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 PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
film
adhesive
epoxy resin
curing agent
electronic component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/017919
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
小雪 坂井
稔 森田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Electric Co Ltd
Original Assignee
Furukawa Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Priority to KR1020237038614A priority Critical patent/KR102705562B1/ko
Priority to EP22860881.6A priority patent/EP4394861A4/en
Priority to MYPI2023007734A priority patent/MY209332A/en
Priority to JP2022545451A priority patent/JP7269446B1/ja
Priority to CN202280035301.0A priority patent/CN117321159A/zh
Priority to PH1/2023/553257A priority patent/PH12023553257A1/en
Publication of WO2023026584A1 publication Critical patent/WO2023026584A1/ja
Priority to US18/537,276 priority patent/US20240141216A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/011—Manufacture or treatment of image sensors covered by group H10F39/12
    • H10F39/026—Wafer-level processing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2463/00—Presence of epoxy resin

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Die Bonding (AREA)
  • Dicing (AREA)
  • Epoxy Resins (AREA)
PCT/JP2022/017919 2021-08-23 2022-04-15 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 Ceased WO2023026584A1 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1020237038614A KR102705562B1 (ko) 2021-08-23 2022-04-15 필름형 접착제, 이것을 사용한 전자 부품 및 그 제조 방법
EP22860881.6A EP4394861A4 (en) 2021-08-23 2022-04-15 FILM-TYPE ADHESIVE AGENT AND ELECTRONIC COMPONENT USING SAME AND PRODUCTION METHOD THEREOF
MYPI2023007734A MY209332A (en) 2021-08-23 2022-04-15 Film adhesive, electronic component using the same, and method of producing the same
JP2022545451A JP7269446B1 (ja) 2021-08-23 2022-04-15 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
CN202280035301.0A CN117321159A (zh) 2021-08-23 2022-04-15 膜状粘接剂、使用其的电子部件及其制造方法
PH1/2023/553257A PH12023553257A1 (en) 2021-08-23 2022-04-15 Film-like adhesive agent, and electronic component using same and method for producing same
US18/537,276 US20240141216A1 (en) 2021-08-23 2023-12-12 Film adhesive, electronic component using the same, and method of producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021135624 2021-08-23
JP2021-135624 2021-08-23

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/537,276 Continuation US20240141216A1 (en) 2021-08-23 2023-12-12 Film adhesive, electronic component using the same, and method of producing the same

Publications (1)

Publication Number Publication Date
WO2023026584A1 true WO2023026584A1 (ja) 2023-03-02

Family

ID=85322672

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/017919 Ceased WO2023026584A1 (ja) 2021-08-23 2022-04-15 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

Country Status (9)

Country Link
US (1) US20240141216A1 (https=)
EP (1) EP4394861A4 (https=)
JP (1) JP7269446B1 (https=)
KR (1) KR102705562B1 (https=)
CN (1) CN117321159A (https=)
MY (1) MY209332A (https=)
PH (1) PH12023553257A1 (https=)
TW (1) TW202309127A (https=)
WO (1) WO2023026584A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250033137A (ko) 2023-04-28 2025-03-07 후루카와 덴키 고교 가부시키가이샤 다이싱 필름 딸린 필름형 접착제, 이것을 사용한 전자 부품 및 그 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015506A (ja) * 2003-06-23 2005-01-20 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いた接着剤シート及びカバーレイフィルム並びに銅張りポリイミドフィルム
JP2005053940A (ja) * 2003-08-01 2005-03-03 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いたカバーレイフィルム、接着剤シート、銅張りポリイミドフィルム
JP2011111530A (ja) 2009-11-26 2011-06-09 Hitachi Chem Co Ltd 接着シート及びその製造方法、並びに、半導体装置の製造方法及び半導体装置
WO2015115553A1 (ja) * 2014-01-29 2015-08-06 日立化成株式会社 接着剤組成物、接着剤組成物を用いた半導体装置の製造方法、及び固体撮像素子
WO2017158994A1 (ja) 2016-03-15 2017-09-21 古河電気工業株式会社 フィルム状接着剤用組成物、フィルム状接着剤、フィルム状接着剤の製造方法、フィルム状接着剤を用いた半導体パッケージおよびその製造方法
JP2019143085A (ja) * 2018-02-23 2019-08-29 旭化成株式会社 熱硬化性エポキシ樹脂組成物、接着剤、エポキシ樹脂硬化物、塩、及び硬化剤
JP2020083998A (ja) * 2018-11-22 2020-06-04 三菱ケミカル株式会社 粘接着剤層、粘接着シート及び積層体
JP2021135624A (ja) 2020-02-26 2021-09-13 久知 竹内 徒歩移動交通安全見守り

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4665414B2 (ja) * 2004-03-24 2011-04-06 東レ株式会社 半導体装置用接着剤組成物およびそれを用いたカバーレイフィルム、接着剤シート、銅張りポリイミドフィルム
WO2008114696A1 (ja) * 2007-03-16 2008-09-25 Hitachi Chemical Company, Ltd. 光導波路用接着剤組成物、これを用いた光導波路用接着フィルムおよび光導波路用粘接着シート、ならびにこれらを用いた光学装置
JP5253315B2 (ja) * 2009-07-27 2013-07-31 大成プラス株式会社 溶剤型エポキシ接着剤及び接着方法
JP5901715B1 (ja) * 2014-09-05 2016-04-13 古河電気工業株式会社 フィルム状接着剤、フィルム状接着剤を用いた半導体パッケージ及びその製造方法
JP7269095B2 (ja) * 2019-05-29 2023-05-08 古河電気工業株式会社 ガラス加工用テープ
KR102734913B1 (ko) * 2020-09-29 2024-11-28 후루카와 덴키 고교 가부시키가이샤 투명 접착제용 조성물 및 필름형 투명 접착제와, 투명 접착제 경화층 딸린 부재의 제조 방법, 전자 부품 및 그 제조 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015506A (ja) * 2003-06-23 2005-01-20 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いた接着剤シート及びカバーレイフィルム並びに銅張りポリイミドフィルム
JP2005053940A (ja) * 2003-08-01 2005-03-03 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いたカバーレイフィルム、接着剤シート、銅張りポリイミドフィルム
JP2011111530A (ja) 2009-11-26 2011-06-09 Hitachi Chem Co Ltd 接着シート及びその製造方法、並びに、半導体装置の製造方法及び半導体装置
WO2015115553A1 (ja) * 2014-01-29 2015-08-06 日立化成株式会社 接着剤組成物、接着剤組成物を用いた半導体装置の製造方法、及び固体撮像素子
WO2017158994A1 (ja) 2016-03-15 2017-09-21 古河電気工業株式会社 フィルム状接着剤用組成物、フィルム状接着剤、フィルム状接着剤の製造方法、フィルム状接着剤を用いた半導体パッケージおよびその製造方法
JP2019143085A (ja) * 2018-02-23 2019-08-29 旭化成株式会社 熱硬化性エポキシ樹脂組成物、接着剤、エポキシ樹脂硬化物、塩、及び硬化剤
JP2020083998A (ja) * 2018-11-22 2020-06-04 三菱ケミカル株式会社 粘接着剤層、粘接着シート及び積層体
JP2021135624A (ja) 2020-02-26 2021-09-13 久知 竹内 徒歩移動交通安全見守り

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4394861A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250033137A (ko) 2023-04-28 2025-03-07 후루카와 덴키 고교 가부시키가이샤 다이싱 필름 딸린 필름형 접착제, 이것을 사용한 전자 부품 및 그 제조 방법

Also Published As

Publication number Publication date
JP7269446B1 (ja) 2023-05-08
US20240141216A1 (en) 2024-05-02
EP4394861A4 (en) 2025-07-16
MY209332A (en) 2025-07-02
CN117321159A (zh) 2023-12-29
KR20240025505A (ko) 2024-02-27
PH12023553257A1 (en) 2024-03-25
KR102705562B1 (ko) 2024-09-12
JPWO2023026584A1 (https=) 2023-03-02
EP4394861A1 (en) 2024-07-03
TW202309127A (zh) 2023-03-01

Similar Documents

Publication Publication Date Title
US11952513B2 (en) Adhesive composition, film-like adhesive and production method thereof, and semiconductor package using film-like adhesive and production method thereof
JP5130397B2 (ja) 熱硬化性樹脂組成物、先塗布型フリップチップ実装用接着剤、半導体装置の製造方法、及び、半導体装置
US12176314B2 (en) Dicing die attach film, and semiconductor package using the same and method of producing semiconductor package
WO2020157805A1 (ja) 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法
JP7269446B1 (ja) 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
WO2019022062A1 (ja) 半導体用接着フィルム及び半導体用接着シート
WO2019150446A1 (ja) 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法
US12570880B2 (en) Transparent adhesive composition, film-shaped transparent adhesive, method of producing transparent adhesive cured layer-attached member, and electronic component and method of producing the same
CN118613558A (zh) 膜状黏合剂、切割晶粒接合一体型膜、以及半导体装置及其制造方法
CN119110836A (zh) 膜状黏合剂、切割晶粒接合一体型膜、以及半导体装置及其制造方法
WO2023053566A1 (ja) 接着剤用組成物及びフィルム状接着剤、並びに、フィルム状接着剤を用いた半導体パッケージ及びその製造方法
WO2024225161A1 (ja) ダイシングフィルム付きフィルム状接着剤、これを用いた電子部品及びその製造方法
CN113165349A (zh) 膜状粘合剂、层叠片、复合片及层叠体的制造方法
JP7470885B1 (ja) エネルギー線硬化型フィルム状透明接着剤、これを含むデバイス及び該デバイスの製造方法
JP7421498B2 (ja) 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
JP2011088966A (ja) 接着剤組成物、接着用シート及びダイシング・ダイアタッチフィルム
JP2017065252A (ja) 積層体及び積層体の製造方法
CN113165350A (zh) 膜状粘合剂、层叠片、复合片及层叠体的制造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022545451

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22860881

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202280035301.0

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 12023553257

Country of ref document: PH

WWE Wipo information: entry into national phase

Ref document number: 2401000970

Country of ref document: TH

WWE Wipo information: entry into national phase

Ref document number: 2022860881

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2022860881

Country of ref document: EP

Effective date: 20240325