ化合物が挙げられる。
<Epoxy compound (b1)>
The epoxy compound (b1) may be either a resin component or a non-resin component.
Examples of the epoxy compound (b1) include known compounds, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and triazine type alicyclic epoxy compound can be mentioned.
 エポキシ化合物(b1)としては、不飽和炭化水素基を有するエポキシ化合物を用いてもよい。不飽和炭化水素基を有するエポキシ化合物は、不飽和炭化水素基を有しないエポキシ化合物よりも、アクリル系樹脂(a)との相溶性が高い。そのため、不飽和炭化水素基を有するエポキシ化合物(b1)を用いることで、フィルム状接着剤を用いて得られたパッケージの信頼性が向上する。 As the epoxy compound (b1), an epoxy compound having an unsaturated hydrocarbon group may be used. The epoxy compound having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin (a) than the epoxy compound having no unsaturated hydrocarbon group. Therefore, by using the epoxy compound (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film adhesive is improved.
 不飽和炭化水素基を有するエポキシ化合物(b1)としては、例えば、多官能系エポキシ化合物のエポキシ基の一部が不飽和炭化水素基を有する基に変換された構造を有する化合物が挙げられる。このような化合物は、例えば、エポキシ基へ(メタ)アクリル酸又はその誘導体を付加反応させることにより得られる。 Examples of the epoxy compound (b1) having an unsaturated hydrocarbon group include compounds having a structure in which a part of the epoxy groups of a polyfunctional epoxy compound is converted to a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition-reacting (meth)acrylic acid or its derivative with an epoxy group.
 また、不飽和炭化水素基を有するエポキシ化合物(b1)としては、例えば、エポキシ化合物を構成する芳香環等に、不飽和炭化水素基を有する基が直接結合した化合物等が挙げられる。
 不飽和炭化水素基は、重合性を有する不飽和基であり、その具体的な例としては、エテニル基(ビニル基)、2-プロペニル基(アリル基)、(メタ)アクリロイル基、(メタ)アクリルアミド基等が挙げられ、アクリロイル基が好ましい。
Moreover, as the epoxy compound (b1) having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy compound can be mentioned.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth) Examples thereof include an acrylamide group, and an acryloyl group is preferable.
 樹脂成分であるエポキシ化合物(b1)(換言するとエポキシ樹脂(b1))の数平均分子量は、特に限定されないが、フィルム状接着剤の硬化性、並びにフィルム状接着剤の硬化物の強度及び耐熱性の点から、300~30000であることが好ましく、400~10000であることがより好ましく、500~3000であることが特に好ましい。
 エポキシ化合物(b1)のエポキシ当量は、100~1000g/eqであることが好ましく、120~600g/eqであることがより好ましい。
The number average molecular weight of the epoxy compound (b1) which is a resin component (in other words, the epoxy resin (b1)) is not particularly limited, but the curability of the film adhesive, and the strength and heat resistance of the cured product of the film adhesive. From the viewpoint of the above, it is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
The epoxy equivalent of the epoxy compound (b1) is preferably 100 to 1000 g/eq, and more preferably 120 to 600 g/eq.
 接着剤組成物及びフィルム状接着剤が含有するエポキシ化合物(b1)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The epoxy compound (b1) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.
 エポキシ化合物(b1)は、脂肪族系化合物であることが好ましい。すなわち、前記フィルム状接着剤は、脂肪族系エポキシ化合物を含有することが好ましい。
 本明細書において、「脂肪族系化合物」とは、脂肪族基を有し、かつ芳香族基を有しない化合物を意味する。また、「脂肪族基」には、鎖状脂肪族基及び脂肪族環式基(別名:脂環式基)が含まれる。また、「芳香族基」には、芳香族炭化水素基及び芳香族複素環式基が含まれる。
 接着剤組成物及びフィルム状接着剤が、エポキシ化合物(b1)として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The epoxy compound (b1) is preferably an aliphatic compound. That is, the film adhesive preferably contains an aliphatic epoxy compound.
In the present specification, the "aliphatic compound" means a compound having an aliphatic group and not an aromatic group. Further, the “aliphatic group” includes a chain aliphatic group and an aliphatic cyclic group (alias: alicyclic group). Further, the “aromatic group” includes an aromatic hydrocarbon group and an aromatic heterocyclic group.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the epoxy compound (b1), the effect of suppressing coloration after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.
 エポキシ化合物(b1)は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、エポキシ化合物(b1)として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The epoxy compound (b1) is selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. It is preferable not to have one kind or two or more kinds.
Coloring after heating (for example, heating at 260° C.) of the film adhesive by containing the epoxy compound (b1) having no bond or group as the epoxy compound (b1) in the adhesive composition and the film adhesive. The effect of suppressing the above is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.
 エポキシ化合物(b1)は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。すなわち、前記フィルム状接着剤は、炭素原子間の三重結合、炭素原子間の二重結合及びシアノ基からなる群から選択される1種又は2種以上を有しない脂肪族系エポキシ化合物を含有することが好ましい。
 接着剤組成物及びフィルム状接着剤が、エポキシ化合物(b1)として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The epoxy compound (b1) is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of That is, the film adhesive contains an aliphatic epoxy compound which does not have one kind or two or more kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms and a cyano group. It is preferable.
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the epoxy compound (b1), heating the film adhesive (for example, heating at 260° C.) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), the above coloring The effect of suppressing is significantly increased.
 接着剤組成物及びフィルム状接着剤において、エポキシ化合物(b1)の含有量は、アクリル系樹脂(a)の含有量100質量部に対して、5~500質量部であることが好ましく、例えば、5~200質量部、5~150質量部、5~110質量部、及び5~100質量部のいずれかであってもよいし、10~110質量部、25~110質量部、及び40~110質量部のいずれかであってもよい。エポキシ化合物(b1)の前記含有量がこのような範囲であることで、フィルム状接着剤と、後述する樹脂フィルム又はダイシングシートと、の間の接着力を調節することがより容易となる。 In the adhesive composition and the film adhesive, the content of the epoxy compound (b1) is preferably 5 to 500 parts by mass relative to 100 parts by mass of the acrylic resin (a), for example, It may be any of 5 to 200 parts by mass, 5 to 150 parts by mass, 5 to 110 parts by mass, and 5 to 100 parts by mass, or 10 to 110 parts by mass, 25 to 110 parts by mass, and 40 to 110 parts by mass. It may be either part by mass. When the content of the epoxy compound (b1) is in such a range, it becomes easier to adjust the adhesive force between the film adhesive and the resin film or the dicing sheet described below.
<リン系酸化防止剤(z)>
 前記フィルム状接着剤は、リン系酸化防止剤(z)を含有していることにより、加熱前後における着色が、より抑制される。
 リン系酸化防止剤(z)は、その構成原子としてリン原子を有し、酸化防止作用を有するものであれば、特に限定されない。
 リン系酸化防止剤(z)としては、例えば、リンの酸化数が3である化合物が挙げられる。
<Phosphoric antioxidant (z)>
Since the film adhesive contains the phosphorus-based antioxidant (z), coloring before and after heating is further suppressed.
The phosphorus-based antioxidant (z) is not particularly limited as long as it has a phosphorus atom as its constituent atom and has an antioxidant action.
Examples of the phosphorus-based antioxidant (z) include compounds in which the oxidation number of phosphorus is 3.
 接着剤組成物及びフィルム状接着剤が含有するリン系酸化防止剤(z)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The phosphorus antioxidant (z) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily set. You can choose.
 リン系酸化防止剤(z)は、脂肪族系化合物であることが好ましい。
 接着剤組成物及びフィルム状接着剤が、リン系酸化防止剤(z)として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The phosphorus-based antioxidant (z) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the phosphorus-based antioxidant (z), coloring of the film adhesive after heating (for example, heating at 260° C.) The inhibitory effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described inhibitory effect of coloring is significantly enhanced.
 リン系酸化防止剤(z)は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、リン系酸化防止剤(z)として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The phosphorus-based antioxidant (z) is a group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. It is preferable not to have one or more selected from
When the adhesive composition and the film adhesive contain a phosphorus-based antioxidant (z) that does not have these bonds or groups, heating of the film adhesive (for example, heating at 260° C.) After that, the effect of suppressing the coloring becomes higher, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-mentioned effect of suppressing coloration becomes remarkable. Get higher
 リン系酸化防止剤(z)は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、リン系酸化防止剤(z)として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The phosphorus-based antioxidant (z) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡). It is preferable not to have one or more selected from the group consisting of N).
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the phosphorus-based antioxidant (z), heating of the film adhesive (for example, at 260° C. The effect of suppressing coloring after heating is further increased, and by containing only an aliphatic compound having no such bond or group (in other words, not containing an aliphatic compound having these bond or group), The effect of suppressing the above coloring is significantly enhanced.
 リン系酸化防止剤(z)は、酸化防止作用を安定して示す点で、亜リン酸エステルであることが好ましい。
 なかでも、リン系酸化防止剤(z)は、脂肪族系亜リン酸エステルであることがより好ましく、脂肪族系亜リン酸トリアルキルエステルであることがさらに好ましい。
 すなわち、前記フィルム状接着剤は、酸化防止剤として、亜リン酸エステルを含有することが好ましく、脂肪族系亜リン酸エステルを含有することがより好ましく、脂肪族系亜リン酸トリアルキルエステルを含有することがさらに好ましい。
The phosphorus-based antioxidant (z) is preferably a phosphite ester because it stably exhibits an antioxidant action.
Among them, the phosphorus-based antioxidant (z) is more preferably an aliphatic phosphite ester, and further preferably an aliphatic phosphite trialkyl ester.
That is, the film adhesive, as an antioxidant, preferably contains a phosphite ester, more preferably contains an aliphatic phosphite ester, an aliphatic phosphite trialkyl ester It is more preferable to contain.
 脂肪族系亜リン酸トリアルキルエステルとしては、例えば、トリエチルホスファイト((CO)P)、トリス(2-エチルヘキシル)ホスファイト((CHCHCHCHCH(CHCH)CHO)P)、トリデシルホスファイト((C1021O)P)、トリラウリルホスファイト((C1225O)P)、トリス(トリデシル)ホスファイト((C1327O)P)、トリステアリルホスファイト((C1837O)P)、ビス(デシル)ペンタエリスリトールジホスファイト(C1021OP(OCHC(CHO)POC1021)、ビス(トリデシル)ペンタエリスリトールジホスファイト(C1327OP(OCHC(CHO)POC1327)、ジステアリルペンタエリスリトールジホスファイト(C1837OP(OCHC(CHO)POC1837)、水添ビスフェノールA-ペンタエリスリトールホスファイトポリマー(式「-(OC12C(CH12OP(OCHC(CHO)P)-」で表される繰り返し単位を有するポリマー)等が挙げられる。 Examples of the aliphatic trialkyl phosphite include triethyl phosphite ((C 2 H 5 O) 3 P), tris(2-ethylhexyl) phosphite ((CH 3 CH 2 CH 2 CH 2 CH 2 CH(CH 2 CH 3) CH 2 O) 3 P), tridecyl phosphite ((C 10 H 21 O) 3 P), trilauryl phosphite ((C 12 H 25 O) 3 P), tris (tridecyl) phosphite ((C 13 H 27 O) 3 P), tristearyl phosphite ((C 18 H 37 O) 3 P), bis(decyl)pentaerythritol diphosphite (C 10 H 21 OP(OCH 2 ) 2 C( CH 2 O) 2 POC 10 H 21), bis (tridecyl) pentaerythritol diphosphite (C 13 H 27 OP (OCH 2) 2 C (CH 2 O) 2 POC 13 H 27), distearyl pentaerythritol diphosphite Fight (C 18 H 37 OP (OCH 2) 2 C (CH 2 O) 2 POC 18 H 37), hydrogenated bisphenol A- pentaerythritol diphosphite polymer (formula "- (OC 6 H 12 C ( CH 3) 2 C 6 H 12 OP(OCH 2 ) 2 C(CH 2 O) 2 P)-” and other polymers).
 接着剤組成物において、溶媒以外の全ての成分の総含有量に対する、リン系酸化防止剤(z)の含有量の割合(すなわち、フィルム状接着剤における、フィルム状接着剤の総質量に対する、リン系酸化防止剤(z)の含有量の割合)は、0.1~5質量%であることが好ましく、0.2~3質量%であることがより好ましく、0.3~1.5質量%であることがさらに好ましく、例えば、0.3~1質量%であってもよい。前記割合が前記下限値以上であることで、リン系酸化防止剤(z)を用いたことによる効果が、より顕著に得られる。前記割合が前記上限値以下であることで、リン系酸化防止剤(z)の過剰使用が抑制される。 In the adhesive composition, the ratio of the content of the phosphorus-based antioxidant (z) with respect to the total content of all components other than the solvent (that is, phosphorus in the film-shaped adhesive with respect to the total mass of the film-shaped adhesive, The ratio of the content of the system antioxidant (z)) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.3 to 1.5% by mass. % Is more preferable, and it may be, for example, 0.3 to 1% by mass. When the ratio is at least the lower limit value, the effect of using the phosphorus-based antioxidant (z) can be more remarkably obtained. When the ratio is not more than the upper limit value, excessive use of the phosphorus-based antioxidant (z) is suppressed.
 前記フィルム状接着剤は、その各種物性を改良するために、アクリル系樹脂(a)、エポキシ化合物(b1)、及びリン系酸化防止剤(z)以外に、さらに必要に応じて、これらのいずれにも該当しない他の成分を含有していてもよい。
 前記フィルム状接着剤が含有する他の成分としては、例えば、フェノール樹脂(b2)、硬化促進剤(c)、充填材(d)、カップリング剤(e)、架橋剤(f)、エネルギー線硬化性樹脂(g)、光重合開始剤(h)、リン系酸化防止剤(z)以外の酸化防止剤(y)(本明細書においては、「他の酸化防止剤(y)」と略記することがある)、アクリル系樹脂(a)以外の熱可塑性樹脂(x)(本明細書においては、「熱可塑性樹脂(x)」と略記することがある)、汎用添加剤(i)等が挙げられる。
In order to improve various physical properties of the film adhesive, any one of these may be used in addition to the acrylic resin (a), the epoxy compound (b1), and the phosphorus antioxidant (z) in order to improve various physical properties. It may also contain other components that do not correspond to the above.
Other components contained in the film adhesive include, for example, phenol resin (b2), curing accelerator (c), filler (d), coupling agent (e), cross-linking agent (f), energy ray. Curing resin (g), photopolymerization initiator (h), antioxidant (y) other than phosphorus-based antioxidant (z) (in the present specification, abbreviated as "other antioxidant (y)") Thermoplastic resin (x) other than acrylic resin (a) (in the present specification, may be abbreviated as "thermoplastic resin (x)"), general-purpose additive (i), etc. Are listed.
<フェノール樹脂(b2)>
 フェノール樹脂(b2)は、エポキシ化合物(b1)に対する熱硬化剤として機能する。
 本実施形態において、エポキシ化合物(b1)及びフェノール樹脂(b2)を併用する場合、これらの組み合わせは、エポキシ系熱硬化性樹脂として機能する。本実施形態においては、このようなエポキシ系熱硬化性樹脂を「エポキシ系熱硬化性樹脂(b)」と称することがある。
<Phenolic resin (b2)>
The phenol resin (b2) functions as a thermosetting agent for the epoxy compound (b1).
In the present embodiment, when the epoxy compound (b1) and the phenol resin (b2) are used together, these combinations function as an epoxy thermosetting resin. In the present embodiment, such an epoxy thermosetting resin may be referred to as "epoxy thermosetting resin (b)".
 フェノール樹脂(b2)は、エポキシ基と反応し得る官能基として、フェノール性水酸基を1分子中に2個以上有するものであればよい。 The phenol resin (b2) may be one having two or more phenolic hydroxyl groups in one molecule as a functional group capable of reacting with an epoxy group.
 フェノール樹脂(b2)としては、例えば、多官能フェノール樹脂、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が挙げられる。 Examples of the phenol resin (b2) include polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin and the like.
 フェノール樹脂(b2)は、不飽和炭化水素基を有していてもよい。
 不飽和炭化水素基を有する他のフェノール樹脂(b2)としては、例えば、フェノール樹脂の水酸基の一部が、不飽和炭化水素基を有する基で置換された構造を有する化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を有する基が直接結合した構造を有する化合物等が挙げられる。
 フェノール樹脂(b2)における前記不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ化合物における不飽和炭化水素基と同様である。
The phenol resin (b2) may have an unsaturated hydrocarbon group.
Examples of the other phenolic resin (b2) having an unsaturated hydrocarbon group include, for example, a compound having a structure in which a part of hydroxyl groups of the phenolic resin is replaced with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenolic resin. Examples thereof include compounds having a structure in which a group having an unsaturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the phenol resin (b2) is the same as the unsaturated hydrocarbon group in the epoxy compound having an unsaturated hydrocarbon group described above.
 フェノール樹脂(b2)は、フィルム状接着剤の接着力を調節することが容易となる点から、軟化点又はガラス転移温度が高いものが好ましい。 The phenolic resin (b2) is preferably one having a high softening point or glass transition temperature because it is easy to adjust the adhesive force of the film adhesive.
 フェノール樹脂(b2)の数平均分子量は、300~30000であることが好ましく、400~10000であることがより好ましく、500~3000であることが特に好ましい。 The number average molecular weight of the phenol resin (b2) is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
 接着剤組成物及びフィルム状接着剤が含有するフェノール樹脂(b2)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The phenol resin (b2) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
 フェノール樹脂(b2)を用いる場合、接着剤組成物において、溶媒以外の全ての成分の総含有量に対する、フェノール樹脂(b2)の含有量の割合(すなわち、フィルム状接着剤における、フィルム状接着剤の総質量に対する、フェノール樹脂(b2)の含有量の割合)は、特に限定されないが、10質量%以下であることが好ましく、7.5質量%以下であることがより好ましく、5質量%以下であることがさらに好ましい。前記割合が前記上限値以下であることで、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなる。
 すなわち、フェノール樹脂(b2)を含有する前記フィルム状接着剤で好ましいものの一例としては、前記フィルム状接着剤における、前記フィルム状接着剤の総質量に対する、フェノール樹脂(b2)の含有量の割合が、10質量%以下である、ものが挙げられる。
When the phenol resin (b2) is used, in the adhesive composition, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent (that is, the film adhesive in the film adhesive The ratio of the content of the phenol resin (b2) with respect to the total mass) is not particularly limited, but is preferably 10% by mass or less, more preferably 7.5% by mass or less, and 5% by mass or less. Is more preferable. When the ratio is less than or equal to the upper limit value, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) becomes higher.
That is, as one preferable example of the film adhesive containing the phenol resin (b2), the ratio of the content of the phenol resin (b2) to the total mass of the film adhesive in the film adhesive is The content is 10% by mass or less.
 フェノール樹脂(b2)を用いる場合、接着剤組成物において、溶媒以外の全ての成分の総含有量に対する、フェノール樹脂(b2)の含有量の割合(すなわち、フィルム状接着剤における、フィルム状接着剤の総質量に対する、フェノール樹脂(b2)の含有量の割合)の下限値は、特に限定されない。
 例えば、フェノール樹脂(b2)を用いたことによる効果が、より顕著に得られる点では、前記割合は、0.5質量%以上であることが好ましい。
When the phenol resin (b2) is used, in the adhesive composition, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent (that is, the film adhesive in the film adhesive The lower limit value of the ratio of the content of the phenol resin (b2) to the total mass of is not particularly limited.
For example, the above ratio is preferably 0.5% by mass or more from the viewpoint that the effect of using the phenol resin (b2) can be more remarkably obtained.
 フェノール樹脂(b2)を用いる場合、前記割合は、上述の下限値と、いずれかの上限値と、を任意に組み合わせて設定される範囲内に、適宜調節できる。例えば、一実施形態において、前記割合は、0.5~10質量%であることが好ましく、0.5~7.5質量%であることがより好ましく、0.5~5質量%であることがさらに好ましい。 When the phenol resin (b2) is used, the ratio can be appropriately adjusted within a range set by arbitrarily combining the above-mentioned lower limit value and any upper limit value. For example, in one embodiment, the ratio is preferably 0.5 to 10% by mass, more preferably 0.5 to 7.5% by mass, and 0.5 to 5% by mass. Is more preferable.
 フェノール樹脂(b2)を用いる場合、接着剤組成物及びフィルム状接着剤において、フェノール樹脂(b2)の含有量は、エポキシ化合物(b1)の含有量100質量部に対して、例えば、3~30質量部、3~25質量部、及び3~20質量部のいずれかであってもよいし、5~30質量部、10~30質量部、及び15~30質量部のいずれかであってもよいし、5~25質量部、及び10~20質量部のいずれかであってもよい。 When the phenol resin (b2) is used, the content of the phenol resin (b2) in the adhesive composition and the film adhesive is, for example, 3 to 30 with respect to 100 parts by mass of the epoxy compound (b1). It may be any one of 3 parts by mass, 3 to 25 parts by mass, and 3 to 20 parts by mass, or 5 to 30 parts by mass, 10 to 30 parts by mass, and 15 to 30 parts by mass. It may be 5 to 25 parts by mass or 10 to 20 parts by mass.
<硬化促進剤(c)>
 硬化促進剤(c)は、接着剤組成物及びフィルム状接着剤の硬化速度を調節するための成分である。
 好ましい硬化促進剤(c)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(1個以上の水素原子が水素原子以外の基で置換されたイミダゾール);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(1個以上の水素原子が有機基で置換されたホスフィン);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;前記イミダゾール類をゲスト化合物とする包接化合物等が挙げられる。
<Curing accelerator (c)>
The curing accelerator (c) is a component for controlling the curing rate of the adhesive composition and the film adhesive.
Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. (one or more hydrogen atoms are other than hydrogen atoms) Substituted with a group of), organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate, triphenylphosphine A tetraphenylboron salt such as tetraphenylborate; an inclusion compound having the above-mentioned imidazole as a guest compound, and the like.
 接着剤組成物及びフィルム状接着剤が含有する硬化促進剤(c)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The curing accelerator (c) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected. ..
 硬化促進剤(c)を用いる場合、接着剤組成物及びフィルム状接着剤において、硬化促進剤(c)の含有量は、エポキシ化合物(b1)及びフェノール樹脂(b2)の総含有量100質量部に対して、0.01~7質量部であることが好ましく、0.1~4質量部であることがより好ましい。硬化促進剤(c)の前記含有量が前記下限値以上であることで、硬化促進剤(c)を用いたことによる効果がより顕著に得られる。硬化促進剤(c)の含有量が前記上限値以下であることで、例えば、高極性の硬化促進剤(c)が、高温・高湿度条件下でフィルム状接着剤中において被着体との接着界面側に移動して偏析することを抑制する効果が高くなり、フィルム状接着剤を用いて得られたパッケージの信頼性がより向上する。なお、フェノール樹脂(b2)を用いない場合には、エポキシ化合物(b1)及びフェノール樹脂(b2)の総含有量は、エポキシ化合物(b1)の含有量を意味する。 When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film adhesive is 100 parts by mass of the total content of the epoxy compound (b1) and the phenol resin (b2). On the other hand, it is preferably 0.01 to 7 parts by mass, and more preferably 0.1 to 4 parts by mass. When the content of the curing accelerator (c) is equal to or more than the lower limit value, the effect of using the curing accelerator (c) can be more remarkably obtained. When the content of the curing accelerator (c) is less than or equal to the upper limit value, for example, the highly polar curing accelerator (c) forms a film with the adherend in a film adhesive under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the bonding interface side is enhanced, and the reliability of the package obtained by using the film adhesive is further improved. When the phenol resin (b2) is not used, the total content of the epoxy compound (b1) and the phenol resin (b2) means the content of the epoxy compound (b1).
<充填材(d)>
 フィルム状接着剤は、充填材(d)を含有することにより、その熱膨張係数の調整が容易となり、この熱膨張係数をフィルム状接着剤の貼付対象物に対して最適化することで、フィルム状接着剤を用いて得られたパッケージの信頼性がより向上する。また、フィルム状接着剤が充填材(d)を含有することにより、フィルム状接着剤の硬化物の吸湿率を低減したり、放熱性を向上させたりすることもできる。
<Filler (d)>
Since the film adhesive contains the filler (d), the coefficient of thermal expansion thereof can be easily adjusted. By optimizing the coefficient of thermal expansion for the object to which the film adhesive is attached, the film adhesive The reliability of the package obtained by using the adhesive tape is further improved. In addition, by containing the filler (d) in the film adhesive, it is possible to reduce the moisture absorption rate of the cured product of the film adhesive or to improve the heat dissipation.
 充填材(d)は、有機充填材及び無機充填材のいずれであってもよいが、無機充填材であることが好ましい。
 好ましい無機充填材としては、例えば、シリカ、アルミナ、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、窒化ホウ素等の粉末;これら無機充填材を球形化したビーズ;これら無機充填材の表面改質品;これら無機充填材の単結晶繊維;ガラス繊維等が挙げられる。
 これらの中でも、無機充填材は、シリカ又はその表面改質品であることが好ましい。
The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or a surface modified product thereof.
 充填材(d)の平均粒子径は、特に限定されないが、10~100nmであることが好ましく、10~80nmであることがより好ましく、10~60nmであることがさらに好ましい。充填材(d)の平均粒子径が前記上限値以下であることで、前記フィルム状接着剤の濁りが高度に抑制され、前記フィルム状接着剤の、光(400~800nm)の前記加熱前直線透過率及び加熱後直線透過率が向上し、その結果、加熱前及び加熱後の前記フィルム状接着剤の像認識性がより高くなる。充填材(d)の平均粒子径が前記下限値以上であることで、充填材(d)を用いたことによる効果がより顕著に得られる。
 なお、本明細書において「平均粒子径」とは、特に断りのない限り、レーザー回折散乱法によって求められた粒度分布曲線における、積算値50%での粒子径(D50)の値を意味する。
The average particle size of the filler (d) is not particularly limited, but is preferably 10 to 100 nm, more preferably 10 to 80 nm, and further preferably 10 to 60 nm. When the average particle diameter of the filler (d) is not more than the upper limit value, turbidity of the film adhesive is highly suppressed, and the straight line of the film adhesive before heating with light (400 to 800 nm) The transmittance and the linear transmittance after heating are improved, and as a result, the image recognizability of the film adhesive before and after heating becomes higher. When the average particle size of the filler (d) is not less than the lower limit value, the effect of using the filler (d) can be more remarkably obtained.
In the present specification, the “average particle diameter” means the value of the particle diameter (D 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. ..
 接着剤組成物及びフィルム状接着剤が含有する充填材(d)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The filler (d) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.
 充填材(d)を用いる場合、接着剤組成物において、溶媒以外の全ての成分の総含有量に対する充填材(d)の含有量の割合(すなわち、フィルム状接着剤における、フィルム状接着剤の総質量に対する、充填材(d)の含有量の割合)は、7.5~50質量%であることが好ましく、例えば、10~45質量%、及び10~40質量%のいずれかであってもよい。充填材(d)の含有量がこのような範囲であることで、上記の熱膨張係数の調整がより容易となる。 When the filler (d) is used, in the adhesive composition, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, in the film adhesive, The ratio of the content of the filler (d) with respect to the total mass) is preferably 7.5 to 50% by mass, for example, 10 to 45% by mass or 10 to 40% by mass. Good. When the content of the filler (d) is in such a range, it becomes easier to adjust the thermal expansion coefficient.
<カップリング剤(e)>
 フィルム状接着剤は、カップリング剤(e)を含有することにより、被着体に対する接着性及び密着性が向上する。また、フィルム状接着剤がカップリング剤(e)を含有することにより、その硬化物は耐熱性を損なうことなく、耐水性が向上する。カップリング剤(e)は、無機化合物又は有機化合物と反応可能な官能基を有する。
<Coupling agent (e)>
By containing the coupling agent (e), the film adhesive has improved adhesiveness and adhesion to the adherend. Further, since the film adhesive contains the coupling agent (e), the cured product has improved water resistance without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.
 カップリング剤(e)は、アクリル系樹脂(a)、エポキシ系熱硬化性樹脂(b)等が有する官能基と反応可能な官能基を有する化合物であることが好ましく、シランカップリング剤であることがより好ましい。
 好ましい前記シラン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エトキシシラン、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-(フェニルアミノ)プロピルトリメトキシシラン、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、オリゴマー型又はポリマー型オルガノシロキサン等が挙げられる。
The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the acrylic resin (a), the epoxy thermosetting resin (b), etc., and is a silane coupling agent. Is more preferable.
Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, and 2-glycidyloxymethyldiethoxysilane. (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-amino Ethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomer type or polymer type organosiloxane, and the like. ..
 カップリング剤(e)は、脂肪族系化合物であることが好ましい。
 接着剤組成物及びフィルム状接着剤が、カップリング剤(e)として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The coupling agent (e) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the coupling agent (e), the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) Is further increased, and by containing only an aliphatic compound (in other words, not containing an aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.
 カップリング剤(e)は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、カップリング剤(e)として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The coupling agent (e) is selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. It is preferable not to have one kind or two or more kinds.
Since the adhesive composition and the film adhesive contain the coupling agent (e) having no such bond or group, after the film adhesive is heated (for example, heated at 260° C.) The effect of suppressing coloration is higher, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced. ..
 カップリング剤(e)は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、カップリング剤(e)として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The coupling agent (e) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the coupling agent (e), the film adhesive is heated (for example, heated at 260° C.). ) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), The effect of suppressing coloring is significantly enhanced.
 カップリング剤(e)のうち、脂肪族系化合物(脂肪族系カップリング剤)として、より具体的には、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エトキシシラン、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-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、オリゴマー型又はポリマー型オルガノシロキサン等が挙げられる。 Among the coupling agents (e), more specific examples of the aliphatic compound (aliphatic coupling agent) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and the like. 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, oligomer type or polymer type organosiloxane and the like.
 接着剤組成物及びフィルム状接着剤が含有するカップリング剤(e)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
 カップリング剤(e)を用いる場合、接着剤組成物及びフィルム状接着剤において、カップリング剤(e)の含有量は、アクリル系樹脂(a)及びエポキシ系熱硬化性樹脂(b)の総含有量100質量部に対して、0.03~20質量部であることが好ましく、0.05~10質量部であることがより好ましく、0.1~5質量部であることが特に好ましい。カップリング剤(e)の前記含有量が前記下限値以上であることで、充填材(d)の樹脂への分散性の向上や、フィルム状接着剤の被着体との接着性の向上など、カップリング剤(e)を用いたことによる効果がより顕著に得られる。カップリング剤(e)の前記含有量が前記上限値以下であることで、アウトガスの発生がより抑制される。 When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film adhesive is the total amount of the acrylic resin (a) and the epoxy thermosetting resin (b). The content is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass. When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved, and the adhesion of the film adhesive to the adherend is improved. The effect of using the coupling agent (e) can be more remarkably obtained. When the content of the coupling agent (e) is equal to or less than the upper limit value, the generation of outgas is further suppressed.
<架橋剤(f)>
 アクリル系樹脂(a)として、上述の他の化合物と結合可能なビニル基、(メタ)アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の官能基を有するものを用いる場合、接着剤組成物及びフィルム状接着剤は、前記官能基を他の化合物と結合させて架橋するための架橋剤(f)を含有していてもよい。架橋剤(f)を用いて架橋することにより、フィルム状接着剤の初期接着力及び凝集力を調節できる。
<Crosslinking agent (f)>
When an acrylic resin (a) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, or an isocyanate group capable of binding to the above-mentioned other compounds is used, an adhesive composition The material and the film-like adhesive may contain a cross-linking agent (f) for binding the functional group to another compound to cross-link it. By crosslinking with the crosslinking agent (f), the initial adhesive force and cohesive force of the film adhesive can be adjusted.
 架橋剤(f)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。 As the cross-linking agent (f), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), etc. Are listed.
 前記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);前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;前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。前記「アダクト体」は、前記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又は脂環族多価イソシアネート化合物と、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又は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。前記アダクト体の例としては、後述するようなトリメチロールプロパンのキシリレンジイソシアネート付加物、トリメチロールプロパンのイソホロンジイソシアネート付加物、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、トリメチロールプロパンのヘキサメチレンジイソシアネート付加物等が挙げられる。また、「末端イソシアネートウレタンプレポリマー」とは、ウレタン結合を有するとともに、分子の末端部にイソシアネート基を有するプレポリマーを意味する。 As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as "aromatic polyvalent isocyanate compound etc." Abbreviated); trimers of the above-mentioned aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds with polyol compounds Etc. The "adduct" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil or the like. Means a reaction product with a molecularly active hydrogen-containing compound. Examples of the adduct, xylylene diisocyanate adduct of trimethylol propane as described below, isophorone diisocyanate adduct of trimethylol propane, tolylene diisocyanate adduct of trimethylol propane, hexamethylene diisocyanate adduct of trimethylol propane. Etc. The term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.
 前記有機多価イソシアネート化合物として、より具体的には、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、イソホロ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のいずれか1種又は2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。 Specific examples of the organic polyvalent isocyanate compound include, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; diphenylmethane- 4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; tri A compound in which one or more of tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of hydroxyl groups of a polyol such as methylolpropane; lysine diisocyanate and the like can be mentioned.
 前記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 the organic polyvalent imine compound include N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinyl propionate, N,N′-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine and the like can be mentioned.
 架橋剤(f)として有機多価イソシアネート化合物を用いる場合、アクリル系樹脂(a)としては、水酸基含有重合体を用いることが好ましい。架橋剤(f)がイソシアネート基を有し、アクリル系樹脂(a)が水酸基を有する場合、架橋剤(f)とアクリル系樹脂(a)との反応によって、フィルム状接着剤に架橋構造を簡便に導入できる。 When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the acrylic resin (a). When the cross-linking agent (f) has an isocyanate group and the acrylic resin (a) has a hydroxyl group, a cross-linking structure can be easily formed on the film adhesive by the reaction between the cross-linking agent (f) and the acrylic resin (a). Can be introduced to.
 架橋剤(f)は、脂肪族系化合物であることが好ましい。
 接着剤組成物及びフィルム状接着剤が、架橋剤(f)として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The cross-linking agent (f) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the cross-linking agent (f), an effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is obtained. When the content is higher, and only the aliphatic compound is contained (in other words, the aromatic compound is not contained), the effect of suppressing the above-mentioned coloring is significantly enhanced.
 架橋剤(f)は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、架橋剤(f)として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The cross-linking agent (f) is selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. It is preferable not to have one kind or two or more kinds.
Coloring after heating (for example, heating at 260° C.) of the film adhesive by containing the adhesive composition and the film adhesive which do not have these bonds or groups as the crosslinking agent (f). The effect of suppressing the above is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.
 架橋剤(f)は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、架橋剤(f)として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The cross-linking agent (f) is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the crosslinking agent (f), heating of the film adhesive (for example, heating at 260° C.) The effect of suppressing the subsequent coloring becomes higher, and by containing only the aliphatic compound having no such bond or group (in other words, not containing the aliphatic compound having these bond or group), the above coloring The effect of suppressing is significantly increased.
 架橋剤(f)は、上記の着色の抑制効果が特に高く、かつ架橋剤として優れた特性を有する点では、脂肪族系有機多価イソシアネート化合物(脂肪族系多価イソシアネート架橋剤)であることが好ましい。
 前記脂肪族系多価イソシアネート架橋剤として、より具体的には、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;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、イソホロンジイソシアネート及びヘキサメチレンジイソシアネートのいずれか1種又は2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。
The cross-linking agent (f) is an aliphatic organic polyvalent isocyanate compound (aliphatic polyvalent isocyanate cross-linking agent) in that it has a particularly high effect of suppressing the above coloring and has excellent properties as a cross-linking agent. Is preferred.
Specific examples of the aliphatic polyvalent isocyanate crosslinking agent include, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4′- Diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compound obtained by adding one or more of tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate to all or part of hydroxyl groups of polyols such as trimethylolpropane. Lysine diisocyanate and the like.
 前記フィルム状接着剤は、アクリル系樹脂(a)及び架橋剤(f)に着目した場合、上記の着色の抑制効果が特に高く、かつ優れた特性を有する点では、架橋剤(f)として、前記脂肪族系多価イソシアネート架橋剤を含有し、かつ、アクリル系樹脂(a)として、前記脂肪族系多価イソシアネート架橋剤と結合可能な官能基を有するものを含有していることが好ましい。 When the film adhesive is focused on the acrylic resin (a) and the cross-linking agent (f), the cross-linking agent (f) has a particularly high effect of suppressing the above-mentioned coloring and has excellent properties. It is preferable to contain the aliphatic polyvalent isocyanate cross-linking agent and to contain, as the acrylic resin (a), a resin having a functional group capable of binding to the aliphatic polyvalent isocyanate cross-linking agent.
 接着剤組成物及びフィルム状接着剤が含有する架橋剤(f)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The cross-linking agent (f) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
 架橋剤(f)を用いる場合、接着剤組成物及びフィルム状接着剤において、架橋剤(f)の含有量は、アクリル系樹脂(a)の含有量100質量部に対して、0.3~12質量部であることが好ましく、0.3~3.5質量部であることがより好ましく、0.3~2質量部であることがさらに好ましい。架橋剤(f)の前記含有量が前記下限値以上であることで、架橋剤(f)を用いたことによる効果がより顕著に得られる。また、架橋剤(f)の前記含有量が前記上限値以下であることで、架橋剤(f)の過剰使用が抑制される。 When the cross-linking agent (f) is used, the content of the cross-linking agent (f) in the adhesive composition and the film adhesive is 0.3 to 100 parts by mass with respect to 100 parts by mass of the acrylic resin (a). The amount is preferably 12 parts by mass, more preferably 0.3 to 3.5 parts by mass, still more preferably 0.3 to 2 parts by mass. When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) can be obtained more significantly. Further, when the content of the crosslinking agent (f) is not more than the upper limit value, excessive use of the crosslinking agent (f) is suppressed.
<エネルギー線硬化性樹脂(g)>
 接着剤組成物及びフィルム状接着剤は、エネルギー線硬化性樹脂(g)を含有していてもよい。フィルム状接着剤は、エネルギー線硬化性樹脂(g)を含有していることにより、エネルギー線の照射によって特性を変化させることができる。
<Energy ray curable resin (g)>
The adhesive composition and the film adhesive may contain an energy ray curable resin (g). Since the film adhesive contains the energy ray curable resin (g), its characteristics can be changed by irradiation with energy rays.
 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し、その例として、紫外線、放射線、電子線等が挙げられる。
 紫外線は、例えば、紫外線源として高圧水銀ランプ、ヒュージョンランプ、キセノンランプ、ブラックライト又はLEDランプ等を用いることで照射できる。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。
 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り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する。
In the present specification, the “energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, electron beams and the like.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light or an LED lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present specification, “energy ray curable” means a property of being cured by irradiation with energy rays, and “non-energy ray curable” means a property of not being cured by irradiation of energy rays. To do.
 エネルギー線硬化性樹脂(g)は、エネルギー線硬化性化合物を重合(硬化)して得られたものである。
 前記エネルギー線硬化性化合物としては、例えば、分子内に少なくとも1個の重合性二重結合を有する化合物が挙げられ、(メタ)アクリロイル基を有するアクリレート系化合物が好ましい。
The energy ray-curable resin (g) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferable.
 前記アクリレート系化合物としては、例えば、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールモノヒドロキシペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート等の鎖状脂肪族骨格含有(メタ)アクリレート;ジシクロペンタニルジ(メタ)アクリレート等の環状脂肪族骨格含有(メタ)アクリレート;ポリエチレングリコールジ(メタ)アクリレート等のポリアルキレングリコール(メタ)アクリレート;オリゴエステル(メタ)アクリレート;ウレタン(メタ)アクリレートオリゴマー;エポキシ変性(メタ)アクリレート;前記ポリアルキレングリコール(メタ)アクリレート以外のポリエーテル(メタ)アクリレート;イタコン酸オリゴマー等が挙げられる。 Examples of the acrylate compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta( (Meth)acrylate containing a chain aliphatic skeleton such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; Cycloaliphatic skeleton-containing (meth)acrylate such as cyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; urethane (meth)acrylate oligomer An epoxy-modified (meth)acrylate; a polyether (meth)acrylate other than the polyalkylene glycol (meth)acrylate; an itaconic acid oligomer and the like.
 エネルギー線硬化性樹脂(g)の重量平均分子量は、100~30000であることが好ましく、300~10000であることがより好ましい。 The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.
 接着剤組成物が含有するエネルギー線硬化性樹脂(g)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The energy ray curable resin (g) contained in the adhesive composition may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
 エネルギー線硬化性樹脂(g)を用いる場合、接着剤組成物において、接着剤組成物の総質量に対する、エネルギー線硬化性樹脂(g)の含有量の割合は、1~95質量%であることが好ましく、5~90質量%であることがより好ましく、10~85質量%であることが特に好ましい。 When the energy ray-curable resin (g) is used, the ratio of the content of the energy ray-curable resin (g) to the total weight of the adhesive composition in the adhesive composition is 1 to 95% by mass. Is more preferable, 5 to 90% by mass is more preferable, and 10 to 85% by mass is particularly preferable.
<光重合開始剤(h)>
 接着剤組成物及びフィルム状接着剤は、エネルギー線硬化性樹脂(g)を含有する場合、エネルギー線硬化性樹脂(g)の重合反応を効率よく進めるために、光重合開始剤(h)を含有していてもよい。
<Photopolymerization initiator (h)>
When the adhesive composition and the film adhesive contain the energy ray-curable resin (g), a photopolymerization initiator (h) is added in order to efficiently proceed the polymerization reaction of the energy ray-curable resin (g). It may be contained.
 前記光重合開始剤(h)としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール等のベンゾイン化合物;アセトフェノン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン等のアセトフェノン化合物;ビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物;ベンジルフェニルスルフィド、テトラメチルチウラムモノスルフィド等のスルフィド化合物;1-ヒドロキシシクロヘキシルフェニルケトン等のα-ケトール化合物;アゾビスイソブチロニトリル等のアゾ化合物;チタノセン等のチタノセン化合物;チオキサントン等のチオキサントン化合物;パーオキサイド化合物;ジアセチル等のジケトン化合物;ベンジル;ジベンジル;ベンゾフェノン;2,4-ジエチルチオキサントン;1,2-ジフェニルメタン;2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノン;1-クロロアントラキノン、2-クロロアントラキノン等のキノン化合物等が挙げられる。
 また、光重合開始剤(h)としては、例えば、アミン等の光増感剤等も挙げられる。
Examples of the photopolymerization initiator (h) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and other benzoin compounds; acetophenone; Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl) Acylphosphine oxide compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol such as 1-hydroxycyclohexyl phenyl ketone Compounds; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Examples of the photopolymerization initiator (h) also include photosensitizers such as amines.
 光重合開始剤(h)は、脂肪族系化合物であることが好ましい。
 接着剤組成物及びフィルム状接着剤が、光重合開始剤(h)として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The photopolymerization initiator (h) is preferably an aliphatic compound.
Since the adhesive composition and the film adhesive contain an aliphatic compound as the photopolymerization initiator (h), suppression of coloring after heating the film adhesive (for example, heating at 260° C.) The effect is further enhanced, and by containing only the aliphatic compound (in other words, not containing the aromatic compound), the above-described effect of suppressing coloring is significantly enhanced.
 光重合開始剤(h)は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、光重合開始剤(h)として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The photopolymerization initiator (h) is selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. It is preferable not to have one or more selected.
After the adhesive composition and the film adhesive contain the photopolymerization initiator (h) having no such bond or group, the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and by containing only those having no such bond or group (in other words, not containing those having these bonds or groups), the above-described effect of suppressing coloration is remarkably high. Become.
 光重合開始剤(h)は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、光重合開始剤(h)として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The photopolymerization initiator (h) is an aliphatic compound, and has a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group consisting of
Since the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as the photopolymerization initiator (h), the film adhesive is heated (for example, at 260° C.). The effect of suppressing coloring after heating is further enhanced, and only an aliphatic compound having no such bond or group is contained (in other words, an aliphatic compound having these bond or group is not contained). The effect of suppressing the coloring is markedly increased.
 光重合開始剤(h)のうち、脂肪族系化合物(脂肪族系光重合開始剤)として、より具体的には、例えば、アシルフォスフィンオキサイド化合物;テトラメチルチウラムモノスルフィド等のスルフィド化合物;アゾビスイソブチロニトリル等のアゾ化合物;パーオキサイド化合物;ジアセチル等のジケトン化合物;アミン等の光増感剤等が挙げられる。
 ここで例示した化合物のうち、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しない光重合開始剤(h)としては、例えば、アゾビスイソブチロニトリル以外の化合物が挙げられる。
Among the photopolymerization initiators (h), more specifically, as the aliphatic compound (aliphatic photopolymerization initiator), for example, an acylphosphine oxide compound; a sulfide compound such as tetramethylthiuram monosulfide; an azo Examples thereof include azo compounds such as bisisobutyronitrile; peroxide compounds; diketone compounds such as diacetyl; photosensitizers such as amines.
Among the compounds exemplified here, the compounds are aliphatic compounds, and have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). Examples of the photopolymerization initiator (h) that does not have one or more selected from the group consisting of include, for example, compounds other than azobisisobutyronitrile.
 接着剤組成物及びフィルム状接着剤が含有する光重合開始剤(h)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The photopolymerization initiator (h) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrarily selected. it can.
 光重合開始剤(h)を用いる場合、接着剤組成物において、光重合開始剤(h)の含有量は、エネルギー線硬化性樹脂(g)の含有量100質量部に対して、0.1~20質量部であることが好ましく、1~10質量部であることがより好ましく、2~5質量部であることが特に好ましい。 When the photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is 0.1 with respect to 100 parts by mass of the energy ray-curable resin (g). It is preferably from 20 to 20 parts by mass, more preferably from 1 to 10 parts by mass, particularly preferably from 2 to 5 parts by mass.
<他の酸化防止剤(y)>
 前記接着剤組成物及びフィルム状接着剤は、本発明の効果を損なわない範囲で、前記他の酸化防止剤(y)を含有していてもよい。
 他の酸化防止剤(y)は、リン系酸化防止剤(z)以外の酸化防止剤であれば、特に限定されず、有機化合物及び無機化合物のいずれであってもよい。
<Other antioxidants (y)>
The adhesive composition and the film adhesive may contain the other antioxidant (y) as long as the effect of the present invention is not impaired.
The other antioxidant (y) is not particularly limited as long as it is an antioxidant other than the phosphorus-based antioxidant (z), and may be an organic compound or an inorganic compound.
 接着剤組成物及びフィルム状接着剤が含有する他の酸化防止剤(y)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The other antioxidant (y) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio may be arbitrarily set. You can choose.
 他の酸化防止剤(y)を用いる場合、接着剤組成物及びフィルム状接着剤において、他の酸化防止剤(y)の含有量は、リン系酸化防止剤(z)の含有量100質量部に対して、10質量部以下であることが好ましく、5質量部以下であることがより好ましく、1質量部以下であることがさらに好ましい。他の酸化防止剤(y)の前記含有量が前記上限値以下であることで、前記フィルム状接着剤の加熱前後における着色が、より抑制される。 When the other antioxidant (y) is used, the content of the other antioxidant (y) in the adhesive composition and the film adhesive is 100 parts by mass of the phosphorus-based antioxidant (z). On the other hand, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less. When the content of the other antioxidant (y) is not more than the upper limit value, the coloring of the film adhesive before and after heating is further suppressed.
 前記接着剤組成物及びフィルム状接着剤は、他の酸化防止剤(y)を含有しないことが好ましい。 The adhesive composition and the film adhesive preferably do not contain any other antioxidant (y).
<熱可塑性樹脂(x)>
 前記接着剤組成物及びフィルム状接着剤は、本発明の効果を損なわない範囲で、前記熱可塑性樹脂(x)を含有していてもよい。
 熱可塑性樹脂(x)を用いることで、例えば、ピックアップ時において、フィルム状接着剤を備えた前記チップの、後述するダイシングシートからの引き離しがより容易となったり、被着体の凹凸面へフィルム状接着剤が追従し易くなり、被着体とフィルム状接着剤との間でボイド等の発生がより抑制されることがある。
<Thermoplastic resin (x)>
The adhesive composition and the film adhesive may contain the thermoplastic resin (x) as long as the effects of the present invention are not impaired.
By using the thermoplastic resin (x), for example, at the time of pickup, it becomes easier to separate the chip provided with the film adhesive from a dicing sheet described later, or a film is formed on an uneven surface of an adherend. The linear adhesive may easily follow, and the occurrence of voids and the like between the adherend and the film adhesive may be further suppressed.
 熱可塑性樹脂(x)は、アクリル系樹脂(a)以外の熱可塑性樹脂であれば、特に限定されない。
 前記熱可塑性樹脂としては、例えば、ポリエステル、ポリウレタン、フェノキシ樹脂、ポリブテン、ポリブタジエン、ポリスチレン等が挙げられる。
The thermoplastic resin (x) is not particularly limited as long as it is a thermoplastic resin other than the acrylic resin (a).
Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene and the like.
 熱可塑性樹脂(x)の重量平均分子量は1000~100000であることが好ましく、3000~80000であることがより好ましい。 The weight average molecular weight of the thermoplastic resin (x) is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.
 熱可塑性樹脂(x)のガラス転移温度(Tg)は、-30~150℃であることが好ましく、-20~120℃であることがより好ましい。 The glass transition temperature (Tg) of the thermoplastic resin (x) is preferably −30 to 150° C., more preferably −20 to 120° C.
 接着剤組成物及びフィルム状接着剤が含有する熱可塑性樹脂(x)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The thermoplastic resin (x) contained in the adhesive composition and the film adhesive may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
 熱可塑性樹脂(x)を用いる場合、接着剤組成物及びフィルム状接着剤において、熱可塑性樹脂(x)の含有量は、アクリル系樹脂(a)の含有量100質量部に対して、10質量部以下であることが好ましく、5質量部以下であることがより好ましく、1質量部以下であることがさらに好ましい。熱可塑性樹脂(x)の前記含有量が前記上限値以下であることで、アクリル系樹脂(a)を用いたことによる効果が、より顕著に得られる。 When the thermoplastic resin (x) is used, in the adhesive composition and the film adhesive, the content of the thermoplastic resin (x) is 10 parts by mass based on 100 parts by mass of the acrylic resin (a). It is preferably not more than 5 parts by mass, more preferably not more than 5 parts by mass, still more preferably not more than 1 part by mass. When the content of the thermoplastic resin (x) is equal to or less than the upper limit value, the effect of using the acrylic resin (a) can be more significantly obtained.
 前記接着剤組成物及びフィルム状接着剤は、熱可塑性樹脂(x)を含有しないことが好ましい。 It is preferable that the adhesive composition and the film adhesive do not contain the thermoplastic resin (x).
<汎用添加剤(i)>
 汎用添加剤(i)は、公知のものでよく、目的に応じて任意に選択でき、特に限定されない。好ましい汎用添加剤(I)としては、例えば、可塑剤、帯電防止剤、着色剤(染料、顔料)、ゲッタリング剤等が挙げられる。
<General-purpose additive (i)>
The general-purpose additive (i) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferable general-purpose additives (I) include plasticizers, antistatic agents, colorants (dyes and pigments), gettering agents, and the like.
 汎用添加剤(i)が有機化合物である場合、このような汎用添加剤(i)(本明細書においては、「有機汎用添加剤」と略記する)は、脂肪族系化合物であることが好ましい。
 接着剤組成物及びフィルム状接着剤が、有機汎用添加剤として、脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、脂肪族系化合物のみを含有する(換言すると、芳香族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
When the general-purpose additive (i) is an organic compound, such general-purpose additive (i) (abbreviated as “organic general-purpose additive” in the present specification) is preferably an aliphatic compound. ..
Since the adhesive composition and the film adhesive contain an aliphatic compound as an organic general-purpose additive, the effect of suppressing coloring after heating the film adhesive (for example, heating at 260° C.) is further improved. The effect of suppressing the above-mentioned coloring is significantly increased by containing only the aliphatic compound (in other words, not containing the aromatic compound).
 有機汎用添加剤は、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)、シアノ基(-C≡N)及び芳香族基からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、有機汎用添加剤として、これら結合又は基を有しないものを含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しないもののみを含有する(換言すると、これら結合又は基を有するものを含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The organic general-purpose additive is selected from the group consisting of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N), and an aromatic group. It is preferable not to have one kind or two or more kinds.
Since the adhesive composition and the film adhesive contain the organic general-purpose additive that does not have these bonds or groups, coloring of the film adhesive after heating (for example, heating at 260° C.) The suppression effect is further enhanced, and by containing only those having no such bond or group (in other words, not containing those having these bond or group), the above-described effect of suppressing coloration is significantly enhanced.
 有機汎用添加剤は、脂肪族系化合物であり、かつ、炭素原子間の三重結合(C≡C)、炭素原子間の二重結合(C=C)及びシアノ基(-C≡N)からなる群から選択される1種又は2種以上を有しないことが好ましい。
 接着剤組成物及びフィルム状接着剤が、有機汎用添加剤として、これら結合又は基を有しない脂肪族系化合物を含有することにより、フィルム状接着剤の加熱(例えば、260℃での加熱)後の着色の抑制効果がより高くなり、これら結合又は基を有しない脂肪族系化合物のみを含有する(換言すると、これら結合又は基を有する脂肪族系化合物を含有しない)ことにより、上記の着色の抑制効果が顕著に高くなる。
The organic general-purpose additive is an aliphatic compound and is composed of a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N). It is preferable not to have one or more selected from the group.
After the adhesive composition and the film adhesive contain an aliphatic compound having no bond or group as an organic general-purpose additive, the film adhesive is heated (for example, heated at 260° C.). The effect of suppressing the coloring is further increased, and only the aliphatic compound having no such bond or group is contained (in other words, the aliphatic compound having these bond or group is not contained), the above-mentioned coloring The suppression effect is remarkably enhanced.
 接着剤組成物及びフィルム状接着剤が含有する汎用添加剤(i)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
 接着剤組成物及びフィルム状接着剤の汎用添加剤(i)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。
The general-purpose additive (i) contained in the adhesive composition and the film adhesive may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected. ..
The content of the general-purpose additive (i) in the adhesive composition and the film adhesive is not particularly limited and may be appropriately selected depending on the purpose.
<溶媒>
 接着剤組成物は、さらに溶媒を含有することが好ましい。溶媒を含有する接着剤組成物は、取り扱い性が良好となる。
 前記溶媒は特に限定されないが、好ましいものとしては、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、イソブチルアルコール(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。
 接着剤組成物が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
<Solvent>
The adhesive composition preferably further contains a solvent. The adhesive composition containing a solvent has good handleability.
The solvent is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the adhesive composition may be only one kind, or may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof may be arbitrarily selected.
 接着剤組成物が含有する溶媒は、接着剤組成物中の含有成分をより均一に混合できる点から、メチルエチルケトン等であることが好ましい。 The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the adhesive composition can be mixed more uniformly.
<<接着剤組成物の製造方法>>
 接着剤組成物は、これを構成するための各成分を配合することで得られる。
 各成分の配合時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。
 溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
<<Production Method of Adhesive Composition>>
The adhesive composition can be obtained by blending each component for constituting the adhesive composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by preliminarily diluting this compounding ingredient by mixing the solvent with any compounding ingredient other than the solvent, or diluting any compounding ingredient other than the solvent beforehand. Alternatively, the solvent may be used as a mixture with these compounding ingredients.
 配合時に各成分を混合する方法は特に限定されず、撹拌子又は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、公知の方法から適宜選択すればよい。
 各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
The method of mixing the components at the time of blending is not particularly limited, and a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by adding ultrasonic waves It may be selected appropriately.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.
 図1は、本発明の一実施形態に係るフィルム状接着剤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、本発明の特徴を分かり易くするために、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。 FIG. 1 is a sectional view schematically showing a film adhesive according to one embodiment of the present invention. It should be noted that, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there may be a case where an essential part is enlarged, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.
 ここに示すフィルム状接着剤13は、その一方の面(本明細書においては、「第1面」と称することがある)13a上に第1剥離フィルム151を備え、前記第1面13aとは反対側の他方の面(本明細書においては、「第2面」と称することがある)13b上に第2剥離フィルム152を備えている。ここでは、このように、第1剥離フィルム151、フィルム状接着剤13及び第2剥離フィルム152がこの順に、これらの厚さ方向において積層されて構成されている積層シートに、符号109を付している。
 このようなフィルム状接着剤13(積層シート109)は、例えば、ロール状として保存するのに好適である。
The film adhesive 13 shown here is provided with a first release film 151 on one surface (sometimes referred to as “first surface” in the present specification) 13a thereof, and the first surface 13a is The second release film 152 is provided on the other surface (may be referred to as “second surface” in this specification) 13b on the opposite side. Here, reference numeral 109 is given to the laminated sheet configured by laminating the first release film 151, the film adhesive 13 and the second release film 152 in this order in this order in the thickness direction. ing.
Such a film-like adhesive 13 (laminated sheet 109) is suitable for storage as a roll, for example.
 フィルム状接着剤13は、上述の光透過性を有する。例えば、フィルム状接着剤13の第1面13a及び第2面13bの少なくとも一方は、実質的に芳香族化合物を含まない。
 フィルム状接着剤13の厚さは、10~40μmであることが好ましい。
 フィルム状接着剤13は、上述の接着剤組成物を用いて形成できる。
The film adhesive 13 has the above-mentioned light transmittance. For example, at least one of the first surface 13a and the second surface 13b of the film adhesive 13 does not substantially contain an aromatic compound.
The thickness of the film adhesive 13 is preferably 10 to 40 μm.
The film adhesive 13 can be formed using the above-mentioned adhesive composition.
 第1剥離フィルム151及び第2剥離フィルム152は、いずれも公知のものでよい。
 第1剥離フィルム151及び第2剥離フィルム152は、互いに同じものであってもよいし、例えば、フィルム状接着剤13から剥離させるときに必要な剥離力が互いに異なるなど、互いに異なるものであってもよい。
Both the first release film 151 and the second release film 152 may be known ones.
The first release film 151 and the second release film 152 may be the same as each other, or different from each other, such as different release forces required when releasing from the film adhesive 13. Good.
 図1に示すフィルム状接着剤13は、第1剥離フィルム151及び第2剥離フィルム152のいずれか一方が取り除かれ、生じた露出面が、その貼付対象物への貼付面となる。ここで、貼付対象物としては、例えば、前記チップ等が挙げられる。フィルム状接着剤13の貼付面は、前記チップの場合にはその回路形成面となる。 In the film adhesive 13 shown in FIG. 1, one of the first peeling film 151 and the second peeling film 152 is removed, and the exposed surface thus formed becomes the sticking surface to the sticking target. Here, as the pasting target, for example, the chip and the like can be mentioned. In the case of the chip, the surface on which the film adhesive 13 is attached becomes the circuit forming surface.
 好ましい前記フィルム状接着剤の一実施形態としては、例えば、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
 前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まず、
 大きさが2mm×2mmで、厚さが20μmである前記フィルム状接着剤と、大きさが30mm×30mmで、厚さが300μmである銅板と、シリコンチップとを用い、前記フィルム状接着剤の、一方の面全面が前記シリコンチップの表面に貼付され、他方の面全面が前記銅板の表面に貼付されて構成され、前記フィルム状接着剤と前記シリコンチップとの側面が位置合わせされた試験片を作製し、23℃の温度条件下で、前記試験片中の、前記位置合わせされた側面において、前記フィルム状接着剤と前記シリコンチップの両方に対して、前記フィルム状接着剤の前記他方の面に対して平行な方向に、200μm/sの速度で力を加え、前記フィルム状接着剤が破壊されるまでに加えられていた力の最大値を、前記フィルム状接着剤のせん断強度(N/2mm□)としたとき、前記せん断強度が20N/2mm□以上であるもの、が挙げられる。
As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
At least one surface of the film adhesive is substantially free of aromatic compounds,
Using the film adhesive having a size of 2 mm×2 mm and a thickness of 20 μm, the copper plate having a size of 30 mm×30 mm and a thickness of 300 μm, and a silicon chip, the film adhesive , A test piece in which the entire surface of one surface is attached to the surface of the silicon chip and the entire surface of the other surface is attached to the surface of the copper plate, and the side surfaces of the film adhesive and the silicon chip are aligned. Under a temperature condition of 23° C., in the aligned side surface in the test piece, for both the film adhesive and the silicon chip, the other of the film adhesive A force is applied in a direction parallel to the surface at a speed of 200 μm/s, and the maximum value of the force applied until the film adhesive is broken is defined as the shear strength (N /2 mm□), the shear strength is 20 N/2 mm□ or more.
 好ましい前記フィルム状接着剤の一実施形態としては、例えば、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
 前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まず、
 前記フィルム状接着剤が、リン系酸化防止剤(z)を含有し、
 前記リン系酸化防止剤(z)が、脂肪族系化合物であり、かつ、炭素原子間の三重結合と、炭素原子間の二重結合と、シアノ基と、からなる群から選択される1種又は2種以上を有しないもの、が挙げられる。
As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
At least one surface of the film adhesive is substantially free of aromatic compounds,
The film adhesive contains a phosphorus-based antioxidant (z),
The phosphorus-based antioxidant (z) is an aliphatic compound, and is one selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Or the thing which does not have 2 or more types is mentioned.
 好ましい前記フィルム状接着剤の一実施形態としては、例えば、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
 前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まず、
 前記フィルム状接着剤が、エポキシ化合物(b1)を含有し、
 前記エポキシ化合物(b1)が、脂肪族系化合物であり、かつ、炭素原子間の三重結合と、炭素原子間の二重結合と、シアノ基と、からなる群から選択される1種又は2種以上を有しないもの、が挙げられる。
As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
At least one surface of the film adhesive is substantially free of aromatic compounds,
The film adhesive contains an epoxy compound (b1),
The epoxy compound (b1) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above.
 好ましい前記フィルム状接着剤の一実施形態としては、例えば、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
 前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まず、
 前記フィルム状接着剤が、アクリル系樹脂(a)と、架橋剤(f)と、を含有し、
 前記アクリル系樹脂(a)が、前記架橋剤(f)と結合可能な官能基を有し、
 前記架橋剤(f)が、脂肪族系化合物であり、かつ、炭素原子間の三重結合と、炭素原子間の二重結合と、シアノ基と、からなる群から選択される1種又は2種以上を有しないもの、が挙げられる。
As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
At least one surface of the film adhesive is substantially free of aromatic compounds,
The film adhesive contains an acrylic resin (a) and a crosslinking agent (f),
The acrylic resin (a) has a functional group capable of binding to the crosslinking agent (f),
The cross-linking agent (f) is an aliphatic compound, and one or two kinds selected from the group consisting of a triple bond between carbon atoms, a double bond between carbon atoms, and a cyano group. Those that do not have the above are included.
 好ましい前記フィルム状接着剤の一実施形態としては、例えば、チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
 前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まず、
 前記フィルム状接着剤が、充填材(d)を含有し、
 前記充填材(d)の平均粒子径が10~100nmであるもの、が挙げられる。
As an embodiment of the preferable film adhesive, for example, a film adhesive for bonding the circuit forming surface of the chip and the light-transmitting cover,
At least one surface of the film adhesive is substantially free of aromatic compounds,
The film adhesive contains a filler (d),
The filler (d) has an average particle diameter of 10 to 100 nm.
◇積層シート及び複合シート
 本発明の一実施形態に係る積層シートは、前記フィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられた樹脂フィルムと、を備えて構成されている。
 また、本発明の一実施形態に係る複合シートは、前記フィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられたダイシングシートと、を備えており、前記ダイシングシートが、基材と、前記基材の一方の面上に設けられた粘着剤層と、を備えており、前記粘着剤層が、前記基材と前記フィルム状接着剤との間に配置されている。
◇ Laminated sheet and composite sheet A laminated sheet according to an embodiment of the present invention is configured to include the film adhesive and a resin film provided on one surface of the film adhesive. ..
A composite sheet according to an embodiment of the present invention includes the film adhesive and a dicing sheet provided on one surface of the film adhesive, and the dicing sheet is a base material. And a pressure-sensitive adhesive layer provided on one surface of the base material, and the pressure-sensitive adhesive layer is disposed between the base material and the film adhesive.
 前記積層シートは、前記フィルム状接着剤の少なくも一方の面上に樹脂フィルムが設けられていればよく、片面上のみに樹脂フィルムが設けられていてもよいし、両面上(すなわち、前記一方の面上と、これとは反対側の他方の面上)に樹脂フィルムが設けられていてもよい。 The laminated sheet, as long as the resin film is provided on at least one side of the film-like adhesive, the resin film may be provided only on one side, or on both sides (that is, the one side A resin film may be provided on the surface of (1) and on the other surface on the opposite side.
 前記積層シートにおいて、前記フィルム状接着剤の両面上に前記樹脂フィルムが設けられている場合には、これら樹脂フィルムは、互いに同一でも異なっていてもよく、これら樹脂フィルムの組み合わせは特に限定されない。 When the resin film is provided on both sides of the film adhesive in the laminated sheet, these resin films may be the same or different from each other, and the combination of these resin films is not particularly limited.
 前記樹脂フィルムは1層(単層)からなるものであってもよいし、2層以上の複数層からなるものであってもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The resin film may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other. The combination of these plural layers is not particularly limited.
 前記樹脂フィルムは、樹脂のみを構成材料とするシートであってもよいし、樹脂とそれ以外の成分とを構成材料とし、樹脂を主たる構成材料とするシートであってもよい。 The resin film may be a sheet containing only resin as a constituent material, or may be a sheet containing resin and other components as constituent materials and resin as a major constituent material.
 前記樹脂フィルムの構成材料である前記樹脂としては、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種以上の前記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等が挙げられる。
 また、前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
 また、前記樹脂としては、例えば、ここまでに例示した前記樹脂の1種又は2種以上が架橋した架橋樹脂;ここまでに例示した前記樹脂の1種又は2種以上を用いたアイオノマー等の変性樹脂も挙げられる。
Examples of the resin that is a constituent material of the resin film include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polymethylpentene. Polyolefin other than polyethylene such as norbornene resin; ethylene such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer -Based copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene; Polycycloolefins; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have aromatic cyclic groups; Poly(meth)acrylic acid ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; polyetherketone and the like. To be
Examples of the resin also include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester is preferably one in which the amount of the resin other than the polyester is relatively small.
Further, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more of the resins exemplified so far; modification of an ionomer or the like using one or more of the resins exemplified so far Resins are also included.
 前記樹脂フィルムは、剥離フィルムであってもよいし、後述する基材であってもよい。 基材については、別途詳しく説明する。 The resin film may be a release film or a base material described later. The base material will be explained in detail separately.
 前記剥離フィルムとしては、例えば、樹脂層と、前記樹脂層の一方の面上に設けられた剥離処理層と、を備えて構成された、複数層からなるものが挙げられる。 The release film includes, for example, a multi-layered film including a resin layer and a release treatment layer provided on one surface of the resin layer.
 前記剥離フィルムは、前記樹脂層の一方の面を剥離処理することで製造できる。
 前記樹脂層は、樹脂を含有する樹脂組成物を成形又は塗工し、必要に応じて乾燥させることで作製できる。
The release film can be manufactured by subjecting one surface of the resin layer to a release treatment.
The resin layer can be prepared by molding or coating a resin composition containing a resin and drying it as necessary.
 前記樹脂層の構成材料である樹脂は、前記樹脂フィルムの構成材料である前記樹脂と同じである。
 前記樹脂層の剥離処理は、例えば、アルキッド系、シリコーン系、フッ素系、不飽和ポリエステル系、ポリオレフィン系又はワックス系等の、公知の各種剥離剤によって行うことができる。
 前記剥離剤は、耐熱性を有する点では、アルキッド系、シリコーン系又はフッ素系の剥離剤であることが好ましい。
The resin that is a constituent material of the resin layer is the same as the resin that is a constituent material of the resin film.
The peeling treatment of the resin layer can be performed with various known peeling agents such as alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based or wax-based release agents.
The release agent is preferably an alkyd-based, silicone-based or fluorine-based release agent in terms of heat resistance.
 前記樹脂層は、1層(単層)からなるものでもよいし、2層以上の複数層からなるものでもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The resin layer may be composed of one layer (single layer) or may be composed of two or more layers, and when composed of a plurality of layers, the plurality of layers may be the same or different from each other, The combination of these plural layers is not particularly limited.
 前記フィルム状接着剤の両面上に、樹脂フィルムとして前記剥離フィルムが設けられて構成された積層シートとしては、例えば、図1に示す積層シート109が挙げられる。 As a laminated sheet configured by providing the release film as a resin film on both surfaces of the film adhesive, for example, the laminated sheet 109 shown in FIG. 1 can be cited.
 前記フィルム状接着剤の片面上のみに樹脂フィルムが設けられて構成された積層シートとしては、例えば、図2に示す積層シート108が挙げられる。
 なお、図2以降の図において、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。
As a laminated sheet configured by providing a resin film only on one surface of the film adhesive, for example, the laminated sheet 108 shown in FIG. 2 can be cited.
2 and subsequent figures, the same components as those shown in the already described figures are designated by the same reference numerals as those in the already described figures, and detailed description thereof will be omitted.
 ここに示す積層シート108は、フィルム状接着剤13の第1面13a上に樹脂フィルム19を備えて、構成されている。
 樹脂フィルム19は、上記のものであり、剥離フィルム(例えば、図1中の第1剥離フィルム151又は第2剥離フィルム152)であってもよいし、後述する基材であってもよい。
The laminated sheet 108 shown here is configured by including the resin film 19 on the first surface 13 a of the film adhesive 13.
The resin film 19 is as described above, and may be a release film (for example, the first release film 151 or the second release film 152 in FIG. 1) or a base material described later.
 前記樹脂フィルムの厚さは、目的に応じて任意に設定でき、特に限定されない。
 前記樹脂フィルムの厚さは、例えば、10~200μmであってもよい。
The thickness of the resin film can be arbitrarily set according to the purpose and is not particularly limited.
The thickness of the resin film may be, for example, 10 to 200 μm.
 本実施形態の積層シートは、図2に示すものに限定されず、本発明の効果を損なわない範囲で、図2に示すものの一部の構成が変更又は削除されたものや、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。より具体的には、以下のとおりである。 The laminated sheet of the present embodiment is not limited to the one shown in FIG. 2, and a configuration in which a part of the configuration shown in FIG. 2 is changed or deleted, or is described so far, within a range that does not impair the effects of the present invention. Other configurations may be added to the above configuration. More specifically, it is as follows.
 例えば、本実施形態の積層シートは、フィルム状接着剤の第2面に何も備えていなくてもよいが、フィルム状接着剤の第2面のうち、周縁部近傍の領域に、積層シートをリングフレーム等の治具に固定するための治具用接着剤層を備えていてもよい。
 治具用接着剤層は、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。
For example, the laminated sheet of the present embodiment may have nothing on the second surface of the film adhesive, but the laminated sheet may be provided on the second surface of the film adhesive in a region near the peripheral portion. A jig adhesive layer for fixing to a jig such as a ring frame may be provided.
The adhesive layer for a jig may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which a layer containing an adhesive component is laminated on both sides of a sheet as a core material. It may be one.
 例えば、積層シートをそのフィルム状接着剤側又は樹脂フィルム側の上方から見下ろして平面視したときに、フィルム状接着剤及び樹脂フィルムの表面積は、同等又はほぼ同等であってもよいが、本実施形態の積層シートにおいては、フィルム状接着剤の表面積が樹脂フィルムの表面積よりも小さく、樹脂フィルムの一部領域が露出していてもよい。その場合、例えば、少なくとも樹脂フィルムの幅方向における周縁部が、フィルム状接着剤で被覆されずに露出していてもよい。このような積層シートは、上記の治具用接着剤層を、この樹脂フィルムの露出面に備えていてもよい。 For example, the surface area of the film-like adhesive and the resin film may be the same or almost the same when the laminated sheet is viewed from above the film-like adhesive side or the resin film side and viewed in a plan view. In the laminated sheet of the embodiment, the surface area of the film adhesive may be smaller than the surface area of the resin film, and a partial region of the resin film may be exposed. In that case, for example, at least the peripheral portion in the width direction of the resin film may be exposed without being covered with the film adhesive. Such a laminated sheet may be provided with the jig adhesive layer on the exposed surface of the resin film.
 図3は、本発明の一実施形態に係る複合シートの一例を模式的に示す断面図である。
 ここに示す複合シート101は、フィルム状接着剤13と、フィルム状接着剤13の第2面13b上に設けられたダイシングシート10と、を備えており、ダイシングシート10が、基材11と、基材11の一方の面(本明細書においては、「第1面」と称することがある)11a上に設けられた粘着剤層12と、を備えており、粘着剤層12が、基材11とフィルム状接着剤13との間に配置されて、構成されている。
 換言すると、複合シート101は、基材11、粘着剤層12及びフィルム状接着剤13がこの順に、これらの厚さ方向において積層されて構成されている。
 ダイシングシート10のフィルム状接着剤13側の面(本明細書においては、「第1面」と称することがある)10aは、粘着剤層12の基材11側とは反対側の面(本明細書においては、「第1面」と称することがある)12aと同じである。
FIG. 3 is a sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention.
The composite sheet 101 shown here includes a film adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film adhesive 13, and the dicing sheet 10 includes a base material 11 and The pressure-sensitive adhesive layer 12 provided on one surface (sometimes referred to as “first surface” in the present specification) 11a of the base material 11, and the pressure-sensitive adhesive layer 12 is a base material. 11 and the film adhesive 13 are arranged and configured.
In other words, the composite sheet 101 is configured by laminating the base material 11, the adhesive layer 12, and the film adhesive 13 in this order in the thickness direction thereof.
The surface 10 a of the dicing sheet 10 on the film adhesive 13 side (may be referred to as “first surface” in the present specification) is a surface opposite to the base material 11 side of the pressure-sensitive adhesive layer 12 (the book). In the specification, it may be referred to as a "first surface") 12a.
 複合シート101は、さらにフィルム状接着剤13上に、剥離フィルム15を備えている。
 複合シート101においては、基材11の第1面11aに粘着剤層12が積層され、粘着剤層12の第1面12aの全面又はほぼ全面に、フィルム状接着剤13が積層され、フィルム状接着剤13の第1面13aの全面又はほぼ全面に、剥離フィルム15が積層されている。
The composite sheet 101 further includes a release film 15 on the film adhesive 13.
In the composite sheet 101, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the film adhesive 13 is laminated on the entire surface or almost all of the first surface 12a of the pressure-sensitive adhesive layer 12 to form a film. The release film 15 is laminated on the entire surface or almost the entire surface of the first surface 13 a of the adhesive 13.
 ダイシングシート10は、公知のものであってよい。
 ダイシングシート10中の基材11及び粘着剤層12について、順次説明する。
The dicing sheet 10 may be a known one.
The base material 11 and the pressure-sensitive adhesive layer 12 in the dicing sheet 10 will be sequentially described.
 ダイシングシート10中の基材11は、シート状又はフィルム状であり、その構成材料としては、例えば、各種樹脂が挙げられる。ダイシングシート10の構成材料である前記樹脂としては、前記積層シート中の前記樹脂フィルムの構成材料である樹脂と同じものが挙げられる。 The base material 11 in the dicing sheet 10 has a sheet shape or a film shape, and examples of the constituent material thereof include various resins. Examples of the resin which is a constituent material of the dicing sheet 10 include the same resin as a constituent material of the resin film in the laminated sheet.
 基材を構成する樹脂は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The resin constituting the base material may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.
 基材は1層(単層)からなるものであってもよいし、2層以上の複数層からなるものであってもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The base material may be composed of one layer (single layer) or may be composed of two or more layers. When composed of a plurality of layers, the plurality of layers may be the same or different from each other. However, the combination of these plural layers is not particularly limited.
 基材11の厚さは、50~300μmであることが好ましく、60~150μmであることがより好ましい。基材11の厚さがこのような範囲であることで、複合シート101の可撓性と、貼付対象物への貼付性がより向上する。
 ここで、「基材の厚さ」とは、基材全体の厚さを意味し、例えば、複数層からなる基材の厚さとは、基材を構成するすべての層の合計の厚さを意味する。
The thickness of the base material 11 is preferably 50 to 300 μm, more preferably 60 to 150 μm. When the thickness of the base material 11 is in such a range, the flexibility of the composite sheet 101 and the sticking property to the sticking target are further improved.
Here, the “thickness of the base material” means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all layers constituting the base material. means.
 基材11は、厚さの精度が高いもの、すなわち、部位によらず厚さのばらつきが抑制されたものが好ましい。上述の構成材料のうち、このような厚さの精度が高い基材を構成するのに使用可能な材料としては、例えば、ポリエチレン、ポリエチレン以外のポリオレフィン、ポリエチレンテレフタレート、エチレン-酢酸ビニル共重合体等が挙げられる。 It is preferable that the base material 11 has a high thickness accuracy, that is, a material in which the thickness variation is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to form such a highly accurate base material include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Are listed.
 基材11は、前記樹脂等の主たる構成材料以外に、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。 The base material 11 contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst and a softening agent (plasticizer) in addition to the main constituent materials such as the resin. May be
 基材11は、透明であってもよいし、不透明であってもよく、目的に応じて着色されていてもよいし、他の層が蒸着されていてもよい。 The base material 11 may be transparent or opaque, and may be colored depending on the purpose, or another layer may be vapor-deposited.
 基材11は、その上に設けられる他の層(ここでは粘着剤層12)等との密着性を向上させるために、サンドブラスト処理、溶剤処理等による凹凸化処理や、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等が表面に施されたものであってもよい。
 また、基材11は、表面がプライマー処理を施されたものであってもよい。
 また、基材11は、帯電防止コート層;複合シートを重ね合わせて保存する際に、基材11が他のシートに接着することや、基材11が吸着テーブルに接着することを防止する層等を有するものであってもよい。
The base material 11 has a roughening treatment such as a sand blasting treatment or a solvent treatment, a corona discharge treatment, an electron beam treatment, or the like in order to improve the adhesion with other layers (here, the pressure-sensitive adhesive layer 12) provided thereon. The surface may be subjected to irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, or the like.
Further, the base material 11 may have a surface subjected to a primer treatment.
Further, the base material 11 is an antistatic coating layer; a layer that prevents the base material 11 from adhering to another sheet and the base material 11 from adhering to the suction table when the composite sheets are stored in a stacked state. Etc. may be included.
 基材11は、公知の方法で製造できる。例えば、樹脂を含有する基材11は、前記樹脂を含有する樹脂組成物を成形することで製造できる。 The base material 11 can be manufactured by a known method. For example, the base material 11 containing a resin can be manufactured by molding a resin composition containing the resin.
 ダイシングシート10中の粘着剤層12は、シート状又はフィルム状であり、粘着剤を含有する。
 前記粘着剤としては、例えば、アクリル系樹脂、ウレタン系樹脂、ゴム系樹脂、シリコーン系樹脂、エポキシ系樹脂、ポリビニルエーテル、ポリカーボネート、エステル系樹脂等の粘着性樹脂が挙げられ、アクリル系樹脂が好ましい。
The pressure-sensitive adhesive layer 12 in the dicing sheet 10 has a sheet shape or a film shape and contains a pressure-sensitive adhesive.
Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin, and acrylic resin is preferable. ..
 なお、本明細書において、「粘着性樹脂」には、粘着性を有する樹脂と、接着性を有する樹脂と、の両方が包含される。例えば、前記粘着性樹脂には、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り粘着性を示す樹脂や、熱又は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まれる。 In the present specification, "adhesive resin" includes both a resin having an adhesive property and a resin having an adhesive property. For example, the adhesive resin is not only the resin having adhesiveness itself, but also the resin that exhibits adhesiveness when used in combination with other components such as additives, and the adhesiveness due to the presence of a trigger such as heat or water. Resins and the like indicating are also included.
 粘着剤層12は1層(単層)からなるものであってもよいし、2層以上の複数層からなるものであってもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The pressure-sensitive adhesive layer 12 may be composed of one layer (single layer) or may be composed of two or more layers. When composed of a plurality of layers, these layers may be the same as each other. They may be different, and the combination of these plural layers is not particularly limited.
 粘着剤層12の厚さは、特に限定されないが、1~100μmであることが好ましく、1~60μmであることがより好ましく、1~30μmであることが特に好ましい。
 ここで、「粘着剤層の厚さ」とは、粘着剤層全体の厚さを意味し、例えば、複数層からなる粘着剤層の厚さとは、粘着剤層を構成するすべての層の合計の厚さを意味する。
The thickness of the pressure-sensitive adhesive layer 12 is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the whole pressure-sensitive adhesive layer, for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.
 粘着剤層12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あってもよいし、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あってもよい。すなわち、粘着剤層12は、エネルギー線硬化性及び非エネルギー線硬化性のいずれであってもよい。エネルギー線硬化性の粘着剤層12は、硬化前及び硬化後での物性を容易に調節できる。例えば、エネルギー線硬化性の粘着剤層12を硬化させることにより、その貼付対象物への粘着力を容易に調節できる。 The adhesive layer 12 may be formed using an energy ray curable adhesive or may be formed using a non-energy ray curable adhesive. That is, the adhesive layer 12 may be either energy ray curable or non-energy ray curable. The energy ray-curable pressure-sensitive adhesive layer 12 can easily adjust physical properties before and after curing. For example, by curing the energy ray-curable pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive force to the attachment target can be easily adjusted.
 粘着剤層12は、粘着剤を含有する粘着剤組成物を用いて形成できる。例えば、粘着剤層12の形成対象面に粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に粘着剤層12を形成できる。粘着剤組成物における、常温で気化しない成分同士の含有量の比率は、通常、粘着剤層12における前記成分同士の含有量の比率と同じとなる。本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、すなわち平常の温度を意味し、例えば、15~25℃の温度等が挙げられる。 The pressure-sensitive adhesive layer 12 can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive composition can be applied to the surface on which the pressure-sensitive adhesive layer 12 is to be formed and, if necessary, dried to form the pressure-sensitive adhesive layer 12 at a desired site. In the pressure-sensitive adhesive composition, the content ratio of the components that do not vaporize at room temperature is usually the same as the content ratio of the components in the pressure-sensitive adhesive layer 12. In the present specification, the “normal temperature” means a temperature at which it is not cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25° C.
 粘着剤組成物の塗工は、公知の方法で行えばよく、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーター等の各種コーターを用いる方法が挙げられる。 The coating of the adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater. Examples include a method using various coaters such as a Meyer bar coater and a kiss coater.
 基材11上に粘着剤層12を設ける場合には、例えば、基材11上に粘着剤組成物を塗工し、必要に応じて乾燥させることで、基材11上に粘着剤層12を積層すればよい。また、基材11上に粘着剤層12を設ける場合には、例えば、剥離フィルム上に粘着剤組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に粘着剤層12を形成しておき、この粘着剤層12の露出面を、基材11の一方の表面(ここでは第1面11a)と貼り合わせることで、基材11上に粘着剤層12を積層してもよい。この場合の剥離フィルムは、複合シート101の製造過程又は使用過程のいずれかのタイミングで、取り除けばよい。 When the pressure-sensitive adhesive layer 12 is provided on the base material 11, for example, the pressure-sensitive adhesive composition is applied on the base material 11 and dried as necessary to form the pressure-sensitive adhesive layer 12 on the base material 11. It may be laminated. When the pressure-sensitive adhesive layer 12 is provided on the base material 11, for example, the pressure-sensitive adhesive composition is applied on the release film and dried as necessary to form the pressure-sensitive adhesive layer 12 on the release film. Even if the pressure-sensitive adhesive layer 12 is laminated on the base material 11 by forming it and bonding the exposed surface of the pressure-sensitive adhesive layer 12 to one surface (here, the first surface 11 a) of the base material 11. Good. In this case, the release film may be removed at any timing during the manufacturing process or the use process of the composite sheet 101.
 粘着剤層12がエネルギー線硬化性である場合、エネルギー線硬化性の粘着剤組成物としては、例えば、非エネルギー線硬化性の粘着性樹脂(I-1a)(以下、「粘着性樹脂(I-1a)」と略記することがある)と、エネルギー線硬化性化合物と、を含有する粘着剤組成物(I-1);前記粘着性樹脂(I-1a)の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂(I-2a)(以下、「粘着性樹脂(I-2a)」と略記することがある)を含有する粘着剤組成物(I-2);前記粘着性樹脂(I-2a)と、エネルギー線硬化性化合物と、を含有する粘着剤組成物(I-3)等が挙げられる。 When the pressure-sensitive adhesive layer 12 is energy ray-curable, the energy ray-curable pressure-sensitive adhesive composition may be, for example, a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, referred to as “pressure-sensitive adhesive (I -1a)") and an energy ray-curable compound; and an unsaturated group in the side chain of the adhesive resin (I-1a). A pressure-sensitive adhesive composition (I-2) containing the introduced energy ray-curable pressure-sensitive adhesive resin (I-2a) (hereinafter, may be abbreviated as “adhesive resin (I-2a)”); Examples thereof include an adhesive composition (I-3) containing an adhesive resin (I-2a) and an energy ray-curable compound.
 粘着剤層12が非エネルギー線硬化性である場合、非エネルギー線硬化性の粘着剤組成物としては、例えば、前記粘着性樹脂(I-1a)を含有する粘着剤組成物(I-4)等が挙げられる。 When the pressure-sensitive adhesive layer 12 is non-energy ray curable, the non-energy ray curable pressure sensitive adhesive composition is, for example, a pressure sensitive adhesive composition (I-4) containing the pressure sensitive adhesive resin (I-1a). Etc.
 フィルム状接着剤13は、上述の光透過性を有する。例えば、フィルム状接着剤13の第1面13a及び第2面13bの少なくとも一方は、実質的に芳香族化合物を含まない。
 フィルム状接着剤13の厚さは、10~40μmであることが好ましい。
 フィルム状接着剤13は、上述の接着剤組成物を用いて形成できる。
The film adhesive 13 has the above-mentioned light transmittance. For example, at least one of the first surface 13a and the second surface 13b of the film adhesive 13 does not substantially contain an aromatic compound.
The thickness of the film adhesive 13 is preferably 10 to 40 μm.
The film adhesive 13 can be formed using the above-mentioned adhesive composition.
 剥離フィルム15は、図1に示す第1剥離フィルム151又は第2剥離フィルム152と同様のものである。 The release film 15 is similar to the first release film 151 or the second release film 152 shown in FIG.
 複合シート101の場合に限らず、本実施形態の複合シートにおいては、剥離フィルム(例えば、図3に示す剥離フィルム15)は任意の構成であり、本実施形態の複合シートは、剥離フィルムを備えていてもよいし、備えていなくてもよい。 Not limited to the case of the composite sheet 101, in the composite sheet of the present embodiment, the release film (for example, the release film 15 shown in FIG. 3) has any configuration, and the composite sheet of the present embodiment includes the release film. It may or may not be provided.
 複合シート101は、剥離フィルム15が取り除かれた状態で、フィルム状接着剤13の第1面13aに、対象物(例えば、チップの回路形成面)が貼付されて、使用される。 The composite sheet 101 is used with an object (for example, a circuit forming surface of a chip) attached to the first surface 13a of the film adhesive 13 with the release film 15 removed.
 本実施形態の複合シートは、図3に示すものに限定されず、本発明の効果を損なわない範囲で、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や、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。より具体的には、以下のとおりである。 The composite sheet of the present embodiment is not limited to the one shown in FIG. 3, and a part of the configuration shown in FIG. 3 has been changed or deleted, or has been described so far, as long as the effect of the present invention is not impaired. Other configurations may be added to the above configuration. More specifically, it is as follows.
 ここまでは、基材及び粘着剤層が積層されて構成されたダイシングシートを備えた複合シートについて説明したが、本実施形態の複合シートは、基材のみからなるダイシングシートを備えていてもよい。すなわち、前記複合シートは、基材と、前記基材の一方の面上に設けられたフィルム状接着剤と、を備え、前記基材と前記フィルム状接着剤との間に、粘着剤層が配置されずに構成されていてもよい。このような複合シートとしては、図2に示す積層シート108において、樹脂フィルム19が基材(例えば、図3に示す基材11)であるものが挙げられる。 Up to this point, the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment may include a dicing sheet including only the base material. .. That is, the composite sheet comprises a base material and a film adhesive provided on one surface of the base material, and a pressure-sensitive adhesive layer is provided between the base material and the film adhesive. It may be configured without being arranged. An example of such a composite sheet is the laminated sheet 108 shown in FIG. 2 in which the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3).
 ここまでは、基材及び粘着剤層が積層されて構成されたダイシングシートを備えた複合シートについて説明したが、本実施形態の複合シートは、基材及び粘着剤層以外に中間層を備えて構成されたダイシングシートを備えていてもよい。このようなダイシングシートとしては、例えば、基材と、前記基材の一方の面上に設けられた粘着剤層と、前記粘着剤層の前記基材側とは反対側の面上に設けられた中間層と、を備えたものが挙げられる。このようなダイシングシートを用いた場合、複合シートにおいては、前記粘着剤層と前記フィルム状接着剤との間に、中間層が配置される。 So far, the composite sheet including the dicing sheet configured by laminating the base material and the pressure-sensitive adhesive layer has been described, but the composite sheet of the present embodiment includes an intermediate layer in addition to the base material and the pressure-sensitive adhesive layer. You may provide the comprised dicing sheet. As such a dicing sheet, for example, a base material, a pressure-sensitive adhesive layer provided on one surface of the base material, and a surface of the pressure-sensitive adhesive layer opposite to the base material side are provided. And an intermediate layer. When such a dicing sheet is used, an intermediate layer is arranged between the pressure-sensitive adhesive layer and the film adhesive in the composite sheet.
 例えば、本実施形態の複合シートは、フィルム状接着剤の第1面に、前記剥離フィルムのみを備えていてもよいが、フィルム状接着剤の第1面のうち、周縁部近傍の領域に、複合シートをリングフレーム等の治具に固定するための治具用接着剤層を備えていてもよい。
 この場合の治具用接着剤層は、先に説明したものと同様である。
For example, the composite sheet of the present embodiment may include only the release film on the first surface of the film adhesive, but in the first surface of the film adhesive, in the region near the peripheral edge, A jig adhesive layer for fixing the composite sheet to a jig such as a ring frame may be provided.
The jig adhesive layer in this case is the same as that described above.
 例えば、複合シートをそのフィルム状接着剤側又はダイシングシート側の上方から見下ろして平面視したときに、フィルム状接着剤及びダイシングシートの表面積は、同等又はほぼ同等であってもよいが、本実施形態の複合シートにおいては、フィルム状接着剤の表面積がダイシングシートの表面積よりも小さく、ダイシングシート(例えば、粘着剤層)の一部領域が露出していてもよい。その場合、例えば、少なくともダイシングシートの幅方向における周縁部が、フィルム状接着剤で被覆されずに露出していてもよい。このような複合シートは、上記の治具用接着剤層を、このダイシングシートの露出面に備えていてもよい。 For example, the surface area of the film-like adhesive and the dicing sheet may be the same or almost the same when the composite sheet is viewed from above the film-like adhesive side or the dicing sheet side and viewed in a plane. In the composite sheet of the embodiment, the surface area of the film adhesive may be smaller than the surface area of the dicing sheet, and a partial area of the dicing sheet (for example, the pressure-sensitive adhesive layer) may be exposed. In that case, for example, at least the peripheral portion in the width direction of the dicing sheet may be exposed without being covered with the film adhesive. Such a composite sheet may include the jig adhesive layer on the exposed surface of the dicing sheet.
 ここまでは、複合シートを構成するものとして、基材、粘着剤層、中間層、フィルム状接着剤、治具用接着剤層及び剥離フィルムを示しているが、本実施形態の複合シートは、これらのいずれにも該当しない、他の層を備えていてもよい。
 前記複合シートが前記他の層を備えている場合、その配置位置は、特に限定されない。
Up to this point, a substrate, a pressure-sensitive adhesive layer, an intermediate layer, a film adhesive, a jig adhesive layer and a release film have been shown as constituting the composite sheet, but the composite sheet of the present embodiment is Other layers that do not correspond to any of these may be provided.
When the composite sheet includes the other layer, the arrangement position is not particularly limited.
 本実施形態の複合シートにおいて、各層の大きさ及び形状は、目的に応じて任意に選択できる。 In the composite sheet of this embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.
◇積層シート(フィルム状接着剤)の使用方法
<<積層体及びその製造方法>>
 本実施形態の積層シート中のフィルム状接着剤は、例えば、センサー等のチップの回路形成面に対して、光透過性カバーを接着するためのフィルムとして使用できる。
 より具体的には、前記フィルム状接着剤を用いることにより、チップと、前記チップの回路形成面上に設けられたフィルム状接着剤と、前記フィルム状接着剤の前記チップ側と反対側の面上に設けられた光透過性カバーと、を備えて構成された積層体を製造できる。前記積層体において、フィルム状接着剤のチップ側の面と、光透過性カバー側の面と、のいずれか一方又は両方は、実質的に芳香族化合物を含まず、両方が実質的に芳香族化合物を含まないことが好ましい。
◇ Usage of laminated sheet (film adhesive) <<<Laminate and its manufacturing method>>
The film adhesive in the laminated sheet of the present embodiment can be used as a film for adhering the light-transmitting cover to the circuit forming surface of a chip such as a sensor.
More specifically, by using the film adhesive, the chip, the film adhesive provided on the circuit forming surface of the chip, and the surface of the film adhesive opposite to the chip side. It is possible to manufacture a laminated body including the light-transmitting cover provided above. In the laminate, one or both of the chip-side surface of the film adhesive and the light-transmissive cover-side surface do not substantially contain an aromatic compound, and both are substantially aromatic. It is preferably free of compounds.
 図4は、前記積層体の一例を模式的に示す断面図である。
 ここに示す積層体801は、チップ8と、チップ8の回路形成面8a上に設けられたフィルム状接着剤13と、フィルム状接着剤13のチップ8側と反対側の面(第1面)13a上に設けられた光透過性カバー7と、を備えて構成されている。
FIG. 4 is a sectional view schematically showing an example of the laminated body.
The laminated body 801 shown here is the chip 8, the film adhesive 13 provided on the circuit forming surface 8a of the chip 8, and the surface of the film adhesive 13 opposite to the chip 8 side (first surface). And a light-transmitting cover 7 provided on 13a.
 積層体801においては、チップ8とフィルム状接着剤13のそれぞれの対向する面、すなわち、チップ8の回路形成面8aと、フィルム状接着剤13のチップ8側の面(第2面)13bと、は直接接触している。また、フィルム状接着剤13と光透過性カバー7のそれぞれの対向する面、すなわち、フィルム状接着剤13の第1面13aと、光透過性カバー7のフィルム状接着剤13側の面(本明細書においては、「第2面」と称することがある)7bと、は直接接触している。
 このように、積層体801は、チップ8と、フィルム状接着剤13と、光透過性カバー7と、がこの順に、これらの厚さ方向において積層され、チップ8の回路形成面8aがフィルム状接着剤13側に配置されて、構成されている。
In the laminated body 801, the surfaces of the chip 8 and the film adhesive 13 that face each other, that is, the circuit forming surface 8a of the chip 8 and the surface (second surface) 13b of the film adhesive 13 on the chip 8 side are formed. , Are in direct contact. In addition, the film adhesive 13 and the light transmissive cover 7 face each other, that is, the first surface 13a of the film adhesive 13 and the film adhesive 13 side of the light transmissive cover 7 (the book In the specification, it may be referred to as the "second surface") 7b, and is in direct contact.
As described above, in the laminated body 801, the chip 8, the film adhesive 13, and the light transmissive cover 7 are laminated in this order in the thickness direction thereof, and the circuit forming surface 8a of the chip 8 is in the film form. It is arranged and configured on the adhesive 13 side.
 積層体801中のフィルム状接着剤13は、例えば、図1に示す積層シート109において、第1剥離フィルム151及び第2剥離フィルム152を取り除いたもの、又は、図2に示す積層シート108において、樹脂フィルム19を取り除いたものである。
 積層体801において、フィルム状接着剤13の第1面13aと第2面13bとのいずれか一方又は両方は、実質的に芳香族化合物を含まず、両方が実質的に芳香族化合物を含まないことが好ましい。
The film adhesive 13 in the laminated body 801 is, for example, the laminated sheet 109 shown in FIG. 1 from which the first release film 151 and the second release film 152 are removed, or the laminated sheet 108 shown in FIG. The resin film 19 is removed.
In the laminate 801, either one or both of the first surface 13a and the second surface 13b of the film adhesive 13 do not substantially contain an aromatic compound, and both do not substantially contain an aromatic compound. It is preferable.
 なお、図4においては、チップ8の回路の図示は省略している。また、符号7aは、光透過性カバー7の前記第2面7bとは反対側の面(本明細書においては、「第1面」と称することがある)を示す。 Note that the circuit of the chip 8 is not shown in FIG. Reference numeral 7a indicates a surface of the light transmissive cover 7 opposite to the second surface 7b (may be referred to as "first surface" in the present specification).
 光透過性カバー7は、チップ8の回路形成面8aを保護するとともに、その第2面7b側の外部を、その第1面7a側の外部から、視認可能とする。
 一方、フィルム状接着剤13は、上述の光透過性を有する。そのため、積層体801においては、光透過性カバー7及びフィルム状接着剤13を介して(光透過性カバー7及びフィルム状接着剤13越しに)、チップ8の回路形成面8aに存在する視覚情報が、視認可能となっている。
 さらに、フィルム状接着剤13は、上述のとおり、加熱前後で光透過性が高く、着色が抑制されている。したがって、積層体801は、チップ8上の視覚情報を安定して高精度に視認可能となっている。
The light transmissive cover 7 protects the circuit forming surface 8a of the chip 8 and makes the outside of the second surface 7b side visible from the outside of the first surface 7a side.
On the other hand, the film adhesive 13 has the above-mentioned light transmittance. Therefore, in the laminated body 801, the visual information existing on the circuit forming surface 8a of the chip 8 through the light transmissive cover 7 and the film adhesive 13 (through the light transmissive cover 7 and the film adhesive 13). However, it is visible.
Furthermore, as described above, the film adhesive 13 has high light transmittance before and after heating and is suppressed from being colored. Therefore, the laminated body 801 can visually recognize the visual information on the chip 8 stably and with high accuracy.
 チップ8としては、例えば、指紋センサーを用いることができ、その場合、積層体801は指紋センサーモジュールとして利用可能である。 As the chip 8, for example, a fingerprint sensor can be used, and in that case, the laminated body 801 can be used as a fingerprint sensor module.
 前記フィルム状接着剤を用いた前記積層体は、図4に示すものに限定されず、本発明の効果を損なわない範囲で、図4に示すものの一部の構成が変更又は削除されたものや、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 laminated body using the film adhesive is not limited to that shown in FIG. 4, and a part of the configuration shown in FIG. 4 is changed or deleted within a range not impairing the effects of the present invention. Further, other configurations may be added to those described above.
 前記積層体は、例えば、前記フィルム状接着剤の一方の面(第2面)に、チップの回路形成面を貼り合わせ、前記フィルム状接着剤の他方の面(第1面)に、光透過性カバーを貼り合わせることにより、製造できる。 In the laminated body, for example, one surface (second surface) of the film adhesive is attached to a circuit forming surface of the chip, and the other surface (first surface) of the film adhesive is optically transparent. It can be manufactured by laminating a flexible cover.
◇複合シートの使用方法
<<積層体及びその製造方法>>
 本実施形態の複合シートは、公知の複合シートの場合と同じ方法で使用できる。
 図5は、本実施形態の複合シートの使用方法の一例を模式的に説明するための断面図である。ここでは、図3に示す複合シート101を用いた場合について示している。
◇How to use composite sheet <<<Laminate and its manufacturing method>>
The composite sheet of this embodiment can be used in the same manner as in the case of known composite sheets.
FIG. 5: is sectional drawing for demonstrating an example of the usage method of the composite sheet of this embodiment typically. Here, the case where the composite sheet 101 shown in FIG. 3 is used is shown.
 ここに示すように、複合シート101は、剥離フィルム15を取り除いた後、フィルム状接着剤13の第1面13aを、チップ8の回路形成面8aに貼付して、使用される。 As shown here, the composite sheet 101 is used by removing the release film 15 and then attaching the first surface 13a of the film adhesive 13 to the circuit forming surface 8a of the chip 8.
 複合シート101をチップ8に貼付した後は、例えば、チップ8をダイシングして個片化し、フィルム状接着剤13を個片化されたチップ8の外周に沿って切断する。このとき、チップ8の個片化と、フィルム状接着剤13の切断は、公知の方法で行うことができ、例えば、これらを同時に行ってもよいし、チップ8を個片化してから、別途、フィルム状接着剤13を切断してもよい。 After attaching the composite sheet 101 to the chip 8, for example, the chip 8 is diced into individual pieces, and the film adhesive 13 is cut along the outer periphery of the individual chips 8. At this time, the chip 8 can be divided into individual pieces and the film adhesive 13 can be cut by a known method. For example, these can be performed at the same time, or the chip 8 can be divided into individual pieces and then separated. The film adhesive 13 may be cut.
 次いで、個片化後のチップ8を、切断後のフィルム状接着剤13ごと、ダイシングシート10から引き離してピックアップする。粘着剤層12がエネルギー線硬化性である場合には、粘着剤層12をエネルギー線硬化させて、フィルム状接着剤13に対する粘着力を低下させてから、ピックアップすることにより、ピックアップをより容易に行うことができる。 Next, the individual chips 8 are separated from the dicing sheet 10 together with the cut film adhesive 13 and picked up. When the pressure-sensitive adhesive layer 12 is energy ray-curable, the pressure-sensitive adhesive layer 12 is cured with energy rays to reduce the adhesive strength to the film adhesive 13 and then picked up to make the pickup easier. It can be carried out.
 次いで、切断及びピックアップ後のフィルム状接着剤13の第2面に、光透過性カバーを貼り合わせることにより、前記積層体(例えば、図4に示す積層体801)を製造できる。
 前記積層体において、フィルム状接着剤の第1面と第2面とのいずれか一方又は両方は、実質的に芳香族化合物を含まず、両方が実質的に芳香族化合物を含まないことが好ましい。
Next, the above-mentioned laminated body (for example, laminated body 801 shown in FIG. 4) can be manufactured by attaching a light-transmitting cover to the second surface of the film adhesive 13 after cutting and picking up.
In the laminate, one or both of the first surface and the second surface of the film adhesive are preferably substantially free of an aromatic compound, and both are preferably substantially free of an aromatic compound. ..
 ここでは、このように、複合シート中のフィルム状接着剤をチップに貼り合わせ、チップの個片化後及びフィルム状接着剤の切断後に、この切断後のフィルム状接着剤に光透過性カバーを貼り合わせる場合について、説明したが、フィルム状接着剤に対するチップ及び光透過性カバーの貼り合わせの順序は、逆であってもよい。すなわち、フィルム状接着剤の第1面を、光透過性カバーの第2面に貼付した後、光透過性カバーをダイシングして個片化し、フィルム状接着剤を切断して、必要に応じて粘着剤層をエネルギー線硬化させてから、個片化後の光透過性カバーを、切断後のフィルム状接着剤ごと、ダイシングシートから引き離してピックアップし、次いで、この切断及びピックアップ後のフィルム状接着剤の第1面に、チップを貼り合わせることでも、前記積層体(例えば、図4に示す積層体801)を製造できる。 Here, in this way, the film-like adhesive in the composite sheet is stuck to the chip, and after the chip is divided into pieces and the film-like adhesive is cut, a light-transmitting cover is attached to the cut film-like adhesive. Although the case of laminating is explained, the order of laminating the chip and the light-transmitting cover to the film adhesive may be reversed. That is, after sticking the first surface of the film-like adhesive to the second surface of the light-transmitting cover, the light-transmitting cover is diced into individual pieces, and the film-like adhesive is cut, and if necessary, After curing the pressure-sensitive adhesive layer with energy rays, the light-transmitting cover after separation into pieces is separated from the dicing sheet together with the film adhesive after cutting and picked up, and then the film bonding after cutting and picking up The laminated body (for example, the laminated body 801 shown in FIG. 4) can also be manufactured by bonding a chip to the first surface of the agent.
 以下、具体的実施例により、本発明についてより詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples described below.
<接着剤組成物の製造原料>
 本実施例及び比較例において、接着剤組成物の製造に用いた原料を以下に示す。
<Manufacturing raw material for adhesive composition>
The raw materials used in the production of the adhesive compositions in the examples and comparative examples are shown below.
[アクリル系樹脂(a)]
 (a)-1:アクリル酸メチル(85質量部)及びアクリル酸2-ヒドロキシエチル(15質量部)を共重合して得られたアクリル系樹脂(重量平均分子量800000、ガラス転移温度6℃)。
 (a)-2:アクリル酸メチル(95質量部)及びアクリル酸2-ヒドロキシエチル(5質量部)を共重合して得られたアクリル系樹脂(重量平均分子量800000、ガラス転移温度9℃)。
[エポキシ化合物(b1)]
 (b1)-1:アクリロイル基が付加されたクレゾールノボラック型エポキシ樹脂(日本化薬社製「CNA147」、エポキシ当量518g/eq、数平均分子量2100、不飽和基の含有量とエポキシ基の含有量とは等量)
 (b1)-2:水添ビスフェノールA型エポキシ樹脂(共栄社化学社製「エポライト4000」、エポキシ当量310~340g/eq)
 (b1)-3:水添ビスフェノール型エポキシ樹脂(三菱ケミカル社製「YX8000」、エポキシ当量205g/eq)
 (b1)-4:トリアジン型脂環式エポキシ化合物(日産化学社製「TEPIC-PAS B22」、エポキシ当量180~200g/eq)
 (b1)-5:トリアジン型脂環式エポキシ化合物(日産化学社製「TEPIC VL」、エポキシ当量125~145g/eq)
 (b1)-6:ビスフェノールA型エポキシ樹脂(三菱ケミカル社製「jER828」、エポキシ当量184~194g/eq)
 (b1)-7:ジシクロペンタジエン型エポキシ樹脂(日本化薬社製「XD-1000-L」、エポキシ当量248g/eq)
 (b1)-8:トリフェニレン型エポキシ樹脂(日本化薬社製「EPPN-502H」、エポキシ当量158~178g/eq)
[フェノール樹脂(b2)]
 (b2)-1:アラルキル型フェノール樹脂(エア・ウォーター・ケミカル社製「HE100C-10」)
[充填材(d)]
 (d)-1:メタクリル基で修飾された球状シリカ(アドマテックス社製「YA050C-MJE」、平均粒子径50nm)
 (d)-2:エポキシ基で修飾された球状シリカ(アドマテックス社製「YA050C-MKK」、平均粒子径50nm)
[架橋剤(f)]
 (f)-1:トリメチロールプロパンのトリレンジイソシアネート三量体付加物(東ソー社製「コロネートL」)
 (f)-2:トリメチロールプロパンのイソホロンジイソシアネート三量体付加物(三井化学社製「D-140N」)
 (f)-3:トリメチロールプロパンのキシリレンジイソシアネート三量体付加物(三井化学社製「D-110N」)
 (f)-4:トリメチロールプロパンのヘキサメチレンジイソシアネート三量体付加物(トーヨーケム社製「Bxx4773」)
[リン系酸化防止剤(z)]
 (z)-1:ビス(デシル)ペンタエリスリトールジホスファイト(城北化学工業社製「JPE-10」、脂肪族系亜リン酸エステル)
 (z)-2:トリス(2-エチルへキシル)ホスファイト(城北化学工業社製「JP-308E」、脂肪族系亜リン酸エステル)
[Acrylic resin (a)]
(A)-1: An acrylic resin (weight average molecular weight 800,000, glass transition temperature 6° C.) obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass).
(A)-2: An acrylic resin (weight average molecular weight 800,000, glass transition temperature 9° C.) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass).
[Epoxy compound (b1)]
(B1)-1: Acryloyl group-added cresol novolac type epoxy resin (“CNA147” manufactured by Nippon Kayaku Co., epoxy equivalent 518 g/eq, number average molecular weight 2100, unsaturated group content and epoxy group content) Is equal to
(B1)-2: Hydrogenated bisphenol A type epoxy resin (“Epolite 4000” manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 310 to 340 g/eq)
(B1)-3: Hydrogenated bisphenol type epoxy resin (“YX8000” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 205 g/eq)
(B1)-4: triazine type alicyclic epoxy compound (“TEPIC-PAS B22” manufactured by Nissan Chemical Co., Ltd., epoxy equivalent 180 to 200 g/eq)
(B1)-5: triazine type alicyclic epoxy compound (“TEPIC VL” manufactured by Nissan Chemical Co., Ltd., epoxy equivalent 125 to 145 g/eq)
(B1)-6: Bisphenol A type epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g/eq)
(B1)-7: Dicyclopentadiene type epoxy resin (“XD-1000-L” manufactured by Nippon Kayaku Co., epoxy equivalent 248 g/eq)
(B1)-8: Triphenylene type epoxy resin (“EPPN-502H” manufactured by Nippon Kayaku Co., epoxy equivalent 158 to 178 g/eq)
[Phenolic resin (b2)]
(B2)-1: Aralkyl type phenolic resin (“HE100C-10” manufactured by Air Water Chemical Co., Ltd.)
[Filler (d)]
(D)-1: Spherical silica modified with methacryl group ("YA050C-MJE" manufactured by Admatechs Co., Ltd., average particle diameter 50 nm)
(D)-2: Spherical silica modified with an epoxy group ("YA050C-MKK" manufactured by Admatex Co., average particle size 50 nm)
[Crosslinking agent (f)]
(F)-1: Tolylene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh Corporation)
(F)-2: Isophorone diisocyanate trimer adduct of trimethylolpropane (“D-140N” manufactured by Mitsui Chemicals, Inc.)
(F)-3: adduct of trimethylolpropane with xylylene diisocyanate trimer (“D-110N” manufactured by Mitsui Chemicals, Inc.)
(F)-4: hexamethylene diisocyanate trimer adduct of trimethylolpropane (“Bxx4773” manufactured by Toyochem Co., Ltd.)
[Phosphoric antioxidant (z)]
(Z)-1: Bis(decyl)pentaerythritol diphosphite (“JPE-10” manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite ester)
(Z)-2: tris(2-ethylhexyl) phosphite (“JP-308E” manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite ester)
[実施例1]
<<フィルム状接着剤の製造>>
<接着剤組成物の製造>
 アクリル系樹脂(a)-1(44.3質量部)、エポキシ化合物(b1)-2(40質量部)、充填材(d)-2(15質量部)、架橋剤(f)-4(0.2質量部)及びリン系酸化防止剤(z)-1(0.5質量部)をメチルエチルケトンに溶解又は分散させて、23℃で撹拌することにより、メチルエチルケトン以外のすべての成分の合計濃度が32質量%である接着剤組成物を得た。なお、ここに示すメチルエチルケトン以外の成分の配合量はすべて、溶媒成分を含まない目的物の配合量である。
[Example 1]
<<Production of film adhesive>>
<Production of adhesive composition>
Acrylic resin (a)-1 (44.3 parts by mass), epoxy compound (b1)-2 (40 parts by mass), filler (d)-2 (15 parts by mass), crosslinking agent (f)-4 ( 0.2 parts by mass) and phosphorus antioxidant (z)-1 (0.5 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23° C. to obtain a total concentration of all components other than methyl ethyl ketone. To obtain 32% by mass of the adhesive composition. In addition, the compounding amounts of the components other than the methyl ethyl ketone shown here are all compounding amounts of the target product containing no solvent component.
<フィルム状接着剤の製造>
 ポリエチレンテレフタレート(PET)製フィルムの片面がシリコーン処理により剥離処理されている剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)を用い、その前記剥離処理面に、上記で得られた接着剤組成物を塗工し、100℃で2分加熱乾燥させることにより、厚さ20μmのフィルム状接着剤を形成し、前記剥離フィルム及びフィルム状接着剤が、これらの厚さ方向において積層されて構成された接着シートを得た。
<Production of film adhesive>
A polyethylene terephthalate (PET) film has a release film (one side of which has been subjected to a release treatment by silicone treatment) (SP-PET381031 manufactured by Lintec Co., Ltd., thickness: 38 μm), and the above-mentioned release treatment is applied to the release-treated surface. The adhesive composition is applied and dried by heating at 100° C. for 2 minutes to form a film adhesive having a thickness of 20 μm, and the release film and the film adhesive are laminated in the thickness direction thereof. A structured adhesive sheet was obtained.
<<フィルム状接着剤の評価>>
<せん断強度の測定>
 テープマウンター(リンテック社製「Adwill RAD2500 m/12」)を用い、貼付温度23℃、貼付速度20mm/sの条件で、ダイシングシート(リンテック社製「Adwill D-678」)を6インチシリコンウエハ(厚さ350μm)に貼付し、このダイシングシート及びシリコンウエハの積層物を、リングフレームに固定した。
 次いで、ダイシング装置(DISCO社製「DFD6362)を用い、ダイシングブレード(DISCO社製「NBC-ZH2050-SE27HECC」によって、ブレード回転数30000rpm、切断速度40mm/sの条件で、ダイシングを行い、大きさが2mm×2mmの複数個のシリコンチップ(以下、「シリコンチップ群」と称することがある)を得た。上記のダイシングシートは、基材と及び粘着剤層が積層されて構成されており、ダイシング時には、このダイシングシート中の基材の深さ20μmの領域まで、ダイシングブレードにより切り込んだ。
<<Evaluation of film adhesive>>
<Measurement of shear strength>
Using a tape mounter (“Adwill RAD2500 m/12” manufactured by Lintec Co., Ltd.), a dicing sheet (“Adwill D-678” manufactured by Lintec Co., Ltd.) was prepared on a 6-inch silicon wafer under conditions of a bonding temperature of 23° C. and a bonding speed of 20 mm/s. It was attached to a thickness of 350 μm), and the laminate of the dicing sheet and the silicon wafer was fixed to a ring frame.
Then, using a dicing device (“DFD6362” manufactured by DISCO), a dicing blade (“NBC-ZH2050-SE27HECC manufactured by DISCO”) was used to perform dicing at a blade rotation speed of 30,000 rpm and a cutting speed of 40 mm/s. A plurality of 2 mm×2 mm silicon chips (hereinafter sometimes referred to as “silicon chip group”) were obtained, and the dicing sheet is formed by laminating a base material and an adhesive layer, and Occasionally, the dicing blade was used to cut into a region having a depth of 20 μm in the dicing sheet.
 次いで、上記で得られたシリコンチップ群に、上記で得られた接着シートを、60℃に加熱しながら、その中のフィルム状接着剤によって貼付した。このとき、接着シートは、シリコンチップ群中のシリコンチップのうち、ダイシングシートが貼付されている側とは反対側の面(露出面)に貼付した。そして、シリコンチップの外周に沿って、この貼付後の接着シートを切断した。
 以上により、ダイシングシート、シリコンチップ及び接着シートがこの順に、これらの厚さ方向において積層されて構成され、大きさが2mm×2mmである積層物を得た。
Next, the adhesive sheet obtained above was attached to the silicon chip group obtained above while being heated to 60° C. with the film-like adhesive therein. At this time, the adhesive sheet was attached to the surface (exposed surface) opposite to the side to which the dicing sheet was attached, of the silicon chips in the silicon chip group. Then, the adhesive sheet after the attachment was cut along the outer periphery of the silicon chip.
As described above, the dicing sheet, the silicon chip, and the adhesive sheet were laminated in this order in the thickness direction to obtain a laminate having a size of 2 mm×2 mm.
 次いで、この積層物中のフィルム状接着剤から前記剥離フィルムを取り除き、マニュアルダイボンダーを用いて、新たに生じたフィルム状接着剤の露出面を、大きさが30mm×30mmで、厚さが300μmである銅板の表面に貼付した。このとき、フィルム状接着剤は、125℃に加熱しながら、2.45N(250gf)の力を加えて銅板に押し付けることにより、貼付した。さらに、これら貼り合わせたものを、175℃で5時間加熱することにより、試験片を得た。 Then, the release film was removed from the film adhesive in this laminate, and the exposed surface of the newly formed film adhesive was measured with a manual die bonder to have a size of 30 mm×30 mm and a thickness of 300 μm. It was attached to the surface of a copper plate. At this time, the film adhesive was applied by applying a force of 2.45 N (250 gf) to the copper plate while heating it to 125°C. Further, the bonded pieces were heated at 175° C. for 5 hours to obtain a test piece.
 次いで、万能型ボンドテスター(ノードソン・アドバンスト・テクノロジー社製「DAGE4000」)を用い、23℃の温度条件下で、シェアツールによって、200μm/sの速度で、前記試験片の側面において、フィルム状接着剤とシリコンチップの両方に対して、フィルム状接着剤の銅板への貼付面に対して平行な方向に力を加えた。そして、フィルム状接着剤が破壊されるまでに加えられていた力の最大値を確認し、これをフィルム状接着剤のせん断強度(N/2mm□)として採用した。結果を表1に示す。 Next, using a universal bond tester (“DAGE4000” manufactured by Nordson Advanced Technology Co., Ltd.), at a temperature of 23° C., with a shear tool, at a speed of 200 μm/s, at the side surface of the test piece, film-like adhesion was performed. A force was applied to both the agent and the silicon chip in a direction parallel to the surface of the film adhesive to be attached to the copper plate. Then, the maximum value of the force applied until the film adhesive was broken was confirmed, and this was adopted as the shear strength (N/2 mm□) of the film adhesive. The results are shown in Table 1.
<光(400~800nm)の加熱前直線透過率の測定>
 上記で得られたフィルム状接着剤を、40℃で加熱しながらガラス製プレパラート(厚さ0.9mm)の一方の面に貼付した。フィルム状接着剤は、その製造直後からこの貼付までの間、加熱処理を行わなかった。
 次いで、貼付後のフィルム状接着剤のうち、ガラス製プレパラートからはみ出している部分を切断し、同じ大きさのフィルム状接着剤とガラス製プレパラートが、これらの周縁部の位置が一致した状態で、これらの厚さ方向において積層されて構成された試験片(以下、「加熱前試験片」と称する)を得た。
<Measurement of linear transmittance of light (400 to 800 nm) before heating>
The film adhesive obtained above was attached to one surface of a glass slide (thickness 0.9 mm) while heating at 40°C. The film adhesive was not subjected to heat treatment immediately after its production and before this attachment.
Then, of the film adhesive after sticking, the part protruding from the glass slide is cut, and the film adhesive of the same size and the glass slide are in a state where the positions of these peripheral portions are the same, A test piece (hereinafter referred to as a “pre-heating test piece”) configured by stacking in the thickness direction was obtained.
 前記加熱前試験片の作製に用いたガラス製プレパラートについて、加熱前試験片の作製前にあらかじめ、分光光度計(Shimadzu社製「UV-3101PC」)を用いて、光(400~800nm)の直線透過率(以下、「基準直線透過率」と称する)を測定した。
 上記で得られた加熱前試験片についても、同じ方法で、光(400~800nm)の直線透過率を測定した。
 加熱前試験片の、各波長での光(400~800nm)の直線透過率の測定値から、同じ波長での前記基準直線透過率の測定値を減じて得られた値を、加熱前のフィルム状接着剤の光(400~800nm)の直線透過率(すなわち、前記加熱前直線透過率)として採用した。結果を表1に示す。
Regarding the glass preparation used in the preparation of the pre-heating test piece, a straight line of light (400 to 800 nm) was prepared in advance using a spectrophotometer (“UV-3101PC” manufactured by Shimadzu Co.) before the preparation of the pre-heating test piece. The transmittance (hereinafter, referred to as “reference linear transmittance”) was measured.
The linear transmittance of light (400 to 800 nm) was also measured for the pre-heated test piece obtained above by the same method.
The value obtained by subtracting the measured value of the reference linear transmittance at the same wavelength from the measured value of the linear transmittance of light (400 to 800 nm) at each wavelength of the test piece before heating is the film before heating. It was adopted as the linear transmittance of light (400 to 800 nm) of the linear adhesive (that is, the linear transmittance before heating). The results are shown in Table 1.
<光(400~800nm)の加熱後直線透過率の測定>
 電気炉を用いて、上記の光(400~800nm)の加熱前直線透過率を測定後の試験片を、260℃で10分加熱した。
 次いで、この加熱後の試験片を、室温と同じ温度になるまで放冷した。
 次いで、この加熱及び放冷後の試験片(以下、「加熱後試験片」と称する)について、上述の加熱前試験片の場合と同じ方法で、光(400~800nm)の直線透過率を測定した。
 加熱後試験片の、各波長での光(400~800nm)の直線透過率の測定値から、同じ波長での前記基準直線透過率の測定値を減じて得られた値を、加熱後のフィルム状接着剤の光(400~800nm)の直線透過率(すなわち、前記加熱後直線透過率)として採用した。結果を表1に示す。
<Measurement of linear transmittance after heating with light (400 to 800 nm)>
An electric furnace was used to heat the test piece after measuring the linear transmittance of the light (400 to 800 nm) before heating at 260° C. for 10 minutes.
Then, the heated test piece was allowed to cool to the same temperature as room temperature.
Then, the linear transmittance of light (400 to 800 nm) of the test piece after heating and cooling (hereinafter, referred to as “test piece after heating”) is measured by the same method as in the case of the test piece before heating. did.
The value obtained by subtracting the measured value of the reference linear transmittance at the same wavelength from the measured value of the linear transmittance of light (400 to 800 nm) at each wavelength of the test piece after heating, the film after heating It was adopted as the linear transmittance of light (400 to 800 nm) of the linear adhesive (that is, the linear transmittance after heating). The results are shown in Table 1.
<RGBによる加熱前の指紋認識性の評価>
 左手人差し指の腹の前に、デジタルカメラ(キャノン社製「IXY650」)を配置し、左手人差し指の腹の表面と、カメラレンズの表面と、の間の距離を50mmに調節して、この状態で左手人差し指の指紋の撮像データ(以下、「基準撮像データ」と称する)をマクロモードで取得した。
 この左手人差し指とデジタルカメラの配置関係を維持したまま、左手人差し指の腹とデジタルカメラとの間に、さらに前記加熱前試験片を配置した。このとき、左手人差し指の腹とデジタルカメラとを結ぶ直線が、前記加熱前試験片中のガラス製プレパラートの露出面(すなわち、フィルム状接着剤との貼付面とは反対側の面)に対して直交し、かつ、前記露出面がデジタルカメラ側となるように、前記加熱前試験片を配置した。この条件で、前記基準撮像データの取得時と同じ方法で、左手人差し指の指紋の撮像データ(以下、「加熱前透過撮像データ」と称する)をマクロモードで取得した。
<Evaluation of fingerprint recognition by RGB before heating>
A digital camera (“IXY650” manufactured by Canon Inc.) is placed in front of the ball of the left index finger, and the distance between the surface of the ball of the left index finger and the surface of the camera lens is adjusted to 50 mm. Imaging data of the fingerprint of the left index finger (hereinafter referred to as “reference imaging data”) was acquired in macro mode.
While maintaining the positional relationship between the left index finger and the digital camera, the pre-heating test piece was further arranged between the belly of the left index finger and the digital camera. At this time, a straight line connecting the pad of the left index finger and the digital camera is to the exposed surface of the glass slide in the pre-heating test piece (that is, the surface opposite to the surface where the film adhesive is attached). The test pieces before heating were arranged so that they were orthogonal to each other and the exposed surface was on the digital camera side. Under this condition, the imaging data of the fingerprint of the left index finger (hereinafter, referred to as "pre-heating transmission imaging data") was acquired in the macro mode by the same method as the acquisition of the reference imaging data.
 グラフィックソフトウェア(マイクロソフト社製「ペイント」)を用いて、上記で得られた基準撮像データ及び加熱前透過撮像データを展開し、それぞれのデータから指紋の山部と谷部の色を抽出して、RGBで数値化した。
 加熱前透過撮像データより取得した指紋の山部のR値から、基準撮像データより取得した指紋の山部のR値を減じて得られた値を、加熱前評価時の指紋の山部のR値として採用した。これと同様の方法で、加熱前評価時の指紋の山部のG値とB値を求めた。
 上記と同様の方法で、加熱前透過撮像データより取得した指紋の谷部のR値から、基準撮像データより取得した指紋の谷部のR値を減じて得られた値を、加熱前評価時の指紋の谷部のR値として採用した。これと同様の方法で、加熱前評価時の指紋の谷部のG値とB値を求めた。
 さらに、前記山部のR値と前記谷部のR値との差の絶対値(以下、「絶対値ΔR」と記載することがある)を算出し、前記山部のG値と前記谷部のG値との差の絶対値(以下、「絶対値ΔG」と記載することがある)を算出し、前記山部のB値と前記谷部のB値との差の絶対値(以下、「絶対値ΔB」と記載することがある)を算出した。
Using the graphic software (“Paint” manufactured by Microsoft Corporation), expand the standard imaging data and the pre-heating transmission imaging data obtained above, extract the color of the ridges and valleys of the fingerprint from each data, It was converted into numerical values in RGB.
The value obtained by subtracting the R value of the fingerprint mountain portion acquired from the reference imaging data from the R value of the fingerprint mountain portion acquired from the pre-heating transmission imaging data is the R value of the fingerprint mountain portion at the time of pre-heating evaluation. Adopted as a value. In the same manner as above, the G value and B value of the ridge portion of the fingerprint at the time of evaluation before heating were obtained.
In the same manner as above, the value obtained by subtracting the R value of the valley portion of the fingerprint acquired from the reference imaging data from the R value of the valley portion of the fingerprint acquired from the transmission imaging data before heating is obtained during the pre-heating evaluation. It was adopted as the R value of the valley part of the fingerprint. In the same manner as above, the G value and B value of the valley portion of the fingerprint at the time of evaluation before heating were determined.
Furthermore, the absolute value of the difference between the R value of the mountain portion and the R value of the valley portion (hereinafter sometimes referred to as “absolute value ΔR”) is calculated, and the G value of the mountain portion and the valley portion are calculated. The absolute value of the difference between the B value of the mountain portion and the B value of the valley portion (hereinafter, referred to as “absolute value ΔG”) is calculated. “Absolute value ΔB” may be described) was calculated.
 これら算出値に基づいて、下記基準に従って、RGBによる加熱前のフィルム状接着剤の指紋認識性を評価した。結果を表1に示す。
(評価基準)
 A:絶対値ΔR、絶対値ΔG及び絶対値ΔBのうち、少なくとも1種が10以上である。
 B:絶対値ΔR、絶対値ΔG及び絶対値ΔBがすべて10未満であり、かつ、絶対値ΔR、絶対値ΔG及び絶対値ΔBのうち、少なくとも1種が5以上である。
 C:絶対値ΔR、絶対値ΔG及び絶対値ΔBがすべて5未満である。
Based on these calculated values, the fingerprint recognizability of the film adhesive before heating by RGB was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: At least one of the absolute value ΔR, the absolute value ΔG, and the absolute value ΔB is 10 or more.
B: The absolute value ΔR, the absolute value ΔG, and the absolute value ΔB are all less than 10, and at least one of the absolute value ΔR, the absolute value ΔG, and the absolute value ΔB is 5 or more.
C: Absolute value ΔR, absolute value ΔG and absolute value ΔB are all less than 5.
<RGBによる加熱後の指紋認識性の評価>
 前記加熱前試験片に代えて前記加熱後試験片を用いた点以外は、上述の「加熱前の指紋認識性の評価」の場合と同じ方法で、RGBによる加熱後のフィルム状接着剤の指紋認識性を評価した。
 より具体的には、本評価時には、前記加熱前透過撮像データに代えて「加熱後透過撮像データ」を取得した。また、この加熱後透過撮像データを用いて、加熱前評価時の指紋の山部のR値、G値及びB値に代えて、加熱後評価時の指紋の山部のR値、G値及びB値を求め、加熱前評価時の指紋の谷部のR値、G値及びB値に代えて、加熱後評価時の指紋の谷部のR値、G値及びB値を求めた。さらに、これらR値、G値及びB値から、加熱前評価時の前記絶対値ΔR、絶対値ΔG及び絶対値ΔBに代えて、加熱後評価時の絶対値ΔR、絶対値ΔG及び絶対値ΔBを算出した。結果を表1に示す。
<Evaluation of fingerprint recognition after heating with RGB>
Fingerprints of the film adhesive after heating by RGB in the same manner as in the above-mentioned “Evaluation of fingerprint recognition property before heating” except that the post-heating test piece was used instead of the pre-heating test piece. The recognizability was evaluated.
More specifically, at the time of this evaluation, “post-heating transmission imaging data” was acquired instead of the pre-heating transmission imaging data. Further, using the post-heating transmission imaging data, instead of the R value, G value, and B value of the fingerprint ridge portion during the pre-heating evaluation, the R value, G value, and The B value was obtained, and instead of the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation before heating, the R value, G value and B value of the valley portion of the fingerprint at the time of evaluation after heating were obtained. Further, from these R value, G value and B value, instead of the absolute value ΔR, absolute value ΔG and absolute value ΔB at the time of evaluation before heating, the absolute value ΔR, absolute value ΔG and absolute value ΔB at the time of evaluation after heating are used. Was calculated. The results are shown in Table 1.
<目視による加熱前の指紋認識性の評価>
 無作為に5名の観察者を選定し、以下に示す方法で、1名ずつ、指紋を目視観察した。
 すなわち、左手人差し指の腹の前に、1名の観察者を配置し、左手人差し指の腹の表面と、観察者の目と、の間の距離を150mmに調節して、この状態で左手人差し指の指紋を直接、目視観察した。
 この左手人差し指と観察者の配置関係を維持したまま、左手人差し指の腹と観察者との間に、さらに前記加熱前試験片を配置した。このときの前記加熱前試験片の配置形態は、上述の「RGBによる加熱前の指紋認識性の評価」時における加熱前試験片の場合と同じとした。この条件で、上記のとおり直接目視観察した場合と同様に、左手人差し指の指紋を、前記加熱前試験片越しに、目視観察した。
<Evaluation of fingerprint recognition by visual inspection before heating>
Five observers were randomly selected and the fingerprints were visually observed one by one by the method described below.
That is, one observer is placed in front of the ball of the left index finger, the distance between the surface of the ball of the left index finger and the eyes of the observer is adjusted to 150 mm, and in this state, The fingerprint was directly observed visually.
The pre-heating test piece was further arranged between the observer and the belly of the left index finger while maintaining the positional relationship between the left index finger and the observer. At this time, the arrangement form of the pre-heating test piece was the same as that of the pre-heating test piece in the above-mentioned “evaluation of fingerprint recognition property before heating by RGB”. Under this condition, the fingerprint of the left index finger was visually observed through the pre-heating test piece as in the case of direct visual observation as described above.
 この方法により、5名の観察者全員で、指紋を直接、及び加熱前試験片越しに、目視観察し、加熱前試験片越しでの指紋の見え方と、直接目視での指紋の見え方と、の比較から、下記基準に従って、目視による加熱前のフィルム状接着剤の指紋認識性を評価した。結果を表1に示す。表1の「指紋認識性」の欄中のカッコ内の数値は、「指紋の見え方に差が無い、と判定した観察者の人数(人)」を示している。
 A: 観察者5名全員が、指紋の見え方に差が無い、と判定した。
 B: 観察者5名中4名が、指紋の見え方に差が無い、と判定した。
 C: 観察者5名中2名以上が、指紋の色が互いに異なっており、見え方に差がある、と判定した。
By this method, all five observers visually observed the fingerprint directly and over the test piece before heating, and the appearance of the fingerprint through the test piece before heating and the appearance of the fingerprint by direct visual observation. According to the following criteria, the fingerprint recognizability of the film adhesive before heating was evaluated by visual observation. The results are shown in Table 1. The numerical value in parentheses in the column of "Fingerprint recognition" in Table 1 indicates "the number of observers (persons) judged to have no difference in the appearance of fingerprints".
A: All five observers judged that there was no difference in the appearance of fingerprints.
B: 4 out of 5 observers judged that there was no difference in the appearance of fingerprints.
C: Two or more out of five observers determined that the fingerprints had different colors and had different appearances.
<目視による加熱後の指紋認識性の評価>
 前記加熱前試験片に代えて前記加熱後試験片を用いた点以外は、上述の「目視による加熱前の指紋認識性の評価」の場合と同じ方法で、目視による加熱後のフィルム状接着剤の指紋認識性を評価した。結果を表1に示す。
<Evaluation of visual recognition of fingerprint after heating>
Except that the post-heating test piece was used in place of the pre-heating test piece, in the same manner as in the above-mentioned "evaluation of fingerprint recognition property before heating by visual observation", the film adhesive after visual heating was used. The fingerprint recognizability was evaluated. The results are shown in Table 1.
<FT-IRによる芳香族化合物の有無の評価>
 フーリエ変換赤外・近遠赤外分光分析装置(PerkinElmer社製「Spectrum100」)を用いて、上記で得られたフィルム状接着剤の一方の面について、ATR法により、波数4000~400cm-1の範囲でFT-IR測定を行った。波数3050~2990cm-1の範囲で、透過率を示す曲線における変曲点の有無を確認し、フィルム状接着剤の前記面における芳香族化合物の有無を確認した。結果を表1に示す。表1の「FT-IR(3050~2990cm-1)変曲点」の欄中のうち、「あり」の場合のカッコ内の数値は、「変曲点が認められた波数(cm-1)」を示している。また、このとき取得したスペクトルデータを図6に示す。
<Evaluation of the presence or absence of aromatic compounds by FT-IR>
Using a Fourier transform infrared/near-infrared spectroscopic analyzer (“Spectrum 100” manufactured by PerkinElmer), one side of the film adhesive obtained above was measured by the ATR method at a wave number of 4000 to 400 cm −1 . FT-IR measurement was performed in the range. In the wave number range of 3050 to 2990 cm −1 , the presence or absence of an inflection point in the curve showing the transmittance was confirmed, and the presence or absence of an aromatic compound on the surface of the film adhesive was confirmed. The results are shown in Table 1. In the “FT-IR (3050 to 2990 cm −1 ) inflection point” column of Table 1, the value in parentheses for “Yes” is “wavenumber at which an inflection point was recognized (cm −1 ). Is shown. The spectrum data acquired at this time is shown in FIG.
<<フィルム状接着剤の製造及び評価>>
[実施例2~4]
 接着剤組成物の含有成分の種類及び含有量が、表1に示すとおりとなるように、接着剤組成物の製造時における、配合成分の種類及び配合量のいずれか一方又は両方を変更した点以外は、実施例1の場合と同じ方法で、フィルム状接着剤を製造し、評価した。結果を表1に示す。
<<Production and Evaluation of Film Adhesive>>
[Examples 2 to 4]
One or both of the types and the amounts of the compounding components during the production of the adhesive composition are changed so that the types and the amounts of the components of the adhesive composition are as shown in Table 1. A film adhesive was produced and evaluated in the same manner as in Example 1 except for the above. The results are shown in Table 1.
[比較例1~3]
 接着剤組成物の含有成分の種類及び含有量が、表2に示すとおりとなるように、接着剤組成物の製造時における、配合成分の種類及び配合量のいずれか一方又は両方を変更した点以外は、実施例1の場合と同じ方法で、フィルム状接着剤の製造及び評価を試みた。結果を表2に示す。
[Comparative Examples 1 to 3]
Either or both of the type and the amount of the compounding component at the time of manufacturing the adhesive composition are changed so that the type and the content of the component of the adhesive composition are as shown in Table 2. The production and evaluation of the film adhesive were tried in the same manner as in Example 1 except for the above. The results are shown in Table 2.
 なお、表1及び2中の含有成分の欄の「-」との記載は、接着剤組成物がその成分を含有していないことを意味する。 Note that the description of "-" in the column of the contained component in Tables 1 and 2 means that the adhesive composition does not contain the component.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 上記結果から明らかなように、実施例1~4においては、260℃で加熱前後のフィルム状接着剤は、いずれも光透過性が高く、着色が抑制されており、指紋認識性が高かった。実施例1~4においては、260℃で加熱前のフィルム状接着剤の光(400~800nm)の直線透過率が95%以上(95~98%)であり、260℃で加熱後のフィルム状接着剤の光(400~800nm)の直線透過率が86%以上(86~95%)であった。 As is clear from the above results, in Examples 1 to 4, the film adhesives before and after heating at 260° C. all had high light transmittance, suppressed coloring, and had high fingerprint recognizability. In Examples 1 to 4, the linear adhesiveness of light (400 to 800 nm) of the film adhesive before heating at 260° C. was 95% or more (95 to 98%), and the film adhesive after heating at 260° C. was used. The linear transmittance of light (400 to 800 nm) of the adhesive was 86% or more (86 to 95%).
 実施例1~4においては、フィルム状接着剤のせん断強度は、48N/2mm□以上(48~80N/2mm□)であり、フィルム状接着剤の接着力が十分に強かった。 In Examples 1 to 4, the shear strength of the film adhesive was 48 N/2 mm□ or more (48 to 80 N/2 mm□), and the adhesive strength of the film adhesive was sufficiently strong.
 実施例1~4においては、フィルム状接着剤がリン系酸化防止剤(z)を含有しており、しかも、このリン系酸化防止剤(z)をはじめとして、すべての成分が芳香族環式基を有していなかったため、加熱による着色が抑制されたと推測された。
 実施例1~4においては、波数3050~2990cm-1の範囲で、透過率を示す曲線において、ノイズとは言えない明確な変曲点が認められず、フィルム状接着剤の前記測定面には、芳香族化合物が実質的に存在しないことを示しており、この結果は、上記の各成分を用いたことと整合していた。図6には、透過率を示す曲線を見易くするために、実施例3~4における結果を示していないが、実施例3~4における曲線も、実施例1~2における曲線と同様の形状であった。
In Examples 1 to 4, the film adhesive contained a phosphorus-based antioxidant (z), and all components including the phosphorus-based antioxidant (z) were aromatic cyclic compounds. Since it did not have a group, it was speculated that coloring due to heating was suppressed.
In Examples 1 to 4, in the wave number range of 3050 to 2990 cm −1 , there was no clear inflection point which could not be called noise in the curve showing the transmittance, and the measurement surface of the film-like adhesive was not observed. , Which indicates the substantial absence of aromatic compounds, a result consistent with the use of each of the above components. FIG. 6 does not show the results in Examples 3 to 4 in order to make the curve showing the transmittance easy to see, but the curves in Examples 3 to 4 also have the same shape as the curves in Examples 1 and 2. there were.
 これに対して、比較例1~3においては、260℃で加熱後のフィルム状接着剤は、光透過性が低く、着色が抑制されておらず、指紋認識性が低かった。比較例1~3においては、260℃で加熱後のフィルム状接着剤の光(400~800nm)の直線透過率が16%以下であった。 On the other hand, in Comparative Examples 1 to 3, the film adhesives after heating at 260° C. had low light transmittance, coloring was not suppressed, and fingerprint recognition was low. In Comparative Examples 1 to 3, the linear transmittance of light (400 to 800 nm) of the film adhesive after heating at 260° C. was 16% or less.
 比較例1及び3においては、フィルム状接着剤がリン系酸化防止剤(z)を含有していたものの、エポキシ化合物(b1)、フェノール樹脂(b2)及び架橋剤(f)がいずれも、芳香族環式基を有していたため、加熱による着色が抑制されなかったと推測された。図5からも明らかなとおり、比較例1及び3においては、波数3050~2990cm-1の範囲で、透過率を示す曲線において、ノイズとは言えない明確な変曲点が認められ、フィルム状接着剤の前記測定面には、芳香族化合物が存在することを示しており。この結果は、上記の各成分を用いたことと整合していた。 In Comparative Examples 1 and 3, although the film adhesive contained the phosphorus-based antioxidant (z), the epoxy compound (b1), the phenol resin (b2), and the cross-linking agent (f) were all aromatic. It was speculated that coloring due to heating was not suppressed because it had a group cyclic group. As is clear from FIG. 5, in Comparative Examples 1 and 3, in the wave number range of 3050 to 2990 cm −1, a clear inflection point which is not noise can be observed in the curve showing the transmittance, and the film-like adhesion is observed. It is shown that an aromatic compound is present on the measurement surface of the agent. This result was consistent with the use of each of the above components.
 比較例2においては、260℃で加熱前のフィルム状接着剤は、光透過性が高く、着色が抑制されていたものの、リン系酸化防止剤(z)をはじめとして、酸化防止剤を全く含有しておらず、しかも、エポキシ化合物(b1)、フェノール樹脂(b2)及び架橋剤(f)がいずれも、芳香族環式基を有していたため、加熱による着色が抑制されなかったと推測された。図5からも明らかなとおり、比較例2においては、波数3050~2990cm-1の範囲で、透過率を示す曲線において、明確な変曲点が認められ、フィルム状接着剤の前記測定面には、芳香族化合物が存在することを示しており。この結果は、上記の各成分を用いたことと整合していた。 In Comparative Example 2, the film adhesive before heating at 260° C. had high light transmittance and suppressed coloring, but did not contain any antioxidants including the phosphorus-based antioxidant (z). Moreover, since the epoxy compound (b1), the phenol resin (b2), and the cross-linking agent (f) each had an aromatic cyclic group, it was speculated that coloring due to heating was not suppressed. .. As is clear from FIG. 5, in Comparative Example 2, a clear inflection point was observed in the curve showing the transmittance in the wave number range of 3050 to 2990 cm −1 , and the measurement surface of the film-like adhesive was observed. , Indicating the presence of aromatic compounds. This result was consistent with the use of each of the above components.
 さらに、比較例2においては、フィルム状接着剤のせん断強度が45N/2mm□であり、フィルム状接着剤の接着力が、実施例1~4の場合よりも弱かった。 Furthermore, in Comparative Example 2, the shear strength of the film adhesive was 45 N/2 mm□, and the adhesive strength of the film adhesive was weaker than that in Examples 1 to 4.
 本発明は、電子機器を構成する各種部品の製造又は加工時に、接着剤として利用可能である。 The present invention can be used as an adhesive at the time of manufacturing or processing various parts constituting an electronic device.
 101・・・複合シート、108,109・・・積層シート、10・・・ダイシングシート、11・・・基材、11a・・・基材の第1面、12・・・粘着剤層、13・・・フィルム状接着剤、13a・・・フィルム状接着剤の第1面、13b・・・フィルム状接着剤の第2面、151・・・第1剥離フィルム、152・・・第2剥離フィルム、19・・・樹脂フィルム、7・・・光透過性カバー、8・・・チップ、8a・・・チップの回路形成面、801・・・積層体 101... Composite sheet, 108, 109... Laminated sheet, 10... Dicing sheet, 11... Base material, 11a... First surface of base material, 12... Adhesive layer, 13 ... film adhesive, 13a ... first surface of film adhesive, 13b ... second surface of film adhesive, 151 ... first release film, 152 ... second release Film, 19... Resin film, 7... Light transmissive cover, 8... Chip, 8a... Chip circuit forming surface, 801... Laminated body

Claims (8)

  1.  チップの回路形成面と光透過性カバーとの貼り合わせ用である、フィルム状接着剤であって、
     前記フィルム状接着剤の少なくとも一方の面が、実質的に芳香族化合物を含まない、フィルム状接着剤。
    A film adhesive for bonding a circuit forming surface of a chip and a light-transmitting cover,
    A film adhesive in which at least one surface of the film adhesive is substantially free of aromatic compounds.
  2.  260℃で加熱する前の前記フィルム状接着剤の、波長が400~800nmである光の直線透過率が、90%以上であり、
     260℃で10分加熱した後の前記フィルム状接着剤の、波長が400~800nmである光の直線透過率が、85%以上であり、
     前記フィルム状接着剤の厚さが10~40μmである、請求項1に記載のフィルム状接着剤。
    The linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive before heating at 260° C. is 90% or more,
    The linear transmittance of light having a wavelength of 400 to 800 nm of the film adhesive after heating at 260° C. for 10 minutes is 85% or more,
    The film-like adhesive according to claim 1, wherein the film-like adhesive has a thickness of 10 to 40 μm.
  3.  前記フィルム状接着剤が、脂肪族系エポキシ化合物を含有する、請求項1又は2に記載のフィルム状接着剤。 The film adhesive according to claim 1 or 2, wherein the film adhesive contains an aliphatic epoxy compound.
  4.  前記フィルム状接着剤が、酸化防止剤として、脂肪族系亜リン酸エステルを含有する、請求項1~3のいずれか一項に記載のフィルム状接着剤。 The film adhesive according to any one of claims 1 to 3, wherein the film adhesive contains an aliphatic phosphite ester as an antioxidant.
  5.  前記フィルム状接着剤が、アクリル系樹脂と、脂肪族多価イソシアネート系架橋剤と、を含有し、
     前記アクリル系樹脂が、前記架橋剤と結合可能な官能基を有する、請求項1~4のいずれか一項に記載のフィルム状接着剤。
    The film adhesive contains an acrylic resin and an aliphatic polyvalent isocyanate crosslinking agent,
    The film adhesive according to any one of claims 1 to 4, wherein the acrylic resin has a functional group capable of binding to the crosslinking agent.
  6.  請求項1~5のいずれか一項に記載のフィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられた樹脂フィルムと、を備えた、積層シート。 A laminated sheet comprising the film adhesive according to any one of claims 1 to 5 and a resin film provided on one surface of the film adhesive.
  7.  請求項1~5のいずれか一項に記載のフィルム状接着剤と、前記フィルム状接着剤の一方の面上に設けられたダイシングシートと、を備えており、
     前記ダイシングシートが、基材と、前記基材の一方の面上に設けられた粘着剤層と、を備えており、
     前記粘着剤層が、前記基材と前記フィルム状接着剤との間に配置されている、複合シート。
    A film-like adhesive according to any one of claims 1 to 5, and a dicing sheet provided on one surface of the film-like adhesive,
    The dicing sheet comprises a base material, and an adhesive layer provided on one surface of the base material,
    The composite sheet, wherein the pressure-sensitive adhesive layer is disposed between the base material and the film adhesive.
  8.  請求項1~5のいずれか一項に記載のフィルム状接着剤の一方の面に、チップの回路形成面を貼り合わせ、前記フィルム状接着剤の他方の面に、光透過性カバーを貼り合わせることにより、前記チップと、前記フィルム状接着剤と、前記光透過性カバーと、がこの順に積層されて構成された積層体を得る、積層体の製造方法。 The circuit forming surface of the chip is attached to one surface of the film adhesive according to any one of claims 1 to 5, and the light transmissive cover is attached to the other surface of the film adhesive. Thus, a method for producing a laminated body, in which the chip, the film adhesive, and the light-transmitting cover are laminated in this order to obtain a laminated body.
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JP2008063551A (en) * 2005-12-13 2008-03-21 Toray Ind Inc Adhesive composition for electronic device, adhesive sheet for electronic device, and electronic component and device using the same
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JP2008063551A (en) * 2005-12-13 2008-03-21 Toray Ind Inc Adhesive composition for electronic device, adhesive sheet for electronic device, and electronic component and device using the same
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