WO2022070503A1 - 透明接着剤用組成物及びフィルム状透明接着剤、並びに、透明接着剤硬化層付部材の製造方法、電子部品及びその製造方法 - Google Patents

透明接着剤用組成物及びフィルム状透明接着剤、並びに、透明接着剤硬化層付部材の製造方法、電子部品及びその製造方法 Download PDF

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Publication number
WO2022070503A1
WO2022070503A1 PCT/JP2021/020043 JP2021020043W WO2022070503A1 WO 2022070503 A1 WO2022070503 A1 WO 2022070503A1 JP 2021020043 W JP2021020043 W JP 2021020043W WO 2022070503 A1 WO2022070503 A1 WO 2022070503A1
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WIPO (PCT)
Prior art keywords
transparent adhesive
film
epoxy resin
curing agent
mass
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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
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PCT/JP2021/020043
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English (en)
French (fr)
Japanese (ja)
Inventor
稔 森田
小雪 坂井
慶太 綿引
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Filing date
Publication date
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Priority to PH1/2022/550506A priority Critical patent/PH12022550506A1/en
Priority to MYPI2022001314A priority patent/MY196339A/en
Priority to JP2021559598A priority patent/JP7687960B2/ja
Priority to EP21859376.2A priority patent/EP4047065B1/en
Priority to KR1020227003101A priority patent/KR102734913B1/ko
Priority to CN202180004621.5A priority patent/CN114599758B/zh
Priority to US17/686,190 priority patent/US12570880B2/en
Publication of WO2022070503A1 publication Critical patent/WO2022070503A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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
    • C09J2301/312—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

Definitions

  • the present invention relates to a composition for a transparent adhesive, a film-shaped transparent adhesive, a method for manufacturing a member with a transparent adhesive cured layer, an electronic component, and a method for manufacturing the same.
  • a transparent member such as a lens or glass is mounted in the optical device via a transparent adhesive (transparent adhesive).
  • transparent adhesive transparent adhesive
  • a paste-like adhesive has been conventionally used.
  • the paste-like adhesive tends to cause problems such as sticking out from the bonded portion at the time of bonding. Therefore, recently, film-like adhesives have come to be widely used as transparent adhesives.
  • the film-shaped transparent adhesive is also used as a die attach film in the manufacture of semiconductor devices for adhesion between a wiring substrate and a semiconductor chip and adhesion between semiconductor chips (so-called die attach).
  • Patent Document 1 describes a film-shaped adhesive containing a binder resin (A), an epoxy resin (B), a thermosetting agent (C) and a filler (D), wherein the epoxy resin (B) is used.
  • the content of the binder resin (A) is 100 to 1000 parts by mass with respect to 100 parts by mass
  • the average particle size of the filler (D) is 50 nm or less
  • the total light transmittance in the D65 standard light source is 70%.
  • a film-like adhesive having a haze value of 50% or less is disclosed, and as a specific embodiment of this film-like adhesive, a form using an acrylic resin as a binder resin is shown.
  • an alignment mark is provided on a part of the transparent member, a film-shaped transparent adhesive is bonded onto the alignment mark by thermocompression bonding, etc., and the bonded film-shaped transparent adhesive is passed through.
  • the transparent member may be attached to another member via the film-like transparent adhesive while optically recognizing the alignment mark.
  • a film-shaped transparent adhesive is used for adhering a transparent member, it is required that the desired transparency can be maintained even after the adhesive is cured.
  • the film-shaped transparent adhesive can be cured in a state of being attached to a transparent member or the like to function as a protective film for the transparent member. Even when used as such a protective film, it may be required to ensure the visibility of the alignment mark through the protective film when mounting the transparent member with the protective film.
  • the film-shaped transparent adhesive is required to have the property of being able to maintain its function as an adhesive until use, that is, storage stability.
  • storage stability when the uncured film-like transparent adhesive is left at room temperature (25 ° C.), for example, the curing reaction gradually progresses, and the desired adhesive performance may not be exhibited. Therefore, improvement of storage stability is important for the performance of the film-shaped transparent adhesive.
  • a film-shaped transparent adhesive using an epoxy resin it is known to use a solid-state adhesive at room temperature as a curing agent for the epoxy resin in order to improve storage stability.
  • a relatively low temperature for example, about 120 ° C.
  • the transparency is improved. It has been found that the temperature is lowered and the alignment mark is poorly recognized through the cured film.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and is a film-like transparent adhesive which exhibits sufficient transparency even after curing and has high storage stability at room temperature, and transparent adhesion using the same.
  • the present inventor has adopted a combination of an epoxy resin, an epoxy resin curing agent, and a phenoxy resin as a raw material for a film-shaped transparent adhesive, and then uses this epoxy resin curing agent as a specific grain. It has been found that the above-mentioned problems can be solved by using a powder having a diameter and having low solvent solubility. Based on these findings, the present invention has been further studied and completed.
  • (1) It is powdery and has a particle size (d90) of 2.0 ⁇ m or less when the cumulative distribution frequency is 90%.
  • Solubility in 100 g of methyl ethyl ketone is 0.1 g or less at 25 ° C.
  • the silica filler (D1) is contained, and the silica filler (D1) satisfies the following (3) and (4), and the epoxy resin (A), the epoxy resin curing agent (B), and the phenoxy resin (
  • the average particle size (d50) is 0.01 to 0.3 ⁇ m.
  • the particle size (d90) at a cumulative distribution frequency of 90% is 1.0 ⁇ m or less
  • a film-shaped transparent adhesive obtained by forming a film of the composition for a transparent adhesive according to any one of [1] to [4].
  • Manufacturing method of parts [10] It is a manufacturing method of electronic parts. The first step of thermocompression bonding the film-shaped transparent adhesive according to any one of [5] to [8] on one surface of the wafer and providing the dicing tape via the film-shaped transparent adhesive. A second step of obtaining a wafer chip with a transparent adhesive layer on a dicing tape by integrally dicing the wafer and the film-shaped transparent adhesive.
  • the fourth step of thermosetting the transparent adhesive layer and Manufacturing methods for electronic components including. [11] An electronic component in which a wafer chip and a wiring substrate and / or a wafer chip are bonded by a thermosetting body of a film-like transparent adhesive according to any one of [5] to [8].
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • (meth) acrylic means one or both of acrylic and methacrylic. The same applies to (meth) acrylate.
  • the film-shaped transparent adhesive of the present invention has excellent transparency even after thermosetting and is also excellent in storage stability at room temperature.
  • the transparent adhesive composition of the present invention can obtain the above-mentioned film-shaped transparent adhesive by forming a film thereof.
  • a member having a cured layer (protective layer or the like) having excellent transparency can be obtained.
  • the electronic component of the present invention having a cured layer having excellent transparency can be obtained.
  • FIG. 1 is a schematic vertical sectional view showing a preferred embodiment of the first step in the method for manufacturing an electronic component of the present invention.
  • FIG. 2 is a schematic vertical sectional view showing a preferred embodiment of the second step in the method for manufacturing an electronic component of the present invention.
  • FIG. 3 is a schematic vertical sectional view showing a preferred embodiment of the third step in the method for manufacturing an electronic component of the present invention.
  • FIG. 4 is a schematic vertical sectional view showing a preferred embodiment of a step of connecting bonding wires in the method for manufacturing an electronic component of the present invention.
  • FIG. 5 is a schematic vertical sectional view showing an example of a multi-stage laminated embodiment in the method for manufacturing an electronic component of the present invention.
  • FIG. 6 is a schematic vertical sectional view showing another example of a multi-stage laminated embodiment in the method for manufacturing an electronic component of the present invention.
  • FIG. 7 is a schematic vertical sectional view showing a preferred embodiment of an electronic component manufactured by the method for manufacturing an electronic component of the present invention.
  • the composition for a transparent adhesive of the present invention contains an epoxy resin (A), an epoxy resin curing agent (B), and a phenoxy resin (C).
  • the epoxy resin curing agent (B) satisfies the following (1) and (2).
  • (1) It is powdery and has a particle size (d90) of 2.0 ⁇ m or less when the cumulative distribution frequency is 90%.
  • (2) At 25 ° C., the solubility in 100 g of methyl ethyl ketone (MEK) is 0.1 g or less (that is, at 25 ° C.). Solubility in MEK is 0.1 g / 100 g-MEK or less (mass of epoxy resin curing agent soluble in 100 g of MEK at 25 ° C is 0.1 g or less))
  • the degree of transparency is not particularly limited as long as it has transparency. For example, it may be colorless and transparent, colored transparent, or translucent.
  • the fact that the epoxy resin curing agent (B) is in the form of powder means that the epoxy resin curing agent (B) is in the form of solid particles at room temperature (25 ° C., the same applies hereinafter).
  • the particle size (d90) of the epoxy resin curing agent (B) at a cumulative distribution frequency of 90% is 2.0 ⁇ m or less.
  • the particle size (d90) when the cumulative distribution frequency is 90% means the particle size when the total volume of particles is 90% in the cumulative distribution measured by the laser diffraction / scattering method. ..
  • the epoxy resin curing agent (B) As the epoxy resin curing agent (B), a commercially available product can also be used, and the above-mentioned “particle size (d90) at a cumulative distribution frequency of 90% is 2.0 ⁇ m or less” by pulverizing, sieving, etc., if necessary. Can also be satisfied.
  • the solubility of the epoxy resin curing agent (B) in MEK at room temperature (25 ° C.) is 0.1 g / 100 g-MEK or less. This solubility means the maximum amount of the epoxy resin curing agent (B) that dissolves in 100 g of MEK at room temperature.
  • MEK is widely used as a solvent used in a liquid composition obtained by dissolving an epoxy resin.
  • the solubility of the epoxy resin curing agent (B) in MEK at room temperature is 0.1 g / 100 g-MEK or less means that the epoxy resin curing agent (B) is difficult to dissolve in the composition for transparent adhesive. It represents that. Even if a solvent other than MEK is used in the composition for transparent adhesive, if the solubility of the epoxy resin curing agent (B) in MEK at room temperature is 0.1 g / 100 g-MEK or less, this epoxy is used. The resin curing agent (B) is difficult to dissolve in the solvent as well as in MEK.
  • the particle size (d90) of the epoxy resin curing agent (B) at a cumulative distribution frequency of 90% is preferably 0.05 to 2.0 ⁇ m, preferably 0.1 to 2.0 ⁇ m. More preferably, 0.2 to 2.0 ⁇ m is further preferable, and 0.3 to 1.0 ⁇ m is particularly preferable.
  • the solubility of the epoxy resin curing agent (B) in MEK at room temperature is preferably 0.005 to 0.1 g / 100 g-MEK, preferably 0.005 to 0.01 g / 100 g. -MEK is more preferred.
  • composition for a transparent adhesive of the present invention may further contain an inorganic filler (D).
  • the inorganic filler (D) will be described later.
  • the epoxy resin (A) is a thermosetting resin having an epoxy group, and has an epoxy equivalent of 500 g / eq or less.
  • the epoxy resin (A) may be liquid, solid or semi-solid.
  • a liquid means a softening point of less than 25 ° C.
  • a solid means a softening point of 60 ° C. or higher
  • a semi-solid means a softening point of the above liquid and a solid. It means that it is between the softening point of (25 ° C or higher and lower than 60 ° C).
  • the epoxy resin (A) used in the present invention has a softening point of 100 ° C.
  • the softening point is a value measured by a softening point test (ring-ball type) method (measurement conditions: based on JIS-2817).
  • the epoxy equivalent is preferably 150 to 450 g / eq from the viewpoint of increasing the crosslink density of the thermosetting body of the film-shaped transparent adhesive.
  • the epoxy equivalent means the number of grams (g / eq) of the resin containing 1 gram equivalent of the epoxy group.
  • the mass average molecular weight of the epoxy resin (A) is usually preferably less than 10,000, more preferably 5,000 or less. The lower limit is not particularly limited, but 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 phenol novolac type, orthocresol novolak type, cresol novolak type, dicyclopentadiene type, biphenyl type, fluorenbisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, Examples thereof include tetraphenyl type, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, and trimethylolmethane type.
  • triphenylmethane type bisphenol A type, cresol novolak type, and orthocresol novolak type are preferable from the viewpoint of obtaining a film-like transparent adhesive having low crystallinity of the resin and having a good appearance.
  • These may be used alone or in combination of two or more, and a combination of triphenylmethane type and bisphenol A type is preferable.
  • the content of the epoxy resin (A) is based on 100 parts by mass of the total content of the components (specifically, components other than the solvent) constituting the film-shaped transparent adhesive in the composition for transparent adhesive of the present invention. 3 to 80 parts by mass is preferable, 30 to 70 parts by mass is more preferable, and 40 to 70 parts by mass is further preferable.
  • 3 to 80 parts by mass is preferable, 30 to 70 parts by mass is more preferable, and 40 to 70 parts by mass is further preferable.
  • Epoxy resin curing agent (B) The epoxy resin curing agent (B) is not particularly limited as long as it satisfies the above (1) and (2), and any curing agent such as amines, acid anhydrides, and polyhydric phenols can be used. Can be used.
  • a latent curing agent it is preferable to use a latent curing agent from the viewpoint of obtaining a film-like transparent adhesive having high storage stability. By using a latent curing agent, it is possible to obtain a film-like transparent adhesive having a low melt viscosity, exhibiting thermosetting property at a high temperature exceeding a certain temperature, and having fast curing property.
  • Potential curing agents include dicyandiamide compounds, imidazole compounds, curing catalyst complex polyvalent phenol compounds, hydrazide compounds, boron trifluorinated-amine complexes, amineimide compounds, polyamine salts, and modified products and microcapsules of these. These include dicyandiamide compounds, imidazole compounds, and hydrazide compounds. These may be used alone or in combination of two or more. It is more preferable to use an imidazole compound from the viewpoint of having more excellent potential (excellent stability at room temperature and exhibiting curability by heating) and a faster curing rate.
  • the epoxy resin curing agent (B) accounts for the total content of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the inorganic filler (D).
  • 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 100 parts by mass, more preferably 1 to 80 parts by mass, still more preferably 2 to 50 parts by mass, and 4 20 parts by mass is more preferable, and 4 to 12 parts by mass is particularly preferable.
  • the curing time can be further shortened, while by setting the content to the above-mentioned preferable upper limit value or less, the residual of excess curing agent in the film-like transparent adhesive is suppressed. be able to.
  • the adsorption of water by the residual curing agent is suppressed, and the reliability of the semiconductor device can be improved.
  • it is preferably within the above range.
  • the phenoxy resin (C) is a component that suppresses film tackiness at room temperature (25 ° C.) and imparts film-forming property (film-forming property) when a film-like transparent adhesive is formed.
  • the phenoxy resin (C) preferably has an elastic modulus of 500 MPa or more at room temperature (25 ° C.).
  • the elastic modulus of the phenoxy resin (C) at room temperature (25 ° C.) is preferably 2000 MPa or less.
  • the elastic modulus at room temperature (25 ° C.) can be 1000 to 2000 MPa or 1500 to 2000 MPa.
  • the elastic modulus at room temperature (25 ° C.) can be determined by the method described later.
  • the elastic modulus at room temperature is the composition for transparent adhesive as a phenoxy resin film for measuring the elastic modulus at room temperature in the method described later. It can be determined by using a film prepared by blending a phenoxy resin in a mixing ratio constituting the above.
  • --Measurement method of normal temperature (25 °C) elastic modulus 30 parts by mass of various phenoxy resins and 70 parts by mass of MEK are heated and stirred in a 500 ml separable flask at a temperature of 110 ° C. for 2 hours to obtain a resin varnish.
  • this resin varnish was applied onto a PET film (release film) having a thickness of 38 ⁇ m and subjected to a mold release treatment, and dried by heating at 130 ° C. for 10 minutes. To get.
  • This phenoxy resin film is cut into a size of 5 mm ⁇ 17 mm, and a dynamic viscoelasticity measuring device (trade name: Rheogel-E4000F, manufactured by UBM Co., Ltd.) is used to measure a temperature range of 0 to 100 ° C. and a temperature rise rate of 5. The measurement is performed under the conditions of ° C./min and a frequency of 1 Hz, and the value of the elastic modulus at 25 ° C. is obtained.
  • the mass average molecular weight of the phenoxy resin (C) is usually 10,000 or more.
  • the upper limit is not particularly limited, but 5,000,000 or less is practical.
  • the mass average molecular weight of the phenoxy resin (C) is determined 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 even 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 at a heating rate of 0.1 ° C./min.
  • the composition for a transparent adhesive contains at least one kind of phenoxy resin as the phenoxy resin (C).
  • the phenoxy resin (C) has an epoxy equivalent (mass of the resin per equivalent epoxy group) exceeding 500 g / eq. That is, a resin having an epoxy equivalent structure of 500 g / eq or less even if it has a phenoxy resin structure is classified as an epoxy resin (A).
  • the phenoxy resin (C) can be obtained by a reaction between a bisphenol or a biphenol compound and epichlorohydrin such as epichlorohydrin, or a reaction between a liquid epoxy resin and a bisphenol or a 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
  • Ra 1 and Ra 2 each independently represent a substituent
  • ma and na each independently represent an integer from 0 to 4.
  • the divalent linking group is preferably an alkylene group, a phenylene group, -O-, -S-, -SO-, -SO 2- , or a group in which an alkylene group and a phenylene group are combined.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms, and most preferably 1.
  • the alkylene group is preferably —C (R ⁇ ) (R ⁇ ) —, where R ⁇ and R ⁇ independently represent a hydrogen atom, an alkyl group and an aryl group, respectively.
  • R ⁇ and R ⁇ may be combined 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, 2-ethylhexyl).
  • the alkylene group is preferably -CH 2- , -CH (CH 3 ), -C (CH 3 ) 2- , more preferably -CH 2- , -CH (CH 3 ), and further -CH 2- . preferable.
  • the phenylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and even more preferably 6.
  • Examples of the phenylene group include p-phenylene, m-phenylene and o-phenylene, and p-phenylene and m-phenylene are preferable.
  • 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 even more preferably a cyclohexane ring.
  • La is preferably a single bond or an alkylene group, —O—, —SO2- , and more preferably an alkylene group.
  • an alkyl group, an aryl group, an alkoxy group, an alkylthio group and a halogen atom are preferable, an alkyl group, an aryl group and a halogen atom are more preferable, and an alkyl group is further preferable.
  • Ma and na are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • the bisphenol or biphenol compound is, for example, 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, cardo skeleton
  • Examples thereof include bisphenol A, bisphenol AD, bisphenol C, bisphenol E, bisphenol F and 4,4'-biphenol, more preferably bisphenol A, bisphenol E and bisphenol F, and particularly preferably bisphenol A.
  • the liquid epoxy resin the aliphatic diol compound diglycidyl ether is preferable, and the compound represented by the following general formula (B) is more preferable.
  • X represents an alkylene group and nb represents an integer of 1 to 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 thereof include ethylene, propylene, butylene, pentylene, hexylene and octylene, with ethylene, trimethylene, tetramethylene, pentamethylene, heptamethylene, hexamethylene and octamethylene being preferred.
  • Nb is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1.
  • nb is 2 to 10
  • ethylene or propylene is preferable for X, and ethylene is more preferable.
  • Examples of the aliphatic diol compound in diglycidyl ether include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, and 1,6.
  • -Hexene diol, 1,7-pentane diol, 1,8-octane diol can be mentioned.
  • the bisphenol, the biphenol compound, and the aliphatic diol compound are each a phenoxy resin obtained by reacting alone, or may be a phenoxy resin obtained by mixing two or more kinds and reacting.
  • 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 more preferably a repeating unit phenoxy resin represented by the following general formula (I).
  • La, Ra1 , Ra2 , ma and na are synonymous with La , Ra1 , Ra2 , ma and na in the general formula ( A ), and the preferred range is also the same.
  • X and nb are synonymous with X and nb in the general formula (B), and the preferred range is also the same.
  • a polymer of bisphenol A and diglycidyl ether of 1,6-hexanediol is preferable. Focusing on the skeleton of the phenoxy resin, in the present invention, a bisphenol A type phenoxy resin and a bisphenol A / F type copolymer phenoxy resin can be preferably used. Further, a low elasticity and high heat resistant phenoxy resin can be preferably used.
  • the mass average molecular weight of the phenoxy resin (C) is preferably 10,000 or more, more preferably 10,000 to 100,000. Further, the amount of the epoxy group slightly remaining in the phenoxy resin (C) is preferably more than 5000 g / eq in terms of epoxy equivalent.
  • the phenoxy resin (C) may be synthesized by the method as described above, or a commercially available product may be used.
  • commercially available products include 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 manufactured by Shin-Nikka Epoxy Mfg. Co., Ltd.
  • FX-316 bisphenol F-type phenoxy resin, manufactured by Shin-Nikka Epoxy Mfg.
  • 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 15 to 50% by mass, and 18 to 45% by mass. It is also preferable to set it to%.
  • an inorganic filler usually used in a composition for a transparent adhesive can be used as long as the effect of the present invention is not impaired.
  • the inorganic filler (D) include ceramics such as silica, clay, gypsum, calcium carbonate, barium sulfate, alumina (aluminum oxide), beryllium oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride, and boron nitride. , Aluminum, copper, silver, gold, nickel, chromium, bell, tin, zinc, palladium, metals such as solder, or alloys, carbon nanotubes, carbons such as graphene and various other inorganic powders.
  • the inorganic filler (D) is a silica filler (D1) from the viewpoint of increasing the melt viscosity and enhancing the reliability (specifically, imparting a low coefficient of linear expansion, a low water absorption rate, etc.). Is preferable. From the viewpoint of storage stability and transparency, the average particle size (d50) of the silica filler (D1) is preferably 0.01 to 1.0 ⁇ m, preferably 0.01 to 0.8 ⁇ m, and 0.01 to 0. .3 ⁇ m is preferable, and 0.01 to 0.2 ⁇ m is more preferable.
  • the particle size (d90) of the silica filler (D1) at a cumulative distribution frequency of 90% is preferably 0.05 to 2.0 ⁇ m, preferably 0.05 to 1.0 ⁇ m. , 0.1-1.0 ⁇ m is more preferable.
  • the particle size (d90) of the silica filler (D1) at a cumulative distribution frequency of 90% is preferably 1.0 ⁇ m or less.
  • the silica filler (D1) is more preferably one that satisfies the following (3) and (4) from the viewpoint of storage stability and transparency.
  • the average particle size (d50) is 0.01 to 0.3 ⁇ m.
  • the particle size (d90) at a cumulative distribution frequency of 90% is 1.0 ⁇ m or less.
  • the average particle size (d50) is the so-called median diameter, and the particles are measured in the cumulative distribution by the laser diffraction / scattering method. It means the particle size when 50% is accumulated when the total volume of is 100%.
  • the particle size (d90) at a cumulative distribution frequency of 90% has the same meaning as the particle size (d90) at a cumulative distribution frequency of 90% described in the epoxy resin curing agent (B).
  • the range and preferable range of the average particle size (d50) of the inorganic filler (D) and the particle size (d90) at a cumulative distribution frequency of 90% are , The range described for the silica filler (D1) and the preferred range can be set.
  • Ratio of the content of the inorganic filler (D) to the total content (total solid content) of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C), and the inorganic filler (D). Is preferably 10 to 50% by mass, more preferably 10 to 30% by mass.
  • the ratio of the content of the silica filler (D1) to the total content of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the silica filler (D1) is 10 to 50. It is preferably by mass%, more preferably 10 to 30% by mass.
  • a method of blending the inorganic filler (D) with the resin components such as the epoxy resin (A), the epoxy resin curing agent (B) and the phenoxy resin (C), a powdery inorganic filler and, if necessary, are used.
  • a method of blending a slurry-like inorganic filler in which the treated inorganic filler is dispersed in an organic solvent can be used.
  • the method for treating the inorganic filler (D) with the silane coupling agent is not particularly limited, and is a wet method in which the inorganic filler (D) and the silane coupling agent are mixed in a solvent, and inorganic filling in the gas phase. Examples thereof include a dry method in which the material (D) and a silane coupling agent are mixed, and the above-mentioned inorganic blending method.
  • the silane coupling agent is one in which at least one hydrolyzable group such as an alkoxy group or an aryloxy group is bonded to a silicon atom, and in addition to this, an alkyl group, an alkenyl group, or an aryl group may be bonded. good.
  • the alkyl group is preferably substituted with an amino group, an alkoxy group, an epoxy group, or a (meth) acryloyloxy group, and is preferably an amino group (preferably a phenylamino group), an alkoxy group (preferably a glycidyloxy group), or a (meth) acryloyl. Those substituted with an oxy group are more preferable.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropylmethyldimethoxy.
  • Silane 3-glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltri Examples thereof include methoxysilane, 3-methacryloyl oxypropylmethyldimethoxysilane, 3-methacryloyl oxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloyl oxypropyltriethoxysilane.
  • the silane coupling agent and the surfactant are preferably contained in an amount of 0.1 to 25.0 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the inorganic filler (D). , 0.1 to 2.0 parts by mass is more preferable.
  • the content of the silane coupling agent or the surfactant in the above preferable range, the aggregation of the inorganic filler (D) is suppressed, and the semiconductor assembly heating step of the excess silane coupling agent or the surfactant (for example). Peeling at the adhesive interface due to volatilization in the reflow step) can be suppressed, the generation of voids can be suppressed, and the die attachability can be improved.
  • Examples of the shape of the inorganic filler (D) include flakes, needles, filaments, spheres, and scales, but spherical particles are preferable from the viewpoint of high filling and fluidity.
  • the silica filler (D1) is not used, and when the silica filler (D1) is used, the average particle size (d50) of the silica filler (D1) is 0.
  • the silica filler is set to 0.01 to 0.3 ⁇ m and accounts for the total content (total solid content) of the epoxy resin (A), the epoxy resin curing agent (B), the phenoxy resin (C) and the silica filler (D1).
  • the ratio of the content of (D1) is preferably 10 to 30% by mass.
  • a preferable form of the composition for a transparent adhesive of the present invention contains a silica filler (D1), the silica filler (D1) satisfies the above (3) and (4), and an epoxy resin (A) and an epoxy.
  • the ratio of the content of the silica filler (D1) to the total content (total solid content) of the resin hardener (B), the phenoxy resin (C) and the silica filler (D1) is 10 to 50% by mass. Is a form.
  • the composition for a transparent adhesive of the present invention contains polymers other than these as long as the effects of the present invention are not impaired. It may contain a compound.
  • the polymer compound include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, silicone rubber, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (meth) acrylic acid ester.
  • the composition for a transparent adhesive of the present invention preferably contains an organic solvent (MEK or the like).
  • MEK organic solvent
  • the proportion of MEK in the solvent is preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more.
  • composition for a transparent adhesive of the present invention may further contain an ion trapping agent (ion trapping agent), a curing catalyst, a viscosity modifier, an antioxidant, a flame retardant, a coloring agent and the like.
  • an ion trapping agent ion trapping agent
  • a curing catalyst ion trapping agent
  • a viscosity modifier ion trapping agent
  • an antioxidant ion trapping agent
  • the composition for a transparent adhesive of the present invention contains an epoxy resin (A), an epoxy resin curing agent (B), a phenoxy resin (C), and an inorganic filler (D), the inorganic filler (A), the inorganic filler (D), the inorganic filler (D), the inorganic filler (A), the epoxy resin curing agent (B), a phenoxy resin (C), and an inorganic filler (D), the inorganic filler (D) can be, for example, 60% by mass or more, preferably 70% by mass or more, further preferably 80% by mass or more, and also 90% by mass or more. Further, the above ratio may be 100% by mass or 95% by mass or less.
  • the composition for a transparent adhesive of the present invention can be suitably used for obtaining the film-shaped transparent adhesive of the present invention.
  • the adhesive is not limited to the transparent adhesive in the form of a film, and can be suitably used for obtaining a liquid adhesive.
  • the composition for a transparent adhesive of the present invention can be obtained by mixing each of the above components at a temperature at which the epoxy resin (A) is substantially not thermoset.
  • the order of mixing is not particularly limited.
  • Resin components such as the epoxy resin (A) and the phenoxy resin (C) may be mixed with a solvent, if necessary, and then the inorganic filler (D) and 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 virtually non-thermosetting, and the resin in the absence of the epoxy resin curing agent (B).
  • the components may be mixed at a higher temperature.
  • composition for a transparent adhesive of the present invention is stored under a temperature condition of 10 ° C. or lower before use (before the film-like transparent adhesive) from the viewpoint of suppressing the thermosetting of the epoxy resin (A). Is preferable.
  • the film-shaped transparent adhesive of the present invention is a film-shaped adhesive obtained by forming a film of the composition for transparent adhesive of the present invention, and is the above-mentioned epoxy resin (A) and epoxy resin curing agent (B). , And a phenoxy resin (C).
  • the invention of the film-shaped transparent adhesive according to the present invention can be specified as follows.
  • (1) It is powdery and has a particle size (d90) of 2.0 ⁇ m or less when the cumulative distribution frequency is 90%.
  • (2) Solubility in 100 g of methyl ethyl ketone is 0.1 g or less at 25 ° C.
  • the film-shaped transparent adhesive of the present invention may contain the above-mentioned inorganic filler (D) in addition to the above-mentioned epoxy resin (A), epoxy resin curing agent (B), and phenoxy resin (C).
  • additives other than the organic solvent may be contained.
  • the organic solvent is usually removed from the transparent adhesive composition by drying in the film forming step of the transparent adhesive composition, but if it is about 0.1 to 1000 ppm, it is contained in the film-shaped transparent adhesive. You may.
  • the film formation is not particularly limited as long as the transparent adhesive composition can be formed into a film. It can be performed by coating or the like described later.
  • the "film” means a film having a thickness of 200 ⁇ m or less.
  • the shape, size, etc. are not particularly limited and can be appropriately adjusted according to the usage mode.
  • the film-shaped transparent adhesive has thermosetting property, can be thermocompression bonded before thermosetting, and does not exhibit thermocompression bonding property after thermosetting.
  • the film-shaped transparent adhesive before thermosetting refers to the one in which the epoxy resin (A) is in a state before thermosetting.
  • the film-shaped transparent adhesive before thermosetting specifically means a film-shaped transparent adhesive that has not been exposed to a temperature condition of 25 ° C. or higher after forming the film-shaped transparent adhesive.
  • the film-shaped transparent adhesive after thermosetting means that the epoxy resin (A) is in a thermosetting state. Specifically, it refers to a film-like transparent adhesive of the present invention exposed to a temperature condition equal to or higher than the thermosetting start temperature.
  • the above description is for clarifying the characteristics of the film-shaped transparent adhesive of the present invention, and the film-shaped transparent adhesive of the present invention is not exposed to a temperature condition of 25 ° C. or higher. Not limited to.
  • the epoxy resin curing agent (B) is an adhesive depending on the type of the epoxy resin curing agent (B) in the film-shaped transparent adhesive after thermocompression bonding and / or heat curing. Although it melts / reacts with the components inside and is incorporated into the resin component, it is preferable that at least a part thereof maintains the powder shape due to recrystallization or the like.
  • the haze value of the film-shaped transparent adhesive of the present invention after thermosetting is not particularly limited, but is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
  • the lower the haze value the easier it is to visually recognize the alignment mark via the film-like transparent adhesive before and after thermosetting.
  • the lower limit of the haze value is not particularly limited, but 1% or more is practical.
  • the haze value is determined according to JIS K 7136. The haze value is determined by the content of the epoxy resin curing agent (B) and / or the inorganic filler (D), the type of the epoxy resin curing agent (B) and / or the inorganic filler (D), and the epoxy resin.
  • the haze value tends to be lower as the average particle size of the epoxy resin curing agent (B) and / or the inorganic filler (D) is smaller or the content is smaller.
  • the film-shaped transparent adhesive of the present invention has a melt viscosity at 120 ° C. when the temperature of the film-shaped transparent adhesive before thermosetting is raised from 25 ° C. to 5 ° C./min.
  • Is preferably in the range of 100 to 10000 Pa ⁇ s, more preferably in the range of 200 to 10000 Pa ⁇ s, more preferably in the range of 500 to 10000 Pa ⁇ s, and in the range of 1000 to 10000 Pa ⁇ s. It is more preferably in the range of 1500 to 10000 Pa ⁇ s, more preferably in the range of 8000 to 10000 Pa ⁇ s, and even more preferably in the range of 8000 to 9200 Pa ⁇ s.
  • the melt viscosity of the film-shaped transparent adhesive of the present invention may be in the range of 300 to 4000 Pa ⁇ s and 1000 to 3500 Pa ⁇ s.
  • the melt viscosity can be determined by the method described in Examples described later.
  • the melt viscosity is determined by adding the content of the epoxy resin curing agent (B) and / or the inorganic filler (D), the type of the epoxy resin curing agent (B) and / or the inorganic filler (D), and the epoxy resin. It can be controlled by the type and content of coexisting compounds or resins such as (A) and phenoxy resin (C).
  • the melt viscosity tends to increase as the average particle size of the epoxy resin curing agent (B) and / or the inorganic filler (D) is smaller and / or the content thereof is larger.
  • the film-shaped transparent adhesive of the present invention preferably has a thickness of 1 to 100 ⁇ m.
  • the thickness is more preferably 1 to 60 ⁇ m, further preferably 3 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the thickness of the film-shaped transparent adhesive can be measured by a contact / linear gauge method (desktop contact type thickness measuring device).
  • the method for preparing the film-shaped transparent adhesive of the present invention is not particularly limited.
  • the transparent adhesive composition (varnish) of the present invention can be prepared, applied on a release-treated base film, and dried if necessary.
  • the composition for a transparent adhesive usually contains an organic solvent.
  • the release-treated base film any known film may be used as long as it functions as a cover film for the obtained film-like transparent adhesive.
  • PP polypropylene
  • PE mold-released polyethylene
  • PET mold-released polyethylene terephthalate
  • the coating method a known method can be appropriately adopted, and examples thereof include a method using a roll knife coater, a gravure coater, a die coater, a reverse coater, and the like. Drying may be performed by removing the organic solvent from the composition for a transparent adhesive without curing the epoxy resin (A) to obtain a film-like transparent adhesive.
  • the drying temperature can be appropriately set depending on the types of the epoxy resin (A), the phenoxy resin (C) and the epoxy resin curing agent (B) used, and is held at a temperature of 80 to 150 ° C. for 1 to 20 minutes, for example. It can be done by doing.
  • the film-shaped transparent adhesive of the present invention may be composed of the film-shaped transparent adhesive of the present invention alone, and the above-mentioned release-treated base film is attached to at least one surface of the film-shaped transparent adhesive. It may be in the form of being combined. Further, the film-shaped transparent adhesive of the present invention may be in the form of a film cut out to an appropriate size, or may be in the form of a roll of the film.
  • the film-like transparent adhesive of the present invention preferably has an arithmetic average roughness Ra of at least one surface (that is, at least one surface to be bonded to the adherend) of 3.0 ⁇ m or less, and is adhered to the adherend. It is more preferable that the arithmetic average roughness Ra of the surfaces on either side to be combined is 3.0 ⁇ m or less.
  • the arithmetic mean roughness Ra is more preferably 2.0 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
  • the lower limit is not particularly limited, but it is practically 0.1 ⁇ m or more.
  • the film-shaped transparent adhesive of the present invention is preferably stored under a temperature condition of 10 ° C. or lower before use (before curing) from the viewpoint of suppressing the curing of the epoxy resin (A).
  • the film-shaped transparent adhesive of the present invention has high storage stability and can maintain sufficiently high transparency even when heat-cured.
  • the epoxy resin, the epoxy resin curing agent, and the phenoxy resin are used, and the epoxy resin curing agent is a powdered epoxy resin curing agent having a specific particle size and solubility. This makes it possible to reduce the haze value after heat curing while reducing the compatibility between the epoxy resin curing agent and the epoxy resin and / or the phenoxy resin to improve storage stability before heat curing. Conceivable.
  • a transparent adhesive cured layer made of a thermosetting body of a film-shaped transparent adhesive is formed by using the film-shaped transparent adhesive of the present invention, and transparently bonded. It can be carried out by a usual method except that the member has a curing layer.
  • the transparent adhesive cured layer functions as, for example, a protective layer for the adherend.
  • a preferred embodiment of the method for producing a member with a transparent adhesive curing layer of the present invention includes thermocompression bonding a film-shaped transparent adhesive onto an adherend member and further thermosetting the film-shaped transparent adhesive.
  • the adherend member examples include a member used for an optical device such as an optical lens, an optical fiber, an optical waveguide, an optical isolator, and a semiconductor laser, and a member used for manufacturing an electronic component described later.
  • the adherend member is preferably a transparent member such as a lens, glass (cover glass, glass substrate, glass wafer, etc.), a resin substrate, or the like.
  • a plurality of film-shaped transparent adhesives may be used to form a transparent adhesive cured layer.
  • the conditions for thermocompression bonding and thermosetting are the same as the conditions for thermocompression bonding and thermosetting in the method for manufacturing electronic components described later.
  • the transparent adhesive cured layer thus formed exhibits the same haze value as the above-mentioned film-shaped transparent adhesive after heat curing. The preferred range is similar.
  • Another preferred embodiment of the method for manufacturing a member with a transparent adhesive cured layer of the present invention is a method for manufacturing electronic components, which will be described later.
  • the adherend member in the method for manufacturing a member with a transparent adhesive curing layer corresponds to a wafer in a method for manufacturing an electronic component, and the member with a transparent adhesive curing layer corresponds to an electronic component.
  • the electronic component of the present invention is formed by adhering at least one between a wafer chip (preferably a semiconductor chip) and a wiring substrate, and between the wafer chips by a heat-cured body of the film-shaped transparent adhesive of the present invention.
  • a wafer chip preferably a semiconductor chip
  • a wiring substrate As the wafer chip and the wiring board, ordinary ones can be used. The bonding conditions will be described later in the description of the manufacturing method.
  • the electronic component is preferably a semiconductor package, a capacitor, a resistor, or the like, and more preferably a semiconductor package.
  • the method for manufacturing an electronic component of the present invention is the same as the method for manufacturing a normal electronic component except that the film-like transparent adhesive of the present invention is used for bonding at least one of the wafer chip and the wiring substrate and between the wafer chips. Can be done.
  • a preferred embodiment of the method for manufacturing an electronic component of the present invention is as follows. That is, it is a manufacturing method of electronic parts.
  • the fourth step of thermosetting the transparent adhesive layer and Manufacturing methods for electronic components including.
  • a normal wafer can be used, and examples thereof include a semiconductor wafer, a glass wafer, and a ceramic wafer.
  • the semiconductor wafer include a silicon wafer, a SiC wafer, a GaAs wafer, and a GaN wafer.
  • a semiconductor circuit may or may not be formed on the surface of the wafer. It is preferable that at least one semiconductor circuit is formed on the surface of the wafer.
  • the other member may be a member constituting an electronic component, and examples thereof include a wiring board, another wafer, and a bonding wire.
  • Another preferred embodiment of the method for manufacturing electronic components of the present invention is as follows. That is, it is a manufacturing method of a semiconductor package.
  • the fourth step of thermosetting the transparent adhesive layer and A method for manufacturing a semiconductor package including.
  • 1 to 7 are schematic vertical sectional views showing a preferred embodiment of each step of the method for manufacturing a semiconductor package, which is a preferred embodiment of the present invention.
  • 1 to 7 are schematic views, and for convenience of explanation, the size and relative magnitude relationship of each member such as a semiconductor wafer may differ from the actual one.
  • a semiconductor wafer 1 having at least one semiconductor circuit formed on its surface is formed.
  • the adhesive layer 2 is provided by thermocompression bonding the film-like transparent adhesive of the present invention on the back surface of the semiconductor wafer 1 (that is, the surface on which the semiconductor circuit of the semiconductor wafer 1 is not formed), and the dicing tape 3 is passed through the adhesive. Is provided.
  • the product in which the adhesive layer 2 and the dicing tape 3 are integrated may be thermocompression bonded to the back surface of the semiconductor wafer 1 at one time.
  • the conditions for thermocompression bonding are such that the epoxy resin (A) is not substantially thermoset.
  • the conditions of 70 ° C. and a pressure of 0.3 MPa can be mentioned.
  • the adhesive layer 2 the film-like transparent adhesive of the present invention may be used alone as one layer or may be used by laminating two or more layers.
  • a method of providing such an adhesive layer 2 on the back surface of the wafer 1 a method capable of laminating a film-like transparent adhesive on the back surface of the semiconductor wafer 1 can be appropriately adopted, and the back surface of the semiconductor wafer 1 can be appropriately adopted.
  • a method of sequentially laminating the film-shaped transparent adhesive until the desired thickness is obtained, or a film-shaped transparent adhesive having a desired thickness in advance examples thereof include a method of laminating on the back surface of the semiconductor wafer 1 and then laminating it on the back surface of the semiconductor wafer 1.
  • the device used when providing such an adhesive layer 2 on the back surface of the semiconductor wafer 1 is not particularly limited, and for example, a known device such as a roll laminator or a manual laminator can be appropriately used.
  • the dicing tape 3 is not particularly limited, and a known dicing tape can be used as appropriate.
  • the semiconductor wafer 1 semiconductor wafer 4
  • the transparent adhesive layer are placed on the dicing tape 3.
  • a semiconductor chip 5 with a transparent adhesive layer comprising 2 is obtained.
  • the device used for dicing is not particularly limited, and a known dicing device can be used as appropriate.
  • the dicing tape 3 is removed from the adhesive layer 2, and the semiconductor chip 5 with the transparent adhesive layer and the wiring substrate 6 are thermocompression bonded via the transparent adhesive layer 2. do.
  • the semiconductor chip 5 with the transparent adhesive layer is mounted on the wiring board 6.
  • a substrate having a semiconductor circuit formed on its surface can be appropriately used.
  • a printed circuit board (PCB) various lead frames, and electronic components such as resistance elements and capacitors are mounted on the surface of the substrate. The board is mentioned.
  • a pick-up method using a normal jig can be adopted, specifically, a needle, a slider, or the like.
  • a method of peeling from the dicing tape 3 with the jig of the above can be mentioned.
  • the method of mounting the semiconductor chip 5 with the transparent adhesive layer on the wiring board 6 is not particularly limited, and the semiconductor chip 5 with the transparent adhesive layer is mounted on the wiring board 6 or the surface of the wiring board 6 by using the transparent adhesive layer 2. Conventional methods that can be adhered to the electronic components mounted on the top can be appropriately adopted.
  • a mounting method conventionally known heating such as a method using a mounting technique using a flip-chip bonder having a heating function from the upper part, a method using a die bonder having a heating function only from the lower part, and a method using a laminator. , Pressurization method can be mentioned.
  • the mounting (thermocompression bonding) conditions are such that the epoxy resin (A) is not substantially thermoset.
  • the conditions of 120 ° C., pressure of 0.1 MPa, and 1.0 second can be mentioned.
  • the semiconductor chip 5 on the wiring board 5 generated by the electronic component is mounted. Since the film-like transparent adhesive can be made to follow the uneven portion, the semiconductor chip 4 and the wiring board 6 can be brought into close contact with each other and fixed.
  • the transparent adhesive layer 2 (the film-shaped transparent adhesive of the present invention) is thermoset to obtain a thermosetting body.
  • the thermosetting temperature is not particularly limited as long as it is equal to or higher than the thermosetting start temperature of the film-shaped transparent adhesive of the present invention, and the epoxy resin (A), phenoxy resin (C) and epoxy resin curing agent (B) to be used are used. It depends on the type of epoxy, and it cannot be said unconditionally, but for example, 100 to 180 ° C is preferable, and 140 to 180 ° C is more preferable from the viewpoint that curing at a higher temperature can be cured in a short time. preferable.
  • thermosetting does not proceed sufficiently and the strength of the adhesive layer 2 tends to decrease.
  • the temperature exceeds the above upper limit, the epoxy in the film-like transparent adhesive during the curing process tends to decrease. Resins, curing agents, additives, etc. tend to volatilize and easily foam.
  • the curing treatment time is preferably, for example, 10 to 120 minutes.
  • connection method is not particularly limited, and a conventionally known method, for example, a wire bonding method, a TAB (Tape Automated Bonding) method, or the like can be appropriately adopted.
  • a plurality of semiconductor chips 4 can be laminated by thermocompression bonding, thermocompression bonding, and reconnecting to the wiring board 6 by a wire bonding method on the surface of the mounted semiconductor chip 4.
  • a method of staggering and laminating semiconductor chips as shown in FIG. 5, or a method of laminating while embedding a bonding wire 7 by thickening the second and subsequent adhesive layers 2 as shown in FIG. be.
  • the semiconductor package 9 can be obtained.
  • the encapsulating resin 8 is not particularly limited, and an appropriately known encapsulating resin that can be used for manufacturing a semiconductor package can be used. Further, the sealing method using the sealing resin 8 is not particularly limited, and a known method can be appropriately adopted.
  • room temperature means 25 ° C.
  • MEK is methyl ethyl ketone
  • PET is polyethylene terephthalate. Details of the pulverization treatment of the epoxy resin curing agent used in each Example and Comparative Example, and a method of measuring the particle size distribution before and after the pulverization treatment will be described separately later.
  • Triphenylmethane type epoxy resin (trade name: EPPN-501H, mass average molecular weight: 1000, softening point: 55 ° C, semi-solid, epoxy equivalent: 167 g / eq, manufactured by Nippon Kayaku Co., Ltd.) 56 parts by mass, bisphenol A Type Epoxy resin (trade name: YD-128, mass average molecular weight: 400, softening point: 25 ° C or less, liquid, epoxy equivalent: 190 g / eq, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.) 49 parts by mass, bisphenol A type Phenoxy resin (trade name: YP-50, mass average molecular weight: 70000, Tg: 84 ° C., room temperature (25 ° C.) elasticity: 1700 MPa, manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.) 30 parts by mass and 67 parts by mass of MEK 1000 ml A resin varnish was obtained by heating and stirring at a temperature of 110 ° C
  • imidazole compound trade name: 2PHZ-PW, Made by Shikoku Kasei Co., Ltd., average particle size (d50): 0.15 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.39 ⁇ m, solubility in MEK at 25
  • the obtained mixed varnish was applied onto a PET film (release film) having a thickness of 38 ⁇ m and subjected to mold release treatment, and dried by heating at 130 ° C. for 10 minutes.
  • a film-like transparent adhesive with a release film was obtained as an adhesive layer.
  • the obtained film-like transparent adhesive with a release film was stored at 10 ° C. or lower. After the above drying, the epoxy resin has not been cured (hereinafter, the same applies to other Examples and Comparative Examples unless otherwise specified).
  • Example 2 Silica slurry filler (trade name: YA010C-MFN, manufactured by Admatex Co., Ltd., average particle size (d50): 0.01 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 0.1 ⁇ m, solid content 30%
  • a film-shaped transparent adhesive with a release film was produced in the same manner as in Example 1 except that the amount of (organic solvent: MEK) used was 203 parts by mass (of which 61 parts by mass of the silica filler).
  • Example 3 Silica slurry filler (trade name: YA010C-MFN, manufactured by Admatex Co., Ltd., average particle size (d50): 0.01 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 0.1 ⁇ m, solid content 30%
  • a film-shaped transparent adhesive with a release film was produced in the same manner as in Example 1 except that the amount of (organic solvent: MEK) used was 477 parts by mass (of which 143 parts by mass of the silica filler).
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m,
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 60% (organic solvent: MEK) and 27 parts by mass (of which 16 parts by mass of silica filler) was replaced.
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m,
  • a film-shaped transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 60% (organic solvent: MEK) and 102 parts by mass (of which 61 parts by mass of silica filler) was replaced.
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m,
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 60% (organic solvent: MEK) and 238 parts by mass (of which 143 parts by mass of silica filler) was replaced.
  • Example 7 Silica slurry filler (trade name: SIRMEK50WT% -M01, manufactured by CIK Nanotech Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 1.0 ⁇ m
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 50% (organic solvent: MEK) and 32 parts by mass (of which 16 parts by mass of silica filler) was replaced.
  • Example 8 Silica slurry filler (trade name: SIRMEK50WT% -M01, manufactured by CIK Nanotech Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 1.0 ⁇ m
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 50% (organic solvent: MEK) and 122 parts by mass (of which 61 parts by mass of the silica filler) was replaced.
  • Example 9 Silica slurry filler (trade name: SIRMEK50WT% -M01, manufactured by CIK Nanotech Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 1.0 ⁇ m
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 1 except that the solid content was 50% (organic solvent: MEK) and replaced with 286 parts by mass (of which 143 parts by mass of silica filler).
  • Example 10 Dicyandiamide obtained by crushing an epoxy resin curing agent (trade name: DICY7, manufactured by Mitsubishi Chemical Co., Ltd., average particle size (d50): 0.5 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.95 ⁇ m, A film-like transparent adhesive with a release film was produced in the same manner as in Example 9 except that the solubility in MEK at 25 ° C. was less than 0.01 g / 100 g-MEK) by 7.5 parts by mass.
  • an epoxy resin curing agent trade name: DICY7, manufactured by Mitsubishi Chemical Co., Ltd., average particle size (d50): 0.5 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.95 ⁇ m
  • Example 11 Organic acid hydrazide obtained by crushing an epoxy resin curing agent (trade name: N14, manufactured by Mitsubishi Chemical Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 2.
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 9 except that the solubility in MEK at 0 ⁇ m and 25 ° C. was less than 0.01 g / 100 g-MEK) by 28.5 parts by mass.
  • Example 12 Silica slurry filler (trade name: SIRMEK50WT% -M01, CIK Nanotech Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 1.0 ⁇ m, solid content 50%
  • Silica slurry filler (trade name: SIRMEK50WT% -M01, CIK Nanotech Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 1.0 ⁇ m, solid content 50%
  • MEK organic solvent
  • Example 1 An imidazole compound obtained by crushing an epoxy resin curing agent (trade name: 2PHZ-PW, manufactured by Shikoku Chemicals Corporation, average particle size (d50): 1.9 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: A film-like transparent adhesive with a release film was produced in the same manner as in Example 3 except that the solubility in MEK at 3.9 ⁇ m and 25 ° C. was less than 0.01 g / 100 g-MEK) by 8.5 parts by mass.
  • an epoxy resin curing agent trade name: 2PHZ-PW, manufactured by Shikoku Chemicals Corporation, average particle size (d50): 1.9 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%:
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 3 except that the solubility in MEK at 3.9 ⁇ m and 25 ° C. was less than 0.01 g / 100 g-MEK) by 8.5 parts by mass.
  • Comparative Example 2 Silica slurry filler (trade name: YA010C-MFN, manufactured by Admatex Co., Ltd., average particle size (d50): 0.01 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 0.1 ⁇ m, solid content 30%
  • a film-shaped transparent adhesive with a release film was produced in the same manner as in Comparative Example 1 except that the amount of (organic solvent: MEK) used was 713 parts by mass (of which 214 parts by mass of the silica filler).
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m,
  • a film-like transparent adhesive with a release film was produced in the same manner as in Comparative Example 1 except that the solid content was 60% (organic solvent: MEK) and 238 parts by mass (of which 143 parts by mass of silica filler) was replaced.
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m,
  • a film-like transparent adhesive with a release film was produced in the same manner as in Comparative Example 1 except that the solid content was 60% (organic solvent: MEK) and 357 parts by mass (of which 214 parts by mass of silica filler) was replaced.
  • the inorganic filler is a silica slurry filler (trade name: YC100C-MLA, manufactured by Admatex Co., Ltd., average particle size (d50): 0.1 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 0.3 ⁇ m, Instead of 272 parts by mass of solid content (organic solvent: MEK) (of which 163 parts by mass of silica filler), an epoxy resin curing agent is crushed and untreated organic acid hydrazide (trade name: N14, Mitsubishi Chemical Co., Ltd., average).
  • a film-like transparent adhesive with a release film was produced in the same manner as in Comparative Example 1 except for the above.
  • the inorganic filler is a silica slurry filler (trade name: SC2050-MNU, manufactured by Admatex Co., Ltd., average particle size (d50): 0.8 ⁇ m, particle size (d90) at a cumulative distribution frequency of 90%: 5.0 ⁇ m,
  • a film-shaped transparent adhesive with a release film was produced in the same manner as in Comparative Example 1 except that the solid content was 70% (organic solvent: MEK) and 204 parts by mass (of which 143 parts by mass of silica filler) was replaced.
  • Example 10 An imidazole compound obtained by crushing an epoxy resin curing agent (trade name: 2E4MZ, manufactured by Shikoku Chemicals Corporation, average particle size (d50): 2.2 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%): 5.
  • An imidazole compound obtained by crushing an epoxy resin curing agent (trade name: 2E4MZ, manufactured by Shikoku Chemicals Corporation, average particle size (d50): 2.2 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%): 5.
  • a film-like transparent adhesive with a release film was produced in the same manner as in Example 12 except that the solubility in MEK at 4 ⁇ m and 25 ° C. was 10 g or more / 100 g-MEK) 8.5 parts by mass.
  • Comparative Example 12 Silica slurry filler (trade name: YA010C-MFN, manufactured by Admatex Co., Ltd., average particle size (d50): 0.01 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 0.1 ⁇ m, solid content 30%
  • Silica slurry filler (trade name: YA010C-MFN, manufactured by Admatex Co., Ltd., average particle size (d50): 0.01 ⁇ m, particle size (d90) when cumulative distribution frequency is 90%: 0.1 ⁇ m, solid content 30%
  • MEK organic solvent
  • the particle size of the epoxy resin curing agent used in each Example and Comparative Example was adjusted by the following pulverization treatment.
  • Various epoxy resin curing agents were treated with a dry crusher (trade name: Dryst Parallel DB-180WP, manufactured by Sugino Machine Limited) at a rotation speed of 5000 rev / min for 3 hours.
  • the particle size distribution of the epoxy resin curing agent used in each Example and Comparative Example before and after the pulverization treatment was measured as follows. (Measurement of particle size distribution of curing agent before and after crushing treatment) 0.1 g of the epoxy resin curing agent and 9.9 g of isopropyl alcohol (IPA) before and after the crushing treatment were weighed, and the mixture thereof was subjected to ultrasonic dispersion treatment for 5 minutes to prepare a sample for measurement. For this measurement sample, the average particle size (d50) and the cumulative particle size (d50) are accumulated from the cumulative curve of the volume fraction of the particle size distribution measured by the laser diffraction / scattering method (model: LMS-2000e, manufactured by Seishin Co., Ltd.). The particle size (d90) at a distribution frequency of 90% was determined. The results are shown in Table 1.
  • the solubility of the epoxy resin curing agent used in each Example and Comparative Example in 100 g of the solvent (MEK) was determined as follows. (Solubility of epoxy resin curing agent (g / 100g-MEK)) 10 g of each epoxy resin curing agent was weighed in a beaker, 100 g of MEK was added, and the mixture was stirred at room temperature (25 ° C.) with a magnetic stirrer for a predetermined time (60 minutes). After stirring, the insoluble epoxy resin curing agent was collected by filtration, the amount of the epoxy resin curing agent in the insoluble component Xg was measured, and the solubility was calculated as (10-X) g.
  • the particle size distribution of the inorganic filler used in each Example and Comparative Example was carried out by the same method as described above (measurement of particle size distribution of the curing agent before and after the crushing treatment).
  • thermosetting film-like transparent adhesive was measured with a haze meter (model; HZ-V3, manufactured by Suga Test Instruments Co., Ltd.) using a measuring hole diameter of 20 mm ⁇ and a light source D65 light.
  • melt viscosity From the film-like transparent adhesive with a release film obtained in each Example and Comparative Example, a square having a size of 5.0 cm in length ⁇ 5.0 cm in width was cut out, and the cut samples were laminated with the release film peeled off, and 70 A test piece having a thickness of about 1.0 mm was obtained by bonding with a hand roller on a stage at ° C. For this test piece, a leometer (RS6000, manufactured by Hake) was used to measure the change in viscous resistance in a temperature range of 20 to 250 ° C. and a heating rate of 5 ° C./min. From the obtained temperature-viscosity resistance curve, the melt viscosity (Pa ⁇ s) at 120 ° C. was calculated.
  • RS6000 manufactured by Hake
  • a dummy film-like transparent adhesive with a release film obtained in each Example and Comparative Example was used at a temperature of 70 ° C. and a pressure of 0.3 MPa using a manual laminator (trade name: FM-114, manufactured by Technovision Co., Ltd.). It was adhered to one surface of a silicon wafer (8 inch size, thickness 100 ⁇ m). Then, after peeling the release film from the film-shaped transparent adhesive, a dicing tape (commodity) is used on the surface of the film-shaped transparent adhesive on the surface opposite to the dummy silicon wafer at room temperature and pressure of 0.3 MPa using the same manual laminator.
  • a manual laminator trade name: FM-114, manufactured by Technovision Co., Ltd.
  • K-13 manufactured by Furukawa Denki Kogyo Co., Ltd.
  • dicing frame (trade name: DTF2-8-1H001, manufactured by DISCO) were adhered.
  • a dicing device (trade name: DFD-6340, manufactured by DISCO) equipped with a two-axis dicing blade (Z1: NBC-ZH2050 (27HEDD), Z2: NBC-ZH127F-SE (BC), DISCO).
  • Z1 NBC-ZH2050 (27HEDD)
  • Z2 NBC-ZH127F-SE (BC)
  • DISCO DISCO
  • the dummy chip with a film-like transparent adhesive was picked up from the dicing tape, and the pressure was 0.1 MPa (load 400 gf) at 120 ° C.
  • the film-shaped transparent adhesive side of the dummy chip with the film-shaped transparent adhesive and the mounting surface side of the lead frame substrate (42 Alloy system, manufactured by Letterpress Printing Co., Ltd.) are bonded together.
  • the mounting surface of the lead frame substrate is a metal surface having a slight surface roughness.
  • an ultrasonic flaw detector (manufactured by Hitachi Power Solutions, FS300III) is used at the interface between the film-shaped transparent adhesive and the lead frame substrate mounting surface. The presence or absence of voids was observed, and the die attachability was evaluated based on the following evaluation criteria. In this test, the evaluation rank "A" is the passing level. Evaluation Criteria A: No voids are observed in all of the 24 dummy chips mounted. B: Voids are observed in 1 or more and 3 or less of the 24 dummy chips mounted. C: Voids are observed in 4 or more of the 24 dummy chips mounted.
  • a film-like transparent adhesive with a release film obtained in each Example and Comparative Example was applied to the surface of a silicon chip (size; 10 ⁇ 10 mm, thickness 350 ⁇ m) having an alignment mark of L mark (side 100 ⁇ m) at a stage of 70 ° C.
  • the film-like transparent adhesive was thermally cured by bonding with a hand roller and heating at a temperature of 180 ° C. for 1 hour.
  • dicing tape trade name: K-13, manufactured by Furukawa Denki Kogyo Co., Ltd.
  • dicing frame (trade name) are placed on the surface of the silicon chip opposite to the surface on which the film-like transparent adhesive is attached.
  • DTF2-8-1H001 manufactured by DISCO
  • a die bonder (trade name: DB-800, manufactured by Hitachi High-Technologies Corporation) recognizes the alignment mark on the chip surface through the thermosetting film-like transparent adhesive, and visually recognizes it based on the following evaluation criteria.
  • Sexual evaluation was performed. The evaluation was performed by adjusting the brightness of the illumination provided by the die bonder between 30 and 70%. In this test, the evaluation rank "A" is the passing level.
  • Occurrence C Of the 24 silicon chips tested, 4 or more recognition errors occurred in the range of brightness: 50 to 70% in the die bonder.
  • the brightness of 100% means the maximum brightness of the lighting provided in the die bonder.
  • the recognizability of the alignment mark was evaluated in the range of brightness of 30 to 70%. With any AA-rated transparent adhesive in the form of a film, the alignment mark can be recognized by using any die bonder (for example, even if the die bonder is worn out and the brightness is reduced).
  • the alignment mark can be recognized in the range of 30% or more and less than 50%, if the alignment mark can be recognized in the range of brightness of 50 to 70% (A evaluation), a normal device (brightness is high).
  • the alignment mark can be sufficiently recognized by adjusting the brightness as necessary using a worn-out die bonder (not a worn-out die bonder that is extremely lowered).
  • the melt viscosity thus obtained was used as the melt viscosity of the test piece after storage. Further, the melt viscosity of the test piece measured by the above-mentioned melt viscosity measurement was taken as the melt viscosity of the test piece before storage.
  • the melt viscosity of the test piece before storage is set to " VA " (initial value)
  • the melt viscosity of the test piece after storage is set to "V B "
  • the storage stability was evaluated based on the following evaluation criteria. In this test, the evaluation rank "A" is the passing level.
  • Evaluation Criteria A The rate of change of the melt viscosity of the test piece after storage with respect to the initial value exceeds -1% and is less than + 1%.
  • B The rate of change of the melt viscosity of the test piece after storage with respect to the initial value is more than -5% and -1% or less, or + 1% or more and less than + 5%.
  • C The rate of change of the melt viscosity of the test piece after storage with respect to the initial value is -5% or less, or + 5% or more.
  • Liquid BisA type epoxy resin Bisphenol A type epoxy resin
  • BisA type phenoxy resin Bisphenol A type phenoxy resin
  • the film-like transparent adhesives obtained by using the compositions for transparent adhesives containing the epoxy resin curing agent which does not satisfy the provisions of the present invention of Comparative Examples 1 to 12 are all visible evaluation and storage stability. At least one of the evaluations failed. Further, Comparative Examples 2 and 4 also failed in the die attachability evaluation.
  • the film-shaped transparent adhesives obtained by using the adhesive compositions of Examples 1 to 12 satisfying the provisions of the present invention are excellent in visibility and storage stability, and also excellent in die attachability. Was there. In particular, visibility is visible even when a large amount of epoxy resin curing agent is added to the epoxy resin (for example, when 2.0 parts by mass or more of the epoxy resin curing agent is contained with respect to 100 parts by mass of the epoxy resin). Was excellent.

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EP21859376.2A EP4047065B1 (en) 2020-09-29 2021-05-26 Transparent adhesive composition, film-like transparent adhesive, method for manufacturing transparent adhesive cured layer-provided member, and electronic component and method for manufacturing same
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4394861A4 (en) * 2021-08-23 2025-07-16 Furukawa Electric Co Ltd FILM-TYPE ADHESIVE AGENT AND ELECTRONIC COMPONENT USING SAME AND PRODUCTION METHOD THEREOF

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6336905B2 (https=) 1982-11-04 1988-07-22 Tokyo Shibaura Electric Co
JPH06256746A (ja) * 1993-03-09 1994-09-13 Hitachi Chem Co Ltd 接着剤組成物および接着フィルム
WO2014054631A1 (ja) * 2012-10-02 2014-04-10 大日本印刷株式会社 接着剤組成物およびそれを用いた接着シート
JP2016058457A (ja) * 2014-09-05 2016-04-21 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
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
JP2020163561A (ja) 2019-03-29 2020-10-08 日本碍子株式会社 円柱状ワークの穴あけ装置、円柱状ワークの穴あけ方法、円柱状製品の製造方法、及び円柱状ワークの検査方法
JP2021034574A (ja) * 2019-08-26 2021-03-01 東レ株式会社 熱硬化接着剤シート、半導体装置および半導体装置の製造方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6336905U (https=) 1986-08-25 1988-03-09
US6294271B1 (en) * 1999-02-12 2001-09-25 Shin-Etsu Chemical Co., Ltd. Flip-chip type semiconductor device sealing material and flip-chip type semiconductor device
JP2006323039A (ja) * 2005-05-18 2006-11-30 Shin Etsu Chem Co Ltd 液晶表示素子用シール剤組成物
CN101379108B (zh) * 2006-02-03 2011-11-30 旭化成电子材料株式会社 微胶囊型环氧树脂用固化剂、母料型环氧树脂用固化剂组合物、单液型环氧树脂组合物、及其加工品
KR20080072321A (ko) * 2007-02-02 2008-08-06 동우 화인켐 주식회사 경화성 수지 조성물 및 액정표시장치
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
JP5871428B2 (ja) * 2011-03-16 2016-03-01 古河電気工業株式会社 高熱伝導性フィルム状接着剤用組成物、高熱伝導性フィルム状接着剤、並びに、それを用いた半導体パッケージとその製造方法
CN104508069B (zh) 2012-08-02 2017-03-29 琳得科株式会社 膜状粘接剂、半导体接合用粘接片、和半导体装置的制造方法
JP2014227423A (ja) * 2013-05-17 2014-12-08 味の素株式会社 プリプレグ及びプリプレグ用エポキシ樹脂組成物
CN107111193A (zh) * 2015-05-20 2017-08-29 积水化学工业株式会社 液晶显示元件用密封剂、上下导通材料及液晶显示元件
JP6606894B2 (ja) * 2015-07-15 2019-11-20 味の素株式会社 エポキシ樹脂組成物の製造方法
JP6619628B2 (ja) * 2015-11-20 2019-12-11 旭化成株式会社 接着フィルム用エポキシ樹脂組成物。
JP6799910B2 (ja) * 2015-11-20 2020-12-16 旭化成株式会社 封止材用エポキシ樹脂組成物、及び封止材。
CN108264726B (zh) * 2016-12-30 2019-11-05 比亚迪股份有限公司 一种环氧树脂复合材料和制品及其制备方法
TWI778041B (zh) * 2017-03-31 2022-09-21 日商日鐵化學材料股份有限公司 纖維強化複合材料用環氧樹脂組成物、纖維強化複合材料及成形體
JP6800129B2 (ja) 2017-11-07 2020-12-16 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の製造方法
CN109554065B (zh) * 2018-10-17 2021-07-13 擎天材料科技有限公司 一种耐海洋性气候的底涂粉末涂料及其制备方法
CN111187438B (zh) * 2020-02-10 2021-03-05 北京航空航天大学 一种真空袋成型工艺用碳纤维/增韧环氧树脂预浸料的制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6336905B2 (https=) 1982-11-04 1988-07-22 Tokyo Shibaura Electric Co
JPH06256746A (ja) * 1993-03-09 1994-09-13 Hitachi Chem Co Ltd 接着剤組成物および接着フィルム
WO2014054631A1 (ja) * 2012-10-02 2014-04-10 大日本印刷株式会社 接着剤組成物およびそれを用いた接着シート
JP2016058457A (ja) * 2014-09-05 2016-04-21 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
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
JP2020163561A (ja) 2019-03-29 2020-10-08 日本碍子株式会社 円柱状ワークの穴あけ装置、円柱状ワークの穴あけ方法、円柱状製品の製造方法、及び円柱状ワークの検査方法
JP2021034574A (ja) * 2019-08-26 2021-03-01 東レ株式会社 熱硬化接着剤シート、半導体装置および半導体装置の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4047065A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4394861A4 (en) * 2021-08-23 2025-07-16 Furukawa Electric Co Ltd FILM-TYPE ADHESIVE AGENT AND ELECTRONIC COMPONENT USING SAME AND PRODUCTION METHOD THEREOF

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