WO2023026584A1 - フィルム状接着剤、これを用いた電子部品及びその製造方法 - Google Patents
フィルム状接着剤、これを用いた電子部品及びその製造方法 Download PDFInfo
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- WO2023026584A1 WO2023026584A1 PCT/JP2022/017919 JP2022017919W WO2023026584A1 WO 2023026584 A1 WO2023026584 A1 WO 2023026584A1 JP 2022017919 W JP2022017919 W JP 2022017919W WO 2023026584 A1 WO2023026584 A1 WO 2023026584A1
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- WIPO (PCT)
- Prior art keywords
- film
- adhesive
- epoxy resin
- curing agent
- electronic component
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly 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
- H01L21/52—Mounting semiconductor bodies in containers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14632—Wafer-level processed structures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
- H01L27/14687—Wafer level processing
Definitions
- the present invention relates to a film adhesive, an electronic component using the same, and a method for manufacturing the same.
- Image sensors such as CMOS (Complementary Metal Oxide Semiconductor) image sensors and CCD (Charge Coupled Device) image sensors are incorporated in imaging equipment such as digital still cameras and digital video cameras.
- the image sensor photoelectrically converts incident light with a photodiode into an electric signal, and forms a digital image through signal processing.
- a color filter, a microlens, etc. are arranged on the surface of the photodiode, if necessary, and a transparent protective film such as a glass plate is usually arranged on the surface thereof.
- a transparent protective film is fixed via a film adhesive or the like.
- An adhesive used for adhering and fixing a transparent protective film of an image sensor is required to be transparent enough to transmit light.
- Various compositions of film-like adhesives are known, and they are widely used not only in image sensors but also in the manufacture of electronic devices and their members. For example, in the manufacturing process of semiconductor chips, a film adhesive is used as a die attach film.
- the film-like adhesive is pre-cut according to its intended use (for example, according to the shape of the adherend), and a laminate obtained by laminating the film-like adhesive (for example, a film-like adhesive and a dicing film). Laminates) are also pre-cut according to their intended use.
- a pre-cutting process it has been proposed to irradiate the film-like adhesive with light and perform highly accurate pre-cutting while sensing the position and shape of the film-like adhesive with an optical sensor.
- the film-like adhesive is transparent, sensing by an optical sensor is difficult.
- it has been proposed to reduce the transparency of the film adhesive by adding a light transmittance adjusting component such as a dye or pigment to the film adhesive (for example, Patent Document 1). ).
- a light transmittance adjusting component such as a pigment
- the light transmittance adjusting component remains in the cured product even after the film adhesive is cured. Remain. Therefore, the transparency remains impaired even after curing, and is not suitable as an adhesive for adhering, for example, a transparent protective film of an image sensor.
- a light transmittance adjusting component such as a pigment acts to reduce the adhesive strength, and may impair the desired strong adhesive strength.
- transparency is suppressed in the state before use as an adhesive (before curing), so it is possible to sense the position and shape of the film adhesive with an optical sensor, and as a result, high-precision precut processing is possible. It is an object of the present invention to provide a film-like adhesive that functions as a transparent film-like cured product that exhibits high transparency and strong adhesive strength when used as an adhesive (after heat curing). do.
- the content of the epoxy resin curing agent (B) is 0.30 to 12.0% by mass
- the film adhesive has a light transmittance T1 of 90% or less at a wavelength of 400 nm
- a cured product obtained by thermally curing the film adhesive has a light transmittance T2 of 85% or more at a wavelength of 400 nm, and satisfies T1 ⁇ T2.
- the epoxy resin curing agent (B) is a powder having a particle size (d90) of 20.0 ⁇ m or less at a cumulative distribution frequency of 90%, and the epoxy resin curing agent (B) is dispersed in the film adhesive.
- a laminate film comprising a laminate of the film adhesive according to any one of [1] to [5] and a dicing film.
- a method for manufacturing an electronic component a first step of obtaining a laminate in which a transparent film-like member, the film-like adhesive according to any one of [1] to [5], and a dicing film are laminated in this order; a second step of obtaining a transparent film-like chip with an adhesive layer on a dicing film by integrally dicing the transparent film-like member and the film-like adhesive; a third step of removing the dicing film from the adhesive layer and thermocompression bonding the transparent film-like chip with the adhesive layer and another member constituting the electronic component via the adhesive layer; a fourth step of thermosetting the adhesive layer;
- a method of manufacturing an electronic component comprising: [8] An electronic component, wherein the transparent film-like chip comprises a structural part incorporated in the electronic component via the thermosetting film adhesive according to any one of [1] to [5].
- a numerical range represented by "-” means a range including the numerical values before and after "-” as lower and upper limits.
- the term “- compound” means "a compound having a skeleton".
- the term “dicyandiamide compound” is meant to include not only dicyandiamide itself, but also forms in which at least some of the hydrogen atoms of dicyandiamide are substituted.
- the film adhesive of the present invention has reduced transparency before it is used as an adhesive (before curing). Precise pre-cut processing can be performed, and in the state of being used as an adhesive (after heat curing), it can function as a transparent film-like cured product that exhibits high transparency and strong adhesive strength.
- FIG. 1 is a cross-sectional view schematically showing the structure of a film-like adhesive with a release film prepared in an example.
- the film adhesive of the present invention contains an epoxy resin (A), an epoxy resin curing agent (B), and a phenoxy resin (C).
- the content of the epoxy resin curing agent (B) in the film adhesive is 0.30 to 12.0% by mass.
- the light transmittance T1 of the film adhesive of the present invention at a wavelength of 400 nm is 90% or less
- the light transmittance T2 of a cured product obtained by thermally curing the film adhesive of the present invention at a wavelength of 400 nm is 85%. It is the above and satisfies T1 ⁇ T2.
- the transparent member can be used for electronic parts and the like. It exhibits excellent optical properties as an adhesive during assembly.
- the light wavelength is not limited to 400 nm when sensing the film-like adhesive of the present invention with an optical sensor. By controlling the light transmittance as described above with a wavelength of 400 nm as an index, it is possible to effectively improve the recognizability of the optical sensor in a wide wavelength range.
- Epoxy resin (A) is a thermosetting resin having an epoxy group, and has an epoxy equivalent of 1000 g/eq or less.
- Epoxy resin (A) may be liquid, solid or semi-solid.
- liquid means that the softening point is less than 25° C.
- solid means that the softening point is 60° C. or higher
- si-solid means that the softening point of the liquid is the same as that of the solid. It means that it is between the softening point of (25 ° C. or more and less than 60 ° C.).
- the epoxy resin (A) used in the present invention has a softening point of 100°C or less from the viewpoint of obtaining a film-like adhesive that can reach a low melt viscosity in a suitable temperature range (for example, 60 to 120°C).
- a softening point is a value measured by a softening point test (ring and ball method) method (measurement conditions: JIS-K7234, 1986).
- the epoxy equivalent is preferably 150 to 800 g/eq from the viewpoint of increasing the crosslink density of the thermoset.
- the term "epoxy equivalent” refers to the number of grams (g/eq) of a resin containing 1 gram equivalent of epoxy groups.
- the weight average molecular weight of the epoxy resin (A) is generally preferably less than 10,000, more preferably 5,000 or less. Although the lower limit is not particularly limited, 300 or more is practical.
- the mass average molecular weight is a value obtained by GPC (Gel Permeation Chromatography) analysis.
- the skeleton of the epoxy resin (A) includes, for example, phenol novolak type, ortho-cresol novolak type, cresol novolak type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, and triphenylmethane. type, tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type.
- the triphenylmethane type, bisphenol A type, cresol novolac type, or ortho-cresol novolac type is preferable from the viewpoint of obtaining a film-like adhesive having low crystallinity and good appearance.
- These may be used singly or in combination of two or more, preferably a combination of triphenylmethane type and bisphenol A type.
- the content of the epoxy resin (A) is preferably 3 to 80 parts by mass, more preferably 30 to 70 parts by mass, based on the total content of 100 parts by mass of the components constituting the film adhesive (specifically, components other than the solvent). parts is more preferred, and 40 to 70 parts by mass is even more preferred. Storage stability and transparency can be improved by setting the content within the above preferable range. Further, by making the content equal to or less than the above preferable upper limit, it is possible to suppress the formation of oligomer components and to make it difficult for slight temperature changes to cause changes in the film state (film tackiness, etc.).
- the epoxy resin curing agent (B) is an important component for controlling the light transmittance defined in the present invention.
- the above epoxy resin curing agent (B) is selected in consideration of the control of the above light transmittance.
- the epoxy resin curing agent (B) is preferably a powder (powder form) having a particle size (d90) of 20.0 ⁇ m or less when the cumulative distribution frequency is 90%.
- that the epoxy resin curing agent (B) is powder means that the epoxy resin curing agent (B) is in the form of solid particles at normal temperature (25° C., hereinafter the same).
- the d90 means the particle diameter at which 90% of the total volume of the particles is 100% in the cumulative distribution measured by the laser diffraction/scattering method.
- the d90 of the epoxy resin curing agent (B) is preferably 0.70 ⁇ m or more, more preferably 0.80 ⁇ m or more, and 0.90 ⁇ m or more. It is also preferable to set As the epoxy resin curing agent (B), a commercially available product can be used, and if necessary, it can be pulverized, sieved, or the like. Even if the light transmittance T1 of the film-like adhesive at a wavelength of 400 nm is reduced to 90% or less by using the powder epoxy resin curing agent, the powder epoxy resin curing agent cannot be used at high temperatures in the heat curing reaction.
- the powdery epoxy resin curing agent (B) is preferably present in a powdery (particulate) state even in the film-like adhesive. That is, it is preferably in a state of being dispersed in the film-like adhesive as fine solid particles. In order to create such a state, the powder epoxy resin curing agent preferably has low solvent solubility at 25°C.
- the solubility in 100 g of methyl ethyl ketone is less than 0.05 g (preferably less than 0.02 g, more preferably less than 0.01 g) at 25° C.
- the varnish for forming the film adhesive or the film adhesive the epoxy resin curing agent can be more reliably present in the form of fine particles, making it easier to achieve the desired decrease in transparency.
- the solubility in methyl ethyl ketone is an index of the solubility of the epoxy resin curing agent in the film adhesive regardless of whether methyl ethyl ketone is used in the varnish for forming the film adhesive.
- Examples of epoxy resin curing agents (B) include amines, acid anhydrides, and polyhydric phenols. From the viewpoint of storage stability of the film adhesive, it is preferable to use a latent curing agent.
- latent curing agents include dicyandiamide compounds, imidazole compounds, curing catalyst complex polyhydric phenol compounds, hydrazide compounds, boron trifluoride-amine complexes, amine imide compounds, polyamine salts, modified products thereof, and microcapsule types. These may be used singly or in combination of two or more. Among them, it is preferable to use at least one of a dicyandiamide compound, an imidazole compound and a hydrazide compound.
- the content of the epoxy resin curing agent (B) in the film-like adhesive of the present invention is 0.00, from the viewpoint of controlling the light transmittances T1 and T2 to the desired level while imparting sufficient curability. 30 to 12.0% by mass.
- the content is preferably 0.40 to 12.0% by mass, more preferably 0.50 to 11.0% by mass, and more preferably 0.55 to 10.0% by mass.
- the content of the epoxy resin curing agent (B) with respect to 100 parts by mass of the epoxy resin (A) is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, from the viewpoint of exhibiting a sufficient curing speed. It is more preferably up to 30 parts by mass, more preferably 3 to 25 parts by mass.
- the phenoxy resin (C) is a component that suppresses film tackiness at room temperature (25° C.) and imparts film forming properties (film formability) when a film adhesive is formed.
- the physical properties of the phenoxy resin (C) are not particularly limited. For example, a phenoxy resin having an elastic modulus at room temperature (25° C.) of 500 MPa or more and 2000 MPa or less can be used.
- the phenoxy resin (C) generally has a mass average molecular weight of 10,000 or more. Although there is no particular upper limit, 5,000,000 or less is practical.
- the mass-average molecular weight of the phenoxy resin (C) is obtained by GPC [Gel Permeation Chromatography] in terms of polystyrene.
- the glass transition temperature (Tg) of the phenoxy resin (C) is preferably less than 120°C, more preferably less than 100°C, and more preferably less than 90°C.
- the lower limit is preferably 0°C or higher, more preferably 10°C or higher.
- the glass transition temperature of the phenoxy resin (C) is the glass transition temperature measured by DSC (Differential Scanning Calorimetry) at a heating rate of 10°C/min.
- the film adhesive of the present invention contains at least one phenoxy resin as the phenoxy resin (C).
- the phenoxy resin (C) has an epoxy equivalent (mass of resin per equivalent of epoxy group) exceeding 1000 g/eq. That is, resins having the structure of a phenoxy resin but having an epoxy equivalent of 1000 g/eq or less are classified as epoxy resins (A).
- the phenoxy resin (C) can be obtained by reacting a bisphenol or biphenol compound with an epihalohydrin such as epichlorohydrin, or by reacting a liquid epoxy resin with a bisphenol or biphenol compound.
- the bisphenol or biphenol compound is preferably a compound represented by the following general formula (A).
- La represents a single bond or a divalent linking group
- R a1 and R a2 each independently represent a substituent
- ma and na each independently represent an integer of 0 to 4;
- the divalent linking group is preferably an alkylene group, a phenylene group, —O—, —S—, —SO—, —SO 2 —, or a combination of an alkylene group and a phenylene group.
- the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms, and most preferably 1 carbon atom.
- the alkylene group is preferably -C(R ⁇ )(R ⁇ )-, where R ⁇ and R ⁇ each independently represent a hydrogen atom, an alkyl group or an aryl group.
- R ⁇ and R ⁇ may combine with each other to form a ring.
- R ⁇ and R ⁇ are preferably hydrogen atoms or alkyl groups (eg, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, hexyl, octyl, or 2-ethylhexyl).
- the alkylene group is preferably -CH 2 -, -CH(CH 3 )- or -C(CH 3 ) 2 -, more preferably -CH 2 - or -CH(CH 3 )-, and -CH 2- is more preferred.
- the phenylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and even more preferably 6 carbon atoms.
- the phenylene group includes, for example, p-phenylene, m-phenylene and o-phenylene, preferably p-phenylene or m-phenylene.
- an alkylene-phenylene-alkylene group is preferable, and -C(R ⁇ )(R ⁇ )-phenylene-C(R ⁇ )(R ⁇ )- is more preferable.
- the ring formed by combining R ⁇ and R ⁇ is preferably a 5- or 6-membered ring, more preferably a cyclopentane ring or a cyclohexane ring, and still more preferably a cyclohexane ring.
- L a is preferably a single bond, an alkylene group, —O—, or SO 2 —, more preferably an alkylene group.
- R a1 and R a2 are preferably an alkyl group, an aryl group, an alkoxy group, an alkylthio group, or a halogen atom, more preferably an alkyl group, an aryl group, or a halogen atom, and still more preferably an alkyl group.
- ma and na are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
- bisphenols or biphenol compounds examples include bisphenol A, bisphenol AD, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH. , bisphenol TMC, bisphenol Z, 4,4'-biphenol, 2,2'-dimethyl-4,4'-biphenol, 2,2',6,6'-tetramethyl-4,4'-biphenol, and cardo bisphenol A, bisphenol AD, bisphenol C, bisphenol E, bisphenol F, or 4,4'-biphenol are preferred, bisphenol A, bisphenol E, or bisphenol F are more preferred, and bisphenol A is particularly preferred. preferable.
- a diglycidyl ether of an aliphatic diol compound is preferable, and a compound represented by the following general formula (B) is more preferable.
- X represents an alkylene group
- nb represents an integer of 1-10.
- the alkylene group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 3 to 8 carbon atoms, particularly preferably 4 to 6 carbon atoms, and most preferably 6 carbon atoms.
- Examples include ethylene, propylene, butylene, pentylene, hexylene, and octylene, preferably ethylene, trimethylene, tetramethylene, pentamethylene, heptamethylene, hexamethylene, or octamethylene.
- nb is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1.
- X is preferably ethylene or propylene, more preferably ethylene.
- Aliphatic diol compounds in diglycidyl ether include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, 1 ,6-hexanediol, 1,7-pentanediol, and 1,8-octanediol.
- each of the bisphenols, biphenol compounds, and aliphatic diol compounds may be a phenoxy resin obtained by reacting alone, or may be a phenoxy resin obtained by reacting a mixture of two or more of them.
- the reaction of diglycidyl ether of 1,6-hexanediol with a mixture of bisphenol A and bisphenol F can be mentioned.
- the phenoxy resin (C) is preferably a phenoxy resin obtained by reacting a liquid epoxy resin with a bisphenol or a biphenol compound, and is a phenoxy resin having a repeating unit represented by the following general formula (I): is more preferable.
- L a , R a1 , R a2 , ma and na are synonymous with L a , R a1 , R a2 , ma and na in general formula (A), and the preferred ranges are also the same.
- X and nb have the same meanings as X and nb in formula (B), and the preferred ranges are also the same.
- a polymer of bisphenol A and diglycidyl ether of 1,6-hexanediol is preferred. Focusing on the skeleton of the phenoxy resin, bisphenol A type phenoxy resin or bisphenol A/F type copolymer phenoxy resin can be preferably used in the present invention. Also, a low-elasticity, high-heat-resistant phenoxy resin can be preferably used.
- the weight average molecular weight of the phenoxy resin (C) is more preferably 10,000 to 100,000. Moreover, the amount of epoxy groups slightly remaining in the phenoxy resin (C) preferably exceeds 5000 g/eq in terms of epoxy equivalent.
- the phenoxy resin (C) may be synthesized by the method described above, or a commercially available product may be used.
- Commercially available products include, for example, 1256 (bisphenol A type phenoxy resin, manufactured by Mitsubishi Chemical Corporation), YP-50 (bisphenol A type phenoxy resin, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.), YP-70 (bisphenol A / F type phenoxy resin, Shin Nikka Epoxy Manufacturing Co., Ltd.), FX-316 (bisphenol F type phenoxy resin, Shin Nikka Epoxy Manufacturing Co., Ltd.), FX-280S (cardo skeleton type phenoxy resin, Shin Nikka Epoxy Manufacturing Co., Ltd.) Chemical Epoxy Manufacturing Co., Ltd.), 4250 (bisphenol A type / F type phenoxy resin, manufactured by Mitsubishi Chemical Corporation), and FX-310 (low elasticity and high heat resistance type phenoxy resin, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.
- the ratio of the phenoxy resin (C) to the total content of the epoxy resin (A) and the phenoxy resin (C) is 10 to 60% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass. %, more preferably 35 to 50% by mass.
- the film-like adhesive of the present invention in addition to the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin (C), satisfies the provisions of the present invention and does not impair the effects of the present invention. , may contain polymer compounds other than these.
- the polymer compound include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, silicone rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester.
- Copolymers polybutadiene resins, polycarbonate resins, thermoplastic polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, (meth) acrylic resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamideimide resins, and fluororesin. These polymer compounds may be used alone or in combination of two or more.
- the total content of the epoxy resin (A) and phenoxy resin (C) contained in the film adhesive of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. It is also preferable to make it 80% by mass or more.
- the film adhesive of the present invention contains an ion trapping agent (ion trapping agent), a curing catalyst, a viscosity modifier, an antioxidant, a flame retardant, a coloring agent, and an inorganic
- ion trapping agent ion trapping agent
- a curing catalyst ion trapping agent
- a viscosity modifier e.g., sodium bicarbonate
- an antioxidant e.g., sodium bicarbonate
- a flame retardant e.g., sodium bicarbonate
- coloring agent e.g., sodium bicarbonate
- inorganic filler e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
- the thickness of the film-like adhesive of the present invention is not particularly limited, and can be appropriately set according to the purpose.
- the film adhesive of the present invention can have a thickness of, for example, 1 to 30 ⁇ m, preferably 1 to 25 ⁇ m, preferably 1 to 20 ⁇ m, and preferably 2 to 20 ⁇ m.
- the thickness is preferably up to 20 ⁇ m, more preferably 4 to 20 ⁇ m.
- the thickness of the film-like adhesive can be measured by a contact/linear gauge method (desktop contact-type thickness measuring device).
- the film adhesive of the present invention has a light transmittance T1 of 90% or less at a wavelength of 400 nm, and a cured product obtained by thermally curing the film adhesive has a light transmittance T2 of 85% or more at a wavelength of 400 nm. , and satisfy T1 ⁇ T2.
- the light transmittance at a wavelength of 400 nm is parallel line transmittance, and is determined by the method described in Examples below.
- the term “cured product obtained by thermally curing a film adhesive” means a cured product obtained by curing a film adhesive by treating it at 150° C. for 1 hour.
- the adhesive has not yet been thermally cured. Specifically, it means a film-like adhesive that has not been exposed to a temperature higher than the temperature at which the epoxy resin is thermally cured after the film-like adhesive is prepared. Preferably, it is a film-like adhesive that has not been exposed to temperature conditions of 25° C. or higher after being prepared.
- the above description is for clarifying the characteristics of the film adhesive of the present invention, and is limited to those that have not been exposed to temperature conditions of 25°C or higher. not to be
- the film adhesive of the present invention has a light transmittance T1 of 90% or less, the position and shape of the film adhesive can be sensed by an optical sensor, and highly accurate precut processing can be performed. can.
- the light transmittance T1 is preferably 89% or less, preferably 88% or less, preferably 87% or less, and preferably 86% or less.
- the light transmittance T1 is usually 60% or more, more preferably 65% or more, from the viewpoint of ensuring transparency after heat curing.
- the above light transmittance T2 is 85% or more, high transparency can be secured after heat curing, and as a transparent film-like cured product, optical properties suitable for adhesion of a transparent protective film etc. can be expressed. can be done.
- the light transmittance T2 is preferably 87% or more, more preferably 88% or more, and even more preferably 90% or more. Further, the light transmittance T2 is preferably 92% or more, more preferably 94% or more. Furthermore, the film-like adhesive of the present invention has a higher light transmittance T2 than the light transmittance T1. That is, heat curing improves the transparency. In other words, in the state of the film-like adhesive before heat curing, the position and shape of the film-like adhesive can be sensed by an optical sensor, high-precision pre-cut processing can be performed, and transparency can be improved by heat curing. It exhibits optical properties suitable for adhesion of transparent protective films such as image sensors.
- the film-like adhesive of the present invention is a composition (film-like adhesive-forming composition ( It can be obtained by forming a film using varnish)).
- the order of mixing is not particularly limited.
- resin components such as epoxy resin (A) and phenoxy resin (C) may be mixed together with a solvent if necessary, and then the epoxy resin curing agent (B) may be mixed.
- the mixing in the presence of the epoxy resin curing agent (B) may be performed at a temperature at which the epoxy resin (A) is practically not thermally cured, and the resin component in the absence of the epoxy resin curing agent (B) may be performed at higher temperatures.
- Film formation using the composition for forming a film-like adhesive is performed, for example, by coating a composition for forming a film-like adhesive on a release-treated substrate film (also referred to as a release film or release film). , can be dried and formed as desired.
- a release film any release film that functions as a cover film for the resulting film-like adhesive can be used, and a normal release film can be appropriately employed. Examples include release-treated polypropylene (PP), release-treated polyethylene (PE), and release-treated polyethylene terephthalate (PET).
- PP release-treated polypropylene
- PE release-treated polyethylene
- PET release-treated polyethylene terephthalate
- the coating method a conventional method can be appropriately employed, and examples thereof include methods using a roll knife coater, gravure coater, die coater, reverse coater, and the like. Drying may be performed at a temperature of 80 to 150° C., as long as the organic solvent is removed from the film adhesive-forming composition without substantially curing the epoxy
- the film-like adhesive of the present invention can have a form in which the above-described release film or the like is attached to at least one surface.
- the release film does not constitute the film adhesive of the present invention, but is regarded as a member laminated on the film adhesive of the present invention.
- the thickness of the film-like adhesive when the thickness of the film-like adhesive is described, the thickness is the thickness of the base film. is not included. That is, the thickness of the film adhesive in the present invention is the thickness of the layer derived from the composition for forming the film adhesive.
- the film-like adhesive of the present invention may be in the form of cutting a film into a suitable size, or in the form of winding a film into a roll.
- the film adhesive of the present invention is preferably stored under temperature conditions of 10°C or less before use.
- the film-like adhesive of the present invention can be used, for example, in the form of a laminated film obtained by laminating a film-like adhesive and a dicing film (dicing tape).
- This laminated film may be further laminated with a release film or the like.
- a transparent film-like member such as a transparent protective film is brought into close contact with the film-like adhesive side of the laminated film, and fixed via a dicing film. It becomes possible to cut (dicing) the transparent film-like member together with the film-like adhesive into a desired size.
- a transparent film-like chip with an adhesive layer cut into a desired size can be obtained on the dicing film.
- the transparent film-like chip with the adhesive layer can be peeled off from the dicing film, and the transparent film-like chip can be incorporated into the electronic component via the adhesive layer.
- the incorporation into the electronic component is performed by thermocompression bonding or the like, and then the adhesive layer is thermally cured, whereby the transparency of the adhesive can be enhanced with the curing reaction.
- the thermocompression bonding is performed at a temperature at which the epoxy resin (A) is practically not thermoset. For example, conditions of 70° C. and pressure of about 0.3 MPa can be mentioned.
- the thermosetting reaction may be performed at a temperature equal to or higher than the thermosetting initiation temperature of the film-like adhesive of the present invention.
- the heat curing initiation temperature varies depending on the types of epoxy resin (A), phenoxy resin (C) and epoxy curing agent (B) used, and cannot be generalized. 140 to 180° C. is more preferable from the viewpoint of achieving curing.
- the temperature is lower than the heat curing initiation temperature, the heat curing reaction does not proceed sufficiently, and the strength of the adhesive layer tends to decrease.
- the curing reaction temperature is too high, the epoxy resin, curing agent, additives, etc. in the film-like adhesive volatilize during the curing reaction, tending to cause foaming.
- the curing treatment time is preferably 10 to 120 minutes, for example.
- the present invention provides the following electronic component manufacturing method.
- a method for manufacturing an electronic component a first step of obtaining a laminate in which a transparent film-like member, a film-like adhesive of the present invention, and a dicing film are laminated in this order; a second step of obtaining a transparent film-like chip with an adhesive layer on the dicing film by integrally dicing the transparent film-like member and the film-like adhesive; a third step of removing the dicing film from the adhesive layer and thermocompression bonding the transparent film-like chip with the adhesive layer and another member via the adhesive layer; a fourth step of thermosetting the adhesive layer;
- a method of manufacturing an electronic component comprising:
- the following electronic component comprising a structure in which a transparent film-like chip is incorporated into the electronic component via the thermosetting film-like adhesive of the present invention.
- the "transparent film chip” means a transparent film processed into a desired shape.
- a transparent film member such as a glass substrate or a transparent resin is cut into a desired shape for incorporation into an electronic component.
- the transparent film-like chip incorporated in the electronic component is preferably a protective film for the photodiode.
- the above describes a preferred embodiment of the film-like adhesive of the present invention, and the present invention is not limited to these embodiments except as defined by the present invention.
- the above electronic parts preferably include members used in optical devices such as optical lenses, optical fibers, optical waveguides, optical isolators, and semiconductor lasers.
- a film-like adhesive with a release film shown in FIG. 1 was prepared as each example and comparative example.
- Epoxy resin (trade name: 828, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 190 g / eq, specific gravity 1.17) 80 parts by mass, epoxy resin (trade name: EPICLON2050, manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 600 g / eq, softening point 80 ° C.) 30 parts by mass, phenoxy resin (trade name: 1256, manufactured by Mitsubishi Chemical Corporation, bisphenol A type phenoxy resin, epoxy equivalent 7500 g / eq) 70 parts by mass, Heated and stirred with MEK in a 1000 ml separable flask at a temperature of 110° C. for 2 hours to obtain a resin varnish.
- epoxy resin trade name: EPICLON2050, manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 600 g / eq, softening point 80 ° C.
- phenoxy resin (trade name: 1256, manufactured by Mitsubishi Chemical Corporation, bisphenol A type phenoxy resin
- this resin varnish is transferred to another flask container, and a crushed epoxy resin curing agent (trade name: DICY7, manufactured by Mitsubishi Chemical Corporation, dicyandiamide compound, particle size at cumulative distribution frequency of 90% (d90): 0 0.95 ⁇ m, solubility in MEK at 25° C. (less than 0.01 g/100 g-MEK) (2.5 parts by mass) was added, and after stirring and mixing at room temperature for 1 hour, vacuum defoaming was performed to obtain a mixed varnish. Furthermore, the obtained mixed varnish was applied on a release-treated PET film (release film) with a thickness of 38 ⁇ m, dried by heating at 130° C.
- DICY7 crushed epoxy resin curing agent
- Example 2 A film-like adhesive with a release film (film-like adhesive having a thickness of 10 ⁇ m) was obtained in the same manner as in Example 1, except that the blending amounts of each resin and epoxy resin curing agent were changed as shown in the table below.
- Example 3 The compounding amount of each resin is as shown in the table below, and the crushed epoxy resin curing agent (trade name: N14, manufactured by Mitsubishi Chemical Corporation, hydrazide compound, particle size at cumulative distribution frequency of 90% ( d90): 2.0 ⁇ m, solubility in MEK at 25° C. Less than 0.01 g/100 g-MEK) Film adhesive with release film in the same manner as in Example 1 (film adhesive thickness of 10 ⁇ m) was obtained.
- the crushed epoxy resin curing agent trade name: N14, manufactured by Mitsubishi Chemical Corporation, hydrazide compound, particle size at cumulative distribution frequency of 90% ( d90): 2.0 ⁇ m, solubility in MEK at 25° C. Less than 0.01 g/100 g-MEK
- Example 4 A film-like adhesive with a release film (film-like adhesive having a thickness of 10 ⁇ m) was obtained in the same manner as in Example 3, except that the blending amounts of each resin and epoxy resin curing agent were changed as shown in the table below.
- Example 5 The blending amount of each resin is as shown in the table below, and the epoxy resin curing agent is an uncrushed curing agent (trade name: DICY7, manufactured by Mitsubishi Chemical Corporation, particle size (d90) at a cumulative distribution frequency of 90%) : 15.0 ⁇ m, solubility in MEK at 25 ° C. less than 0.01 g / 100 g-MEK) Film adhesive with release film in the same manner as in Example 1 (thickness of film adhesive 20 ⁇ m) was obtained.
- the epoxy resin curing agent is an uncrushed curing agent (trade name: DICY7, manufactured by Mitsubishi Chemical Corporation, particle size (d90) at a cumulative distribution frequency of 90%) : 15.0 ⁇ m, solubility in MEK at 25 ° C. less than 0.01 g / 100 g-MEK)
- Film adhesive with release film in the same manner as in Example 1 was obtained.
- Example 6 The blending amount of each resin is as shown in the table below, and the epoxy resin curing agent is an uncrushed curing agent (trade name: N14, manufactured by Mitsubishi Chemical Corporation, particle size (d90) at a cumulative distribution frequency of 90%) : 18.0 ⁇ m, solubility in MEK at 25 ° C. less than 0.01 g / 100 g-MEK) Film adhesive with release film in the same manner as in Example 1 (thickness of film adhesive 20 ⁇ m) was obtained.
- the epoxy resin curing agent is an uncrushed curing agent (trade name: N14, manufactured by Mitsubishi Chemical Corporation, particle size (d90) at a cumulative distribution frequency of 90%) : 18.0 ⁇ m, solubility in MEK at 25 ° C. less than 0.01 g / 100 g-MEK)
- Film adhesive with release film in the same manner as in Example 1 was obtained.
- each resin is as shown in the table below, and the epoxy resin curing agent is an untreated curing agent (trade name: SI-150, manufactured by Sanshin Chemical Industry Co., Ltd., cationic polymerization initiator, against MEK at 25 ° C.
- a film-like adhesive with a release film was obtained in the same manner as in Example 1, except that the solubility was changed to 5 parts by mass (10 g or more/100 g-MEK).
- each resin is as shown in the table below, and the epoxy resin curing agent is a pigment (trade name: CI Pig Black 7, manufactured by Mitsubishi Chemical Corporation, solubility in MEK at 25 ° C. less than 0.01 g/100 g- MEK) was changed to 5 parts by mass, and a film adhesive with a release film (thickness of film adhesive: 5 ⁇ m) was produced in the same manner as in Example 1.
- the epoxy resin curing agent is a pigment (trade name: CI Pig Black 7, manufactured by Mitsubishi Chemical Corporation, solubility in MEK at 25 ° C. less than 0.01 g/100 g- MEK) was changed to 5 parts by mass, and a film adhesive with a release film (thickness of film adhesive: 5 ⁇ m) was produced in the same manner as in Example 1.
- Example 3 A film-like adhesive with a release film (thickness of the film-like adhesive of 5 ⁇ m) was carried out in the same manner as in Example 1, except that the blending amount of each resin was as shown in the table below, and the epoxy resin curing agent was not added. ).
- Example 4 A film-like adhesive with a release film (thickness of film-like adhesive: 5 ⁇ m) was prepared in the same manner as in Example 1, except that the blending amounts of each resin and curing agent were as shown in the table below.
- Example 5 A film-like adhesive with a release film (thickness of film-like adhesive: 5 ⁇ m) was prepared in the same manner as in Example 1, except that the blending amounts of each resin and curing agent were as shown in the table below.
- each resin is as shown in the table below, and the epoxy resin curing agent is an untreated curing agent (trade name: Milex XLC-LL, manufactured by Mitsui Chemicals, Inc., phenol compound, solubility in MEK at 25 ° C. 10 g Above / 100 g-MEK) 35 parts by mass, further pigment (trade name: CI Pig Black 7, manufactured by Mitsubishi Chemical Corporation, solubility in MEK at 25 ° C. less than 0.01 g / 100 g-MEK) 4.2 mass A film-like adhesive with a release film (thickness of the film-like adhesive of 5 ⁇ m) was obtained in the same manner as in Example 1, except that parts were added.
- the epoxy resin curing agent is an untreated curing agent (trade name: Milex XLC-LL, manufactured by Mitsui Chemicals, Inc., phenol compound, solubility in MEK at 25 ° C. 10 g Above / 100 g-MEK) 35 parts by mass, further pigment (trade name: CI Pig Black
- each resin is as shown in the table below, and the epoxy resin curing agent is an untreated curing agent (trade name: Milex XLC-LL, Mitsui Chemicals, Inc., phenol compound, solubility in MEK at 25 ° C. 10 g or more /100 g-MEK)
- a film-like adhesive with a release film was obtained in the same manner as in Example 1, except that the content was changed to 35 parts by mass.
- the resin type and compounding amount are as shown in the table below, and the epoxy curing agent is a liquid curing agent (trade name: MH-700, manufactured by Shin Nippon Rika Co., Ltd., alicyclic acid anhydride, solubility in MEK at 25 ° C.
- a film-like adhesive with a release film was obtained in the same manner as in Example 1, except that the content was changed to 24 parts by mass (10 g or more/100 g-MEK).
- the pulverization method of the epoxy resin curing agent in each of the above examples and comparative examples is as follows.
- the epoxy resin curing agent was pulverized with a dry pulverizer (trade name: Dri-Bast Parallel DB-180WP, manufactured by Sugino Machine) at a rotation speed of 5000 rev/min for 3 hours.
- a dry pulverizer trade name: Dri-Bast Parallel DB-180WP, manufactured by Sugino Machine
- the particle size distribution of the epoxy resin curing agent used in each of the above examples and comparative examples was determined as follows.
- ⁇ Particle size distribution measurement of epoxy resin curing agent > 0.1 g of epoxy resin curing agent and 9.9 g of MEK were weighed, and the mixture was subjected to ultrasonic dispersion treatment for 5 minutes to prepare a measurement sample.
- the particle size at a cumulative distribution frequency of 90% A diameter (d90) was obtained. Table 1 shows the results.
- the transmittance of the film-like adhesives before and after heat curing was determined as follows.
- a film adhesive with a release film was cut into a circular shape with a diameter of 220 mm.
- a dicing film was laminated at room temperature on the film-like adhesive side of this circular-shaped film-like adhesive with a release film.
- the film with a circular release film was pre-cut into a circular shape with a diameter of 290 mm concentrically with the adhesive (a shape matching the shape of the wafer ring frame).
- an optical sensor recognizes the difference in transmittance between the layered portion of the circular film adhesive with release film and the dicing film and the single-layer portion of the dicing film only, and A predetermined position of the dicing film was cut by grasping the place where the film-like adhesive with a release film was attached.
- 300 sheets were pre-cut and the processing success rate (%) was evaluated.
- the uniform dispersibility of the epoxy resin curing agent in the film-like adhesives was evaluated as follows, using the appearance as an index under microscopic observation. .
- ⁇ Appearance of film adhesive> The appearance of the film adhesive formed on the release film was observed using a transmission optical microscope. Four fields of view (four different areas, each area size of 50 mm ⁇ 50 mm) were observed at random, and the number of fields in which lumps shown in the evaluation criteria below were confirmed in planar view was examined and evaluated. This makes it possible to evaluate the uniform dispersibility of the epoxy resin curing agent.
- the adhesion reliability was evaluated using the shear peel strength as an index. It was evaluated as follows.
- the film-like adhesive with release film obtained in each example and comparative example was laminated with a dummy silicon at a temperature of 70 ° C. and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, manufactured by Technovision). It was thermocompression bonded to one surface of a wafer (8 inch size, 350 ⁇ m thickness). Then, after peeling off the release film from the film-like adhesive, a dicing film (trade name: K-13, manufactured by Furukawa Electric Co., Ltd.) and a dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were crimped.
- a dicing device (trade name: DFD-6340, (manufactured by DISCO Co.), dicing (cutting) from the dummy silicon wafer side in the thickness direction of the film adhesive to the entire thickness of the film adhesive so as to have a size of 2 mm ⁇ 2 mm.
- a dummy chip with an adhesive was obtained on the dicing film.
- the dummy chip with the adhesive was picked up from the dicing film by a die bonder (trade name: DB-800, manufactured by Hitachi High-Technologies Corporation), and the temperature was 120° C., pressure 0.1 MPa (load 400 gf), time 1.0 second.
- the film-like adhesive could not exhibit sufficient transparency after the curing reaction (Comparative Examples 5, 7 and 8).
- the film adhesives of Examples 1 to 6, which satisfy the provisions of the present invention can reduce the light transmittance T1 at a wavelength of 400 nm to 90% or less by blending epoxy resin curing agents without using pigments. It was also found that these film-like adhesives are highly recognizable by optical sensors irrespective of wavelength, and that these film-like adhesives exhibit enhanced transparency after curing.
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Abstract
Description
フィルム状接着剤それ自体は種々の組成のものが知られており、イメージセンサに限らず、電子機器やその部材の製造等において広く用いられている。例えば、半導体チップの製造工程では、フィルム状接着剤がダイアタッチフィルムとして用いられている。
本発明は、接着剤として使用する前(硬化前)の状態では透明性が抑えられ、それゆえ光学センサによるフィルム状接着剤の位置や形状のセンシングを可能とし、結果、高精度のプリカット加工をすることができ、接着剤として使用された状態(熱硬化後)においては高度な透明性と強固な接着力を示す透明フィルム状硬化物として機能する、フィルム状接着剤を提供することを課題とする。
〔1〕
エポキシ樹脂(A)、エポキシ樹脂硬化剤(B)、及びフェノキシ樹脂(C)を含有するフィルム状接着剤であって、
前記フィルム状接着剤中、前記エポキシ樹脂硬化剤(B)の含有量が0.30~12.0質量%であり、
前記フィルム状接着剤の波長400nmの光透過率T1が90%以下、前記フィルム状接着剤を熱硬化してなる硬化物の波長400nmの光透過率T2が85%以上、かつT1<T2を満たす、フィルム状接着剤。
〔2〕
前記エポキシ樹脂硬化剤(B)が、累積分布頻度90%時の粒径(d90)が20.0μm以下の粉体であり、前記エポキシ樹脂硬化剤(B)が前記フィルム状接着剤中に分散してなる、〔1〕に記載のフィルム状接着剤。
〔3〕
前記フィルム状接着剤の厚さが1~20μmである、〔1〕又は〔2〕に記載のフィルム状接着剤。
〔4〕
前記フィルム状接着剤が着色剤を含有しない、〔1〕~〔3〕のいずれか1つに記載のフィルム状接着剤。
〔5〕
前記フィルム状接着剤が無機充填材を含有しない、〔1〕~〔4〕のいずれか1つに記載のフィルム状接着剤。
〔6〕
〔1〕~〔5〕のいずれか1つに記載のフィルム状接着剤とダイシングフィルムとの積層体を含む、積層フィルム。
〔7〕
電子部品の製造方法であって、
透明フィルム状部材と、〔1〕~〔5〕のいずれか1つに記載のフィルム状接着剤と、ダイシングフィルムとがこの順に積層された積層体を得る第1の工程と、
前記透明フィルム状部材と前記フィルム状接着剤とを一体にダイシングすることにより、ダイシングフィルム上に、接着剤層付き透明フィルム状チップを得る第2の工程と、
前記接着剤層から前記ダイシングフィルムを取り除き、前記接着剤層付き透明フィルム状チップと電子部品を構成する他の部材とを前記接着剤層を介して熱圧着する第3の工程と、
前記接着剤層を熱硬化する第4の工程と、
を含む電子部品の製造方法。
〔8〕
透明フィルム状チップが、〔1〕~〔5〕のいずれか1つに記載のフィルム状接着剤の熱硬化体を介して電子部品中に組み込まれた構造部を含む、電子部品。
〔9〕
前記電子部品がイメージセンサである、〔8〕に記載の電子部品。
〔10〕
前記透明フィルム状チップがフォトダイオードの保護フィルムとして組み込まれている、〔9〕に記載の電子部品。
本発明において「~化合物」という場合、「~骨格を有する化合物」を意味する。例えば「ジシアンジアミド化合物」は、ジシアンジアミドそのものに加え、ジシアンジアミドが有する水素原子の少なくとも一部が置換された形態も包含する意味である。
本発明のフィルム状接着剤は、エポキシ樹脂(A)、エポキシ樹脂硬化剤(B)、及びフェノキシ樹脂(C)を含有する。本発明のフィルム状接着剤は、フィルム状接着剤中、前記エポキシ樹脂硬化剤(B)の含有量が0.30~12.0質量%である。
また、本発明のフィルム状接着剤の波長400nmの光透過率T1は90%以下であり、本発明のフィルム状接着剤を熱硬化してなる硬化物の波長400nmの光透過率T2は85%以上であり、かつ、T1<T2を満たす。このような透過率特性を有することにより、光学センサを用いたプリカット加工を高効率に行うことが可能になり、かつ、硬化反応後には高い透明性を示すことから、透明部材を電子部品等に組み込む際の接着剤として優れた光学特性を示す。なお、プリカット加工等において、本発明のフィルム状接着剤を光学センサによりセンシングするに当たり、光波長は400nmに限定されるものではない。波長400nmを指標として光透過性を上記の通り制御することにより、幅広い波長域における光学センサによる認識性を効果的に高めることができる。
上記エポキシ樹脂(A)は、エポキシ基を持つ熱硬化型の樹脂であり、エポキシ当量は1000g/eq以下である。エポキシ樹脂(A)は液体、固体又は半固体のいずれであってもよい。本発明において液体とは、軟化点が25℃未満であることをいい、固体とは、軟化点が60℃以上であることをいい、半固体とは、軟化点が上記液体の軟化点と固体の軟化点との間(25℃以上60℃未満)にあることをいう。本発明で使用するエポキシ樹脂(A)としては、好適な温度範囲(例えば60~120℃)で低溶融粘度に到達することができるフィルム状接着剤を得る観点から、軟化点が100℃以下であることが好ましい。なお、本発明において、軟化点とは、軟化点試験(環球式)法(測定条件:JIS-K7234 1986年に準拠)により測定した値である。
エポキシ樹脂(A)の質量平均分子量は、通常、10000未満が好ましく、5000以下がより好ましい。下限値に特に制限はないが、300以上が実際的である。
質量平均分子量は、GPC(Gel Permeation Chromatography)分析による値である。
上記エポキシ樹脂硬化剤(B)は、本発明で規定する上記の光透過率の制御に重要な成分である。上記の光透過率の制御を考慮して、上記エポキシ樹脂硬化剤(B)を選択する。
上記の光透過率の制御のために、上記エポキシ樹脂硬化剤(B)は、累積分布頻度90%時の粒径(d90)が20.0μm以下の粉体(粉末状)であることが好ましい。本発明において、エポキシ樹脂硬化剤(B)が粉体であるとは、エポキシ樹脂硬化剤(B)が、常温(25℃、以下同様。)において固体粒子状であることをいう。また、上記d90とは、レーザー回折・散乱法により測定した累積分布において粒子の全体積を100%としたときに90%累積となるときの粒径を意味する。上記エポキシ樹脂硬化剤(B)が所定の粉体としてフィルム状接着剤中に分散していることにより、波長400nmの光透過率T1を90%以下へと低減することができる。上記エポキシ樹脂硬化剤(B)は、d90が、10.0μm以下が好ましく、5.0μm以下がより好ましく、3.0μm以下がさらに好ましく、2.0μm以下とすることも好ましい。また、光透過率T1を、より確実に90%以下に制御するために、上記エポキシ樹脂硬化剤(B)のd90は0.70μm以上が好ましく、0.80μm以上がより好ましく、0.90μm以上とすることも好ましい。
エポキシ樹脂硬化剤(B)は、市販品を使用することもでき、必要により粉砕処理、篩分け等することもできる。
粉体のエポキシ樹脂硬化剤を用いて、フィルム状接着剤の、波長400nmの光透過率T1を90%以下に低減しても、熱硬化反応においては、粉体のエポキシ樹脂硬化剤が高温下で溶融等しながらフィルム内で樹脂成分と反応し、熱硬化後の透明性を高めることが可能になる。つまり、熱硬化前においては透明性がより低く、熱硬化後においては透明性が高められる光学特性を発現させることができる。
上記の通り、粉体のエポキシ樹脂硬化剤(B)は、フィルム状接着剤中においても粉体(粒子状)の状態で存在していることが好ましい。つまり、微細な固体粒子としてフィルム状接着剤中に分散した状態にあることが好ましい。このような状態を作り出すために、粉体のエポキシ樹脂硬化剤は、25℃における溶媒溶解性が低いことが好ましい。例えば、メチルエチルケトン100gに対する溶解度が、25℃で0.05g未満(好ましくは0.02g未満、さらに好ましくは0.01g未満)であると、フィルム状接着剤形成用のワニスないしフィルム状接着剤中において、エポキシ樹脂硬化剤は、より確実に微粒子状に存在することができ、目的の透明性の低下を実現しやすいものとなる。メチルエチルケトンに対する溶解性は、フィルム状接着剤形成用のワニスにメチルエチルケトンを用いるか否かにかかわらず、フィルム状接着剤中へのエポキシ樹脂硬化剤の溶解性の指標となるものである。
逆に、メチルエチルケトンに対する溶解性が高い場合には、フィルム状接着剤の透明性を90%以下にできたとしても、硬化反応後において透明性を高めることが難しい。また、フィルム状接着剤中に粒子状で存在しない場合、フィルム状接着剤の透明性を90%以下としても、光学センサによる認識性に劣る傾向にある。
フェノキシ樹脂(C)は、フィルム状接着剤を形成した際に、常温(25℃)でのフィルムタック性を抑制し、造膜性(フィルム形成性)を付与する成分である。
上記フェノキシ樹脂(C)の物性は特に制限されない。例えば、常温(25℃)弾性率が500MPa以上2000MPa以下のフェノキシ樹脂を用いることができる。
上記フェノキシ樹脂(C)の質量平均分子量は、GPC〔ゲル浸透クロマトグラフィー(Gel Permeation Chromatography)〕によるポリスチレン換算で求める。
上記フェノキシ樹脂(C)のガラス転移温度は、昇温速度10℃/分でDSC(Differential Scanning Calorimetry)により測定されたガラス転移温度である。
なお、本発明においてフェノキシ樹脂(C)とは、エポキシ当量(1当量のエポキシ基あたりの樹脂の質量)が1000g/eqを越えるものである。つまり、フェノキシ樹脂の構造を有していても、エポキシ当量が1000g/eq以下である樹脂はエポキシ樹脂(A)に分類される。
いずれの反応においても、ビスフェノールもしくはビフェノール化合物としては、下記一般式(A)で表される化合物が好ましい。
アルキレン基は、炭素数が1~10が好ましく、1~6がより好ましく、1~3がさらに好ましく、1又は2が特に好ましく、1が最も好ましい。
アルキレン基は、-C(Rα)(Rβ)-が好ましく、ここで、Rα及びRβは各々独立に、水素原子、アルキル基、アリール基を表す。RαとRβが互いに結合して、環を形成してもよい。Rα及びRβは、水素原子又はアルキル基(例えば、メチル、エチル、イソプロピル、n-プロピル、n-ブチル、イソブチル、ヘキシル、オクチル、又は2-エチルヘキシル)が好ましい。アルキレン基は、なかでも-CH2-、-CH(CH3)-、又は-C(CH3)2-が好ましく、-CH2-、又は-CH(CH3)-がより好ましく、-CH2-がさらに好ましい。
アルキレン基とフェニレン基が組み合わされた基としては、アルキレン-フェニレン-アルキレン基が好ましく、-C(Rα)(Rβ)-フェニレン-C(Rα)(Rβ)-がより好ましい。
RαとRβが結合して形成する環は、5又は6員環が好ましく、シクロペンタン環、又はシクロヘキサン環がより好ましく、シクロヘキサン環がさらに好ましい。
例えば、エチレン、プロピレン、ブチレン、ペンチレン、へキシレン、及びオクチレンが挙げられ、エチレン、トリメチレン、テトラメチレン、ペンタメチレン、ヘプタメチレン、ヘキサメチレン、又はオクタメチレンが好ましい。
フェノキシ樹脂の骨格に着目すると、本発明では、ビスフェノールA型フェノキシ樹脂、又はビスフェノールA・F型共重合型フェノキシ樹脂を好ましく用いることができる。また、低弾性高耐熱型フェノキシ樹脂を好ましく用いることができる。
また、フェノキシ樹脂(C)中に僅かに残存するエポキシ基の量は、エポキシ当量で、5000g/eqを越えることが好ましい。
エポキシ樹脂(A)とフェノキシ樹脂(C)の各含有量の合計に占めるフェノキシ樹脂(C)の割合は10~60質量%であり、20~50質量%とすることも好ましく、30~50質量%とすることも好ましく、35~50質量%とすることも好ましい。
本発明のフィルム状接着剤は、エポキシ樹脂(A)、エポキシ樹脂硬化剤(B)、及びフェノキシ樹脂(C)の他に、本発明の規定を満たし、また本発明の効果を損なわない範囲で、これら以外の高分子化合物を含有してもよい。
上記高分子化合物としては、例えば、天然ゴム、ブチルゴム、イソプレンゴム、クロロプレンゴム、シリコーンゴム、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、ポリブタジエン樹脂、ポリカーボネート樹脂、熱可塑性ポリイミド樹脂、6-ナイロンや6,6-ナイロン等のポリアミド樹脂、(メタ)アクリル樹脂、ポリエチレンテレフタレート及びポリブチレンテレフタレート等のポリエステル樹脂、ポリアミドイミド樹脂、及びフッ素樹脂等が挙げられる。これらの高分子化合物は単独で用いてもよく、また2種以上を組み合わせて用いてもよい。
本発明のフィルム状接着剤に含まれるエポキシ樹脂(A)及びフェノキシ樹脂(C)の合計含有量は、50質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上がさらに好ましく、80質量%以上とすることも好ましい。
また、本発明のフィルム状接着剤は、本発明で規定する要件を満たす範囲で、イオントラップ剤(イオン捕捉剤)、硬化触媒、粘度調整剤、酸化防止剤、難燃剤、着色剤、及び無機充填材(無機フィラー)等をさらに含有していてもよい。例えば、国際公開第2017/158994号のその他の添加物を含むことができる。
なお、接着信頼性の観点からは、本発明のフィルム状接着剤は、染料や顔料などの着色剤を含有しないことが好ましい。また、無機充填材を含有しない形態であることも好ましい。
本発明のフィルム状接着剤の厚さは特に制限されず、目的に応じて適宜に設定することができる。本発明のフィルム状接着剤は、厚さを例えば1~30μmとすることができ、1~25μmとすることも好ましく、1~20μmとすることも好ましく、2~20μmとすることも好ましく、3~20μmとすることも好ましく、4~20μmとすることも好ましい。フィルム状接着剤の厚みは、接触・リニアゲージ方式(卓上型接触式厚み計測装置)により測定することができる。
本発明のフィルム状接着剤は、波長400nmの光透過率T1が90%以下であり、フィルム状接着剤を熱硬化してなる硬化物の、波長400nmの光透過率T2が85%以上であり、かつ、T1<T2を満たす。波長400nmの光透過率は、平行線透過率であり、後述する実施例に記載の方法により決定される。「フィルム状接着剤を熱硬化してなる硬化物」とは、フィルム状接着剤を、150℃で1時間処理して硬化させた硬化物を意味する。なお、本発明ないし明細書において、フィルム状接着剤の特性の説明で単に「本発明のフィルム状接着剤」という場合、熱硬化前のものを意味する。具体的には、フィルム状接着剤を調製後、エポキシ樹脂が熱硬化する温度以上の温度に曝されていないフィルム状接着剤を意味する。好ましくは、フィルム状接着剤を調製後、25℃以上の温度条件下に曝されていないフィルム状接着剤である。なお、上記の説明は、本発明のフィルム状接着剤の特性を明確にするためのものであり、本発明のフィルム状接着剤が、25℃以上の温度条件下に曝されていないものに限定されるものではない。
また、上記の光透過率T2が85%以上であることにより、熱硬化後において高い透明性を確保でき、透明フィルム状硬化物として、透明保護フィルムなどの接着に好適な光学特性を発現することができる。上記の光透過率T2は87%以上が好ましく、88%以上がより好ましく、90%以上がさらに好ましい。また、上記の光透過率T2は92%以上であることも好ましく、94%以上であることも好ましい。
さらに、本発明のフィルム状接着剤は、上記の光透過率T1よりも、上記の光透過率T2の方が高いものである。つまり、熱硬化により、透明性が向上するものである。すなわち、熱硬化前のフィルム状接着剤の状態では、光学センサによるフィルム状接着剤の位置や形状のセンシングを可能とし、高精度のプリカット加工をすることができ、かつ、熱硬化により透明性が高まり、イメージセンサなどの透明保護フィルムなどの接着に好適な光学特性を発現する。
本発明のフィルム状接着剤は、フィルム状接着剤を構成する各成分を、エポキシ樹脂(A)が事実上、熱硬化しない温度において混合してなる組成物(フィルム状接着剤形成用組成物(ワニス))を用いて成膜することにより得ることができる。混合の順は特に限定されない。例えば、エポキシ樹脂(A)、フェノキシ樹脂(C)等の樹脂成分を必要に応じて溶媒と共に混合し、その後、エポキシ樹脂硬化剤(B)を混合してもよい。この場合、エポキシ樹脂硬化剤(B)の存在下における混合を、エポキシ樹脂(A)が事実上、熱硬化しない温度で行えばよく、エポキシ樹脂硬化剤(B)の非存在下での樹脂成分の混合はより高い温度で行ってもよい。
上記のフィルム状接着剤形成用組成物を用いた成膜は、例えば、離型処理された基材フィルム(離型フィルム又は剥離フィルムとも称す)上にフィルム状接着剤形成用組成物を塗布し、必要に応じて乾燥させて形成することができる。
離型フィルムとしては、得られるフィルム状接着剤のカバーフィルムとして機能するものであればよく、通常のものを適宜採用することができる。例えば、離型処理されたポリプロピレン(PP)、離型処理されたポリエチレン(PE)、及び離型処理されたポリエチレンテレフタレート(PET)が挙げられる。
塗工方法としては、通常の方法を適宜採用することができ、例えば、ロールナイフコーター、グラビアコーター、ダイコーター、及びリバースコーター等を用いた方法が挙げられる。
乾燥は、エポキシ樹脂(A)が実質的に硬化せずに、フィルム状接着剤形成用組成物から有機溶媒を除去してフィルム状接着剤が得られればよく、例えば、80~150℃の温度で1~20分保持することにより行うことができる。
また、本発明のフィルム状接着剤は、フィルムを適当な大きさに切り出した形態であってもよく、フィルムをロール状に巻いてなる形態であってもよい。
上記熱圧着の条件は、エポキシ樹脂(A)が事実上、熱硬化しない温度で行う。一例を挙げれば、70℃、圧力0.3MPa程度の条件が挙げられる。
上記熱硬化反応は、本発明のフィルム状接着剤の熱硬化開始温度以上で行えばよい。熱硬化開始温度は、使用するエポキシ樹脂(A)、フェノキシ樹脂(C)及びエポキシ硬化剤(B)の種類により異なり、一概に言えるものではないが、例えば、100~180℃が好ましく、短時間の硬化を実現する観点から、140~180℃がより好ましい。温度が熱硬化開始温度未満であると、熱硬化反応が十分に進まず、接着層の強度が低下する傾向にある。他方、硬化反応の温度が高すぎると硬化反応中にフィルム状接着剤中のエポキシ樹脂、硬化剤、及び添加剤等が揮発して発泡しやすくなる傾向にある。また、硬化処理の時間は、例えば、10~120分間が好ましい。
上述した実施形態に関し、本発明によれば、次に示す電子部品の製造方法が提供される。
透明フィルム状部材と、本発明のフィルム状接着剤と、ダイシングフィルムとがこの順に積層された積層体を得る第1の工程と、
前記透明フィルム状部材と前記フィルム状接着剤とを一体にダイシングすることにより、前記ダイシングフィルム上に、接着剤層付き透明フィルム状チップを得る第2の工程と、
前記接着剤層から前記ダイシングフィルムを取り除き、前記接着剤層付き透明フィルム状チップと他の部材とを前記接着剤層を介して熱圧着する第3の工程と、
前記接着剤層を熱硬化する第4の工程と、
を含む電子部品の製造方法。
透明フィルム状チップが、本発明のフィルム状接着剤の熱硬化体を介して電子部品中に組み込まれた構造部を含む、電子部品。
本発明において「透明フィルム状チップ」とは、所望の形状に加工された透明フィルムを意味する。典型的には、ガラス基板や透明樹脂等の透明フィルム部材を、電子部品に組み込むために所望の形状に切り出したものである。
下記記載において、室温とは25℃を意味する。また、「MEK」はメチルエチルケトン、「PET」はポリエチレンテレフタレートである。
エポキシ樹脂(商品名:828、三菱ケミカル株式会社製、ビスフェノールA型エポキシ樹脂、エポキシ当量190g/eq、比重1.17)80質量部、エポキシ樹脂(商品名:EPICLON2050、DIC株式会社製、ビスフェノールA型エポキシ樹脂、エポキシ当量600g/eq、軟化点80℃)30質量部、フェノキシ樹脂(商品名:1256、三菱ケミカル株式会社製、ビスフェノールA型フェノキシ樹脂、エポキシ当量7500g/eq)70質量部を、1000mlのセパラブルフラスコ中において温度110℃で2時間、MEKとともに加熱攪拌し、樹脂ワニスを得た。次いで、この樹脂ワニスを別のフラスコ容器に移し、破砕処理済みのエポキシ樹脂硬化剤(商品名:DICY7、三菱ケミカル株式会社製、ジシアンジアミド化合物、累積分布頻度90%時の粒径(d90):0.95μm、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)2.5質量部を加えて、室温において1時間攪拌混合後、真空脱泡して混合ワニスを得た。さらに、得られた混合ワニスを厚み38μmの離型処理されたPETフィルム(剥離フィルム)上に塗布して、130℃で10分間加熱乾燥し、縦300mm、横300mm、厚みが5μmのフィルム状接着剤層を形成した。得られた剥離フィルム付きフィルム状接着剤は、10℃以下で保存した。上記乾燥後に、エポキシ樹脂は硬化していない(以下、特に言及のない場合、他の実施例及び比較例においても同じ)。
各樹脂とエポキシ樹脂硬化剤の配合量を下表の通りに変更したこと以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ10μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を破砕処理済みの硬化剤(商品名:N14、三菱ケミカル株式会社製、ヒドラジド化合物、累積分布頻度90%時の粒径(d90):2.0μm、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)1質量部に変更した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ10μm)を得た。
各樹脂とエポキシ樹脂硬化剤の配合量を下表の通りに変更したこと以外は、実施例3と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ10μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を未破砕処理品の硬化剤(商品名:DICY7、三菱ケミカル株式会社製、累積分布頻度90%時の粒径(d90):15.0μm、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)15質量部に変更した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ20μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を未破砕処理品の硬化剤(商品名:N14、三菱ケミカル株式会社製、累積分布頻度90%時の粒径(d90):18.0μm、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)15質量部に変更した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ20μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を未処理の硬化剤(商品名:SI-150、三新化学工業株式会社製、カチオン重合開始剤、25℃におけるMEKに対する溶解度10g以上/100g-MEK)5質量部に変更した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を顔料(商品名:C.I.Pig Black7、三菱ケミカル株式会社製、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)5質量部に変更した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を作製した。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を添加しなかったこと以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を得た。
各樹脂および硬化剤の配合量を下表の通りとしたこと以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を作製した。
各樹脂および硬化剤の配合量を下表の通りとしたこと以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を作製した。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を、未処理の硬化剤(商品名:ミレックスXLC-LL、三井化学株式会社製、フェノール化合物、25℃におけるMEKに対する溶解度10g以上/100g-MEK)35質量部に代え、さらに顔料(商品名:C.I.Pig Black7、三菱ケミカル株式会社製、25℃におけるMEKに対する溶解度0.01g未満/100g-MEK)4.2質量部を添加した以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を得た。
各樹脂の配合量を下表の通りとし、また、エポキシ樹脂硬化剤を未処理の硬化剤(商品名:ミレックスXLC-LL、三井化学株式会社製、フェノール化合物、25℃におけるMEKに対する溶解度10g以上/100g-MEK)35質量部に代えた以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ5μm)を得た。
樹脂の種類と配合量を下表の通りとし、また、エポキシ硬化剤を液状硬化剤(商品名:MH-700、株式会社新日本理化製、脂環式酸無水物、25℃におけるMEKに対する溶解度10g以上/100g-MEK)24質量部に代えた以外は、実施例1と同様にして剥離フィルム付きフィルム状接着剤(フィルム状接着剤の厚さ20μm)を得た。
エポキシ樹脂硬化剤を乾式粉砕機(商品名:ドライバースト・パラレルDB-180WP、スギノマシン製)にて回転数5000rev/minで3時間粉砕処理した。
エポキシ樹脂硬化剤0.1gとMEK9.9gを秤量し、これらの混合物に超音波分散処理を5分行い、測定用試料を調製した。この測定用試料について、レーザー回折・散乱法(型式:LMS-2000e、(株)セイシン企業製)により測定した粒度分布の粒径の体積分率の累積カーブから、累積分布頻度90%時の粒径(d90)を求めた。結果を表1に示す。
剥離フィルム上のフィルム状接着剤をガラス板に70℃で加熱貼合した後、剥離フィルムを剥がし、フィルム状接着剤付きガラスサンプルを得た。ガラス板単体の透過率をベースラインとし、熱硬化の前後におけるフィルム状接着剤の平行線透過率を、分光光度計(日立ハイテクノロジーズ社製、分光光度計U-4100型固体資料測定システム)を用いて測定した。硬化反応の条件は、150℃で1時間の熱処理とした。こうして各フィルム状接着剤の波長400nmの光透過率を決定した。
剥離フィルム付きフィルム状接着剤を、直径220mmの円形状に切り出した。この円形状の剥離フィルム付きフィルム状接着剤のフィルム状接着剤の側にダイシングフィルムを室温でラミネートした。次いで、円形状の剥離フィルム付きフィルム状接着剤よりも外側に位置するダイシングフィルムに対して、光学センサ(レーザーセンサ、波長600~700nm)を使用してセンシングしながら、円形状の剥離フィルム付きフィルム状接着剤と同心円状(ウエハリングフレーム形状に合わせた形状)に、ダイシングフィルムを直径290mmの円形状にプリカット加工した。このプリカット加工では、光学センサにより、円形状の剥離フィルム付きフィルム状接着剤とダイシングフィルムとの積層部分と、ダイシングフィルムのみの単層部分との透過率差を光学センサで認識し、円形状の剥離フィルム付きフィルム状接着剤が貼合されている場所を把握することで、ダイシングフィルムの所定の位置へ切り込みを入れた。各実施例および比較例において、それぞれ300枚のプリカット加工を実施し、加工成功率(%)を評価した。
剥離フィルム上に形成されたフィルム状接着剤の外観を、透過型光学顕微鏡を用いて観察した。無作為に4視野(4つの異なる領域、1領域の大きさ50mm×50mm)を観察し、平面視で下記評価基準に示す塊が確認された視野数を調べ、評価した。これにより、エポキシ樹脂硬化剤の均一分散性を評価することができる。
-評価基準-
A:使用した硬化剤のd90に対して1.5倍以上の最大寸法を有する塊が1つ以上確認された視野数が0視野
B:使用した硬化剤のd90に対して1.5倍以上の最大寸法を有する塊が1つ以上確認された視野数が1視野
C:使用した硬化剤のd90に対して1.5倍以上の最大寸法を有する塊が1つ以上確認された視野数が2視野以上
上記「最大寸法」とは、塊に外接する最小面積の長方形の長辺の長さを意味する。
なお、比較例2及び6については、上記評価基準における「使用した硬化剤のd90」ではなく「使用した顔料のd90」を基準にして評価した。また、粉体の硬化剤又は顔料を使用していない比較例7及び8は塊が認められなかったため、評価Aとした。
各実施例及び比較例において得られた剥離フィルム付フィルム状接着剤を、先ず、マニュアルラミネーター(商品名:FM-114、テクノビジョン社製)を用いて温度70℃、圧力0.3MPaにおいてダミーシリコンウェハ(8inchサイズ、厚さ350μm)の一方の面に熱圧着させた。その後、フィルム状接着剤から剥離フィルムを剥離した後、同マニュアルラミネーターを用いて室温、圧力0.3MPaにおいてフィルム状接着剤の前記ダミーシリコンウェハとは反対側の面上にダイシングフィルム(商品名:K-13、古河電気工業社製)及びダイシングフレーム(商品名:DTF2-8-1H001、DISCO社製)を圧着させた。次いで、2軸のダイシングブレード(Z1:NBC-ZH2050(27HEDD)、DISCO社製/Z2:NBC-ZH127F-SE(BC)、DISCO社製)が設置されたダイシング装置(商品名:DFD-6340、DISCO社製)を用いて2mm×2mmのサイズになるようにダミーシリコンウェハ側からフィルム状接着剤の厚さ方向に、フィルム状接着剤の厚さ全体に至る深さまでをダイシング(切断)して、ダイシングフィルム上に、接着剤付きダミーチップを得た。
次いで、ダイボンダー(商品名:DB-800、日立ハイテクノロジーズ社製)にて前記接着剤付きダミーチップをダイシングフィルムからピックアップし、120℃、圧力0.1MPa(荷重400gf)、時間1.0秒の条件において前記接着剤付きダミーチップの接着剤側と、被着体基板としてのダミーシリコンウエハ(厚さ700μm)とを貼り合わせて熱圧着した。次いで、温度150℃で1時間加熱することにより、接着剤を熱硬化させた。接着剤の熱硬化物を介して接着された被着体基板とダミーチップとの接着力を、せん断剥離力を指標にして評価した。せん断剥離力は、万能型ボンドテスター(商品名:シリーズ4000PXY、ノードソンアドバンストテクノロジー社製)を用いて測定した。
-評価基準-
A:せん断剥離力が20MPa以上
B:せん断剥離力が5MPa以上20MPa未満
C:せん断剥離力が5MPa未満
これに対し、本発明の規定を満たす実施例1~6のフィルム状接着剤は、顔料を用いずとも、エポキシ樹脂硬化剤の配合によって波長400nmの光透過率T1を90%以下へと低減でき、波長によらずに光学センサによる認識性に優れ、また、これらのフィルム状接着剤は、硬化後には透明性が高められ、優れた透明性を発現することもわかった。
2 離型フィルム
Claims (10)
- エポキシ樹脂(A)、エポキシ樹脂硬化剤(B)、及びフェノキシ樹脂(C)を含有するフィルム状接着剤であって、
前記フィルム状接着剤中、前記エポキシ樹脂硬化剤(B)の含有量が0.30~12.0質量%であり、
前記フィルム状接着剤の波長400nmの光透過率T1が90%以下、前記フィルム状接着剤を熱硬化してなる硬化物の波長400nmの光透過率T2が85%以上、かつT1<T2を満たす、フィルム状接着剤。 - 前記エポキシ樹脂硬化剤(B)が、累積分布頻度90%時の粒径(d90)が20.0μm以下の粉体であり、前記エポキシ樹脂硬化剤(B)が前記フィルム状接着剤中に分散してなる、請求項1に記載のフィルム状接着剤。
- 前記フィルム状接着剤の厚さが1~20μmである、請求項1又は2に記載のフィルム状接着剤。
- 前記フィルム状接着剤が着色剤を含有しない、請求項1~3のいずれか1項に記載のフィルム状接着剤。
- 前記フィルム状接着剤が無機充填材を含有しない、請求項1~4のいずれか1項に記載のフィルム状接着剤。
- 請求項1~5のいずれか1項に記載のフィルム状接着剤とダイシングフィルムとの積層体を含む、積層フィルム。
- 電子部品の製造方法であって、
透明フィルム状部材と、請求項1~5のいずれか1項に記載のフィルム状接着剤と、ダイシングフィルムとがこの順に積層された積層体を得る第1の工程と、
前記透明フィルム状部材と前記フィルム状接着剤とを一体にダイシングすることにより、ダイシングフィルム上に、接着剤層付き透明フィルム状チップを得る第2の工程と、
前記接着剤層から前記ダイシングフィルムを取り除き、前記接着剤層付き透明フィルム状チップと電子部品を構成する他の部材とを前記接着剤層を介して熱圧着する第3の工程と、
前記接着剤層を熱硬化する第4の工程と、
を含む電子部品の製造方法。 - 透明フィルム状チップが、請求項1~5のいずれか1項に記載のフィルム状接着剤の熱硬化体を介して電子部品中に組み込まれた構造部を含む、電子部品。
- 前記電子部品がイメージセンサである、請求項8に記載の電子部品。
- 前記透明フィルム状チップがフォトダイオードの保護フィルムとして組み込まれている、請求項9に記載の電子部品。
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