WO2022097442A1 - Film adhésif, film adhésif avec feuille de support, corps durci et procédé de production de structure - Google Patents

Film adhésif, film adhésif avec feuille de support, corps durci et procédé de production de structure Download PDF

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Publication number
WO2022097442A1
WO2022097442A1 PCT/JP2021/038057 JP2021038057W WO2022097442A1 WO 2022097442 A1 WO2022097442 A1 WO 2022097442A1 JP 2021038057 W JP2021038057 W JP 2021038057W WO 2022097442 A1 WO2022097442 A1 WO 2022097442A1
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adhesive film
temperature
adhesive
heat
film
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PCT/JP2021/038057
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English (en)
Japanese (ja)
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功 市川
毅朗 吉延
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リンテック株式会社
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Priority to CN202180070981.5A priority Critical patent/CN116348564A/zh
Priority to JP2022560692A priority patent/JPWO2022097442A1/ja
Priority to KR1020237005868A priority patent/KR20230098130A/ko
Publication of WO2022097442A1 publication Critical patent/WO2022097442A1/fr

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    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive

Definitions

  • the present invention relates to an adhesive film having excellent thermal conductivity and a method for producing the same, an adhesive film with a support sheet, a cured product and a method for producing the same, and a method for producing a structure.
  • thermoelectric conversion devices thermoelectric conversion devices
  • photoelectric conversion devices photoelectric conversion devices
  • semiconductor devices such as large-scale integrated circuits
  • heat-dissipating members having thermal conductivity have been used in order to dissipate heat generated.
  • a sheet-shaped heat radiating member film, sheet
  • a heat radiating member having excellent thermal conductivity is provided between the semiconductor device and the heat sink. ing.
  • the above-mentioned film or sheet is coated with a coating liquid of a heat-dissipating material containing an adhesive resin, an inorganic filler, a curing agent and a solvent on a release sheet or a base material.
  • a coating liquid of a heat-dissipating material containing an adhesive resin, an inorganic filler, a curing agent and a solvent on a release sheet or a base material.
  • the inorganic filler silica, alumina, glass, titanium oxide and the like are used.
  • the present invention has been made in view of such an actual situation, and provides an adhesive film having excellent thermal conductivity and a method for producing the same, an adhesive film with a support sheet, a cured product and a method for producing the same, and a method for producing a structure.
  • the purpose is to provide.
  • the present invention comprises a heat conductive filler (A) composed of at least one of a graphene having a two-dimensional structure and a single-layer boron nitride, a heat-curable component (B), and a heat-curable component (B).
  • the preheating step is a step of holding the preheating step at a temperature of the following temperature (T) or lower for 30 minutes or more (Invention 1).
  • Temperature (T) The adhesive film before any heat treatment was subjected to thermal weight measurement under the condition of raising the temperature from 40 ° C. to 400 ° C. at a heating rate of 10 ° C./min under an atmospheric atmosphere, and the adhesive film was measured. The temperature at which the weight is reduced by 0.5%.
  • the adhesive film according to the above invention (Invention 1) has excellent thermal conductivity by containing the above-mentioned specific heat conductive filler (A) and by using it in the above-mentioned applications.
  • the present invention contains a thermally conductive filler (A) composed of at least one of a graphene having a two-dimensional structure and a single-layer boron nitride, a thermosetting component (B), and a binder polymer (C).
  • An adhesive film made of an adhesive resin composition, wherein the area ratio of the void portion in the thickness direction cross section of the cured product obtained by heat-treating the adhesive film under the following conditions is 10% or less.
  • the heat treatment includes a preheating step and a complete curing step of completely curing the adhesive film after the preheating step, and the preheating step includes an atmospheric atmosphere for the adhesive film before any heat treatment.
  • the adhesive film according to the above invention (Invention 2) is used by containing the above-mentioned specific heat conductive filler (A) and by heat-treating under the above-mentioned conditions to obtain the above-mentioned cured product. , It has excellent thermal conductivity.
  • the content of the thermally conductive filler (A) is preferably 5% by mass or more and 60% by mass or less (Invention 3).
  • thermosetting component (B) is preferably an epoxy resin (Invention 4).
  • inventions 1 to 4 it is preferable that the invention is hot-pressed (invention 5).
  • the arithmetic average roughness (Ra) of at least one surface is 0.01 ⁇ m or more and 0.5 ⁇ m or less (Invention 6).
  • the present invention further comprises mixing a thermally conductive filler (A) consisting of at least one of graphene and single-layer boron nitride having a two-dimensional structure and a binder polymer (C) in a solvent.
  • a method for producing an adhesive film which comprises obtaining an adhesive resin composition by mixing a thermosetting component (B) and forming the obtained adhesive resin composition into a film. (Invention 7).
  • the heating temperature of the hot press is lower than the curing reaction temperature of the thermosetting component (B) (Invention 9).
  • the arithmetic mean roughness (Ra) of at least one surface of the adhesive film after hot pressing is preferably 0.01 ⁇ m or more and 0.5 ⁇ m or less (invention). 10).
  • the present invention provides an adhesive film with a support sheet including the adhesive film (inventions 1 to 6) and a support sheet laminated on at least one surface side of the adhesive film (invention 11).
  • the present invention contains a thermally conductive filler (A) composed of at least one of graphene and single-layer boron nitride having a two-dimensional structure, a thermosetting component (B), and a binder polymer (C).
  • A thermally conductive filler
  • B thermosetting component
  • C binder polymer
  • a cured product obtained by subjecting an adhesive film made of an adhesive resin composition to be heat-treated, wherein the area ratio of the void portion in the cross section in the thickness direction is 10% or less.
  • the maximum area of the void portion in the cross section in the thickness direction is 100 ⁇ m 2 or less (Invention 13).
  • the heat treatment includes a preheating step and a complete curing step of completely curing the adhesive film after the preheating step, and the preheating step is an arbitrary heat treatment.
  • the weight of the adhesive film is reduced by 0.5% when the thermal weight measurement is performed under the condition that the temperature of the adhesive film is raised from 40 ° C. to 400 ° C. at a temperature increase rate of 10 ° C./min in an air atmosphere. It is preferable to include a step of holding the film at a temperature equal to or lower than the temperature for 30 minutes or more (Invention 14).
  • the present invention contains a thermally conductive filler (A) composed of at least one of graphene and single-layer boron nitride having a two-dimensional structure, a thermosetting component (B), and a binder polymer (C).
  • a method for producing a cured product which comprises heat-treating an adhesive film made of an adhesive resin composition to form a cured product. The heat treatment completely completes the adhesive film after a preheating step and a preheating step.
  • the preheating step includes a complete curing step of curing, and the preheating step is a condition in which the temperature of the adhesive film before any heat treatment is raised from 40 ° C. to 400 ° C. at a heating rate of 10 ° C./min under an air atmosphere.
  • the present invention provides a method for producing a cured product, which comprises a step of holding the adhesive film at a temperature equal to or lower than a temperature at which the weight is reduced by 0.5% by 0.5% for 30 minutes or more when a thermal weight measurement is performed (Invention 15).
  • invention 15 it is preferable to heat-press the adhesive film before the heat treatment (invention 16).
  • the area ratio of the void portion in the thickness direction cross section of the cured product is preferably 10% or less (invention 17).
  • the present invention contains a heat conductive filler (A) composed of at least one of a graphene having a two-dimensional structure and a single-layer boron nitride, a heat-curable component (B), and a binder polymer (C).
  • the heat treatment includes a preheating step and a complete curing step of completely curing the adhesive film after the preheating step, and the adhesive film before the preheating step performs an arbitrary heat treatment. 30 minutes at a temperature below the temperature at which the adhesive film loses 0.5% by weight when the thermal weight is measured under the condition that the temperature rises from 40 ° C to 400 ° C at a heating rate of 10 ° C / min under an air atmosphere.
  • a method for manufacturing a structure which comprises the above-mentioned holding step (Invention 18).
  • the area ratio of the void portion in the cross section in the thickness direction of the cured product is preferably 10% or less (invention 20).
  • the first member is a flexible sheet-like member, and a laminate of the sheet-like member and the heat-pressed adhesive film is used as the second member. It is preferable to perform the bonding at a temperature equal to or higher than the temperature showing the peak of loss tangent (tan ⁇ ) obtained by measuring the viscoelasticity of the adhesive film before any heat treatment. ..
  • the inventions include a step of attaching the adhesive film to the first member or the second member, and have viscoelasticity of the adhesive film before any heat treatment. It is preferable to perform the pasting at a temperature equal to or higher than the temperature indicating the peak of the loss tangent (tan ⁇ ) obtained by the measurement.
  • the adhesive film, the adhesive film with a support sheet, the cured body and the structure according to the present invention are excellent in thermal conductivity. Further, according to the method for producing an adhesive film according to the present invention, it is possible to produce an adhesive film having excellent thermal conductivity. Further, according to the method for producing a cured product according to the present invention, a cured product having excellent thermal conductivity can be produced, and according to the method for producing a structure according to the present invention, a structure having excellent thermal conductivity can be produced. The body can be manufactured.
  • the adhesive film according to the present embodiment includes a thermally conductive filler (A) composed of at least one of graphene and single-layer boron nitride having a two-dimensional structure, a thermosetting component (B), and a binder polymer (C). It is made of an adhesive resin composition containing the above (hereinafter, may be referred to as "adhesive resin composition R").
  • the adhesive resin composition R preferably contains a curing agent (D), and more preferably contains a curing accelerator (E).
  • the adhesive film according to the present embodiment is first used to perform a heat treatment including a preheating step and a complete curing step of completely curing the adhesive film after the preheating step. It is preferable to include a step of holding at a temperature of the following temperature (T) or less for 30 minutes or more.
  • T temperature of the following temperature
  • the number of voids is reduced inside the obtained cured product.
  • the area ratio of the void portion in the cross section in the thickness direction of the obtained cured product can be 10% or less. Details regarding the heat treatment will be described later.
  • the area ratio of the void portion in the cross section in the thickness direction of the cured product obtained by heat-treating the adhesive film under the following conditions is 10% or less. preferable.
  • the heat treatment includes a preheating step and a complete curing step of completely curing the adhesive film after the preheating step.
  • the adhesive film before any heat treatment is subjected to thermal weight measurement under the condition of raising the temperature from 40 ° C. to 400 ° C. at a heating rate of 10 ° C./min in an air atmosphere. This is a step of holding the film at a temperature lower than the temperature at which the weight is reduced by 0.5% for 30 minutes or more.
  • the thermally conductive filler (A) composed of at least one of graphene and single-layer boron nitride having a two-dimensional structure has a characteristic of having a large specific surface area because it has a two-dimensional structure having a thickness on the order of several tens of nm. Therefore, in the adhesive film, the heat conductive fillers (A) are in contact with each other, and a heat conduction path for transferring heat is likely to be formed. In particular, by performing the predetermined heat treatment as described above and using the cured product, the voids inside the obtained cured product can be reduced, whereby even a small amount of the heat conductive filler (A) added is excellent. It can show thermal conductivity.
  • the heat conductive filler (A) when used as a filler for the adhesive resin composition, excellent heat conductivity can be imparted without high filling. Further, since the above-mentioned heat conductive filler (A) has a two-dimensional structure having a thickness on the order of several tens of nm and has flexibility in itself, the adhesive film containing the heat conductive filler (A) can be used. , It will be excellent in flexibility. Moreover, since it is not necessary to highly fill the thermally conductive filler (A) as described above, the adhesive film is prevented from becoming mechanically brittle.
  • the adhesive film has excellent flexibility, it becomes difficult for air to be entrained when the adhesive film is attached to the adherend, and it is possible to suppress the formation of voids at the interface between the adhesive film and the adherend, and to reduce the contact area between the adhesive film and the adherend. Can be made larger. That is, it is possible to suppress the increase in thermal resistance due to the voids at the interface between the adhesive film and the adherend, and it is possible to improve the thermal conductivity between the adhesive film and the adherend. Further, if the adhesive film is prevented from becoming mechanically brittle as described above, the probability of occurrence of process defects such as generation of broken debris during use is reduced.
  • the surface roughness of the adhesive film becomes large and tack becomes difficult to develop.
  • the heat conductive filler (A) in the present embodiment can obtain high heat conductivity without being highly filled as described above, the surface roughness of the adhesive film can be lowered, thereby lowering the surface roughness.
  • the adhesive film is attached to the adherend, the appropriate adhesive force can be exhibited by adjusting the attachment temperature.
  • Thermally conductive filler (A) in the present embodiment comprises at least one of graphene having a two-dimensional structure and monolayer boron nitride.
  • Graphene has a two-dimensional structure in which carbon atoms are regularly arranged in a hexagon
  • single-layer boron nitride has a two-dimensional structure in which boron atoms and nitrogen atoms are regularly arranged in a hexagon. It is a dimensional compound.
  • the “graphene or single-layer boron nitride having a two-dimensional structure” in the present specification may be a multi-layered one, preferably having a thickness of 1/10 or less of the shortest length in a plan view shape.
  • graphene in the present specification includes those produced by thinly peeling graphite, and single-layer boron nitride includes those produced by thinly peeling boron nitride.
  • graphite itself does not fall under the above-mentioned "graphene having a two-dimensional structure”.
  • graphene or single-layer boron nitride having a two-dimensional structure may be a single layer or a multi-layer. In the case of a plurality of layers, it is usually about 2 to 1,000 layers.
  • the plan-view shape of graphene and single-layer boron nitride having a two-dimensional structure is not particularly limited.
  • the average particle size of the thermally conductive filler (A) is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, particularly preferably 3.0 ⁇ m or more, and further preferably 5.0 ⁇ m.
  • the above is preferable.
  • the heat conductive fillers (A) are easily brought into contact with each other, and a heat conduction path is easily formed. Therefore, the characteristics of the two-dimensional structure function, and the obtained adhesive film has excellent heat conductivity.
  • the average particle size of the heat conductive filler (A) is preferably 30 ⁇ m or less, particularly preferably 20 ⁇ m or less, and further preferably 15 ⁇ m or less. As a result, the dispersed state is maintained in other materials such as the solvent and the binder polymer (C), the heat conduction path is suppressed from being formed due to segregation, and the adhesive film becomes more excellent in heat conductivity.
  • the thickness of the thermally conductive filler (A) is preferably 500 nm or less, more preferably 300 nm or less, particularly preferably 200 nm or less, and further preferably 100 nm or less.
  • the lower limit of the thickness of the heat conductive filler (A) is not particularly limited, but is usually 0.7 nm or more, preferably 5.0 nm or more, and particularly preferably 10 nm or more from the viewpoint of heat conductivity. It is preferably 15 nm or more, and more preferably 15 nm or more.
  • the content of the heat conductive filler (A) in the adhesive resin composition R is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. It is preferable, more preferably 20% by mass or more. Since the lower limit of the content of the heat conductive filler (A) is as described above, the heat conductive fillers (A) are likely to come into contact with each other and a heat conductive path is easily formed, so that the obtained adhesive film can be obtained. It becomes superior in thermal conductivity.
  • the content of the thermally conductive filler (A) in the adhesive resin composition R is preferably 60% by mass or less, more preferably 55% by mass or less, and particularly preferably 50% by mass or less. It is preferably 40% by mass or less.
  • the upper limit of the content of the thermally conductive filler (A) is as described above, the obtained adhesive film is suppressed from becoming mechanically brittle, and the flexibility becomes more excellent.
  • the desired heat conductivity can be obtained even with a relatively small content as described above.
  • thermosetting component (B) in the present embodiment is not particularly limited as long as it enables thermosetting of the adhesive resin composition R and exhibits adhesiveness by thermosetting, and is not particularly limited, for example, an epoxy resin or a phenol resin. , Melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, benzoxazine resin, phenoxy resin and the like. These can be used alone or in combination of two or more. Among these, an epoxy resin is preferable from the viewpoint of dispersibility and adhesiveness of the thermally conductive filler (A).
  • the "epoxy resin” in the present specification also includes a non-polymerized or low molecular weight epoxy compound for convenience.
  • epoxy resin examples include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenylnovolac and cresolnovolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; phthalic acid and isophthalic acid.
  • Glycidyl ether of carboxylic acid such as tetrahydrophthalic acid
  • glycidyl type or alkyl glycidyl type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is replaced with a glycidyl group
  • vinylcyclohexanediepoxide 3,4-epoxycyclohexyl
  • Intramolecular carbon-carbon such as methyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, etc.
  • alicyclic epoxide in which an epoxy is introduced by oxidizing a double bond can be mentioned.
  • an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclopentadiene skeleton, a dicyclopentadiene skeleton, a naphthalene skeleton, an anthracene skeleton, or the like, or a polyfunctional epoxy resin can also be used.
  • These epoxy resins can be used alone or in combination of two or more.
  • thermosetting component (B) in the present embodiment it is preferable to use at least an epoxy resin having a ⁇ -conjugated mesogen skeleton from the viewpoint of dispersibility of the thermally conductive filler (A).
  • an epoxy resin having a ⁇ -conjugated mesogen skeleton an epoxy resin having a naphthalene skeleton or an epoxy resin having a biphenyl skeleton is preferable, and an epoxy resin having a naphthalene skeleton is particularly preferable.
  • the epoxy resin having a naphthalene skeleton for example, those represented by the following formula (1) are preferably mentioned.
  • n is an integer greater than or equal to 0.
  • the epoxy equivalent of the epoxy resin having the ⁇ -conjugated mesogen skeleton is preferably 100 g / eq or more, particularly preferably 150 g / eq or more, and further preferably 180 g / eq or more.
  • the epoxy equivalent is preferably 500 g / eq or less, particularly preferably 400 g / eq or less, and more preferably 300 g / eq or less.
  • the epoxy equivalent in the present specification is a value measured according to JIS K7236.
  • the softening point of the epoxy resin having the ⁇ -conjugated mesogen skeleton is preferably 40 ° C. or higher, particularly preferably 50 ° C. or higher, and further preferably 60 ° C. or higher.
  • the softening point is preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower, and further preferably 120 ° C. or lower.
  • the softening point in the present specification is a value measured according to the measurement method by the ring-and-ball method described in JIS K7234: 1986.
  • thermosetting component (B) in the present embodiment it is preferable to use a phenolic glycidyl ether from the viewpoint of adjusting the adhesiveness and adhesiveness together with the above-mentioned epoxy resin having a ⁇ -conjugated mesogen skeleton.
  • a phenolic glycidyl ether examples include those described above, and among them, it is preferable to use a bisphenol F type epoxy resin.
  • the epoxy equivalent of the glycidyl ether of the above phenols is preferably 100 g / eq or more, particularly preferably 120 g / eq or more, and further preferably 150 g / eq or more.
  • the epoxy equivalent is preferably 500 g / eq or less, particularly preferably 400 g / eq or less, and more preferably 300 g / eq or less.
  • the content of the thermosetting component (B) in the adhesive resin composition R is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. It is preferable, more preferably 20% by mass or more.
  • the adhesive resin composition R can be sufficiently cured, and more excellent mechanical strength and adhesiveness can be exhibited.
  • the content is preferably 45% by mass or less, more preferably 40% by mass or less, particularly preferably 35% by mass or less, and further preferably 30% by mass or less. ..
  • the upper limit of the content of the thermosetting component (B) is as described above, the content of other components can be secured.
  • the blending ratio (mass standard) thereof is preferably 20:80 to 95: 5, and 40:60 to 90:
  • the ratio is more preferably 10, particularly preferably 50:50 to 85:15, and further preferably 60:40 to 80:20. This makes it possible to achieve a good balance between the dispersibility of the heat conductive filler (A) and the adhesiveness / adhesiveness of the adhesive film.
  • Binder polymer (C) The binder polymer (C) is blended for the purpose of forming the adhesive resin composition R into a film, giving an appropriate tack to the obtained adhesive film, and the like.
  • a binder polymer for example, an acrylic polymer, a polyester resin, a phenoxy resin, a urethane resin, a silicone resin, a rubber polymer and the like are used, and an acrylic polymer is particularly preferably used.
  • acrylic acid polymer examples include a (meth) acrylic acid ester polymer obtained by polymerizing a (meth) acrylic acid ester monomer and the like.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • the concept of "polymer” shall be included in “polymer”.
  • Examples of the monomer constituting the (meth) acrylate polymer include carbons of alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Examples thereof include (meth) acrylic acid alkyl esters having a number of 1 to 18, and functional group-containing monomers having a functional group in the molecule.
  • Examples of the functional group-containing monomer include a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), a monomer having a carboxy group in the molecule (carboxy group-containing monomer), and a monomer having an amino group in the molecule (amino group-containing monomer). ) And the like. These may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester polymer used as the binder polymer (C) in the present embodiment is a copolymerization of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms and a functional group-containing monomer. It is preferable that it is an ester.
  • the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 9, particularly preferably 1 to 6, and further preferably 1 to 3.
  • methyl (meth) acrylate is particularly preferable, and methyl acrylate is most preferable.
  • a hydroxyl group-containing monomer is preferable.
  • the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth).
  • Acrylic acid (meth) Acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylic acid can be mentioned.
  • 2-hydroxyethyl (meth) acrylate is particularly preferable, and 2-hydroxyethyl acrylate is most preferable.
  • the thermally conductive filler (A) can be easily dispersed in the adhesive resin composition R.
  • the (meth) acrylic acid ester polymer obtained by copolymerizing the above (meth) acrylic acid alkyl ester and a functional group-containing monomer is used as the binder polymer (C), the (meth) acrylic acid ester polymer is contained.
  • the structural unit derived from the functional group-containing monomer is preferably contained in the range of 5 to 50% by mass, particularly preferably in the range of 8 to 30% by mass, and further preferably in the range of 10 to 20% by mass. It is preferably contained.
  • the weight average molecular weight of the acrylic polymer ((meth) acrylic acid ester polymer) as the binder polymer (C) is preferably 50,000 or more, more preferably 100,000 or more, and particularly preferably 150,000 or more. It is preferably present, and more preferably 200,000 or more.
  • the weight average molecular weight is preferably 1 million or less, more preferably 700,000 or less, particularly preferably 500,000 or less, and further preferably 400,000 or less. When the weight average molecular weight is in the above range, the film forming property and the adhesiveness become good, and the dispersibility of the heat conductive filler (A) becomes better.
  • the weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.
  • the glass transition temperature (Tg) of the acrylic polymer ((meth) acrylic acid ester polymer) as the binder polymer (C) is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 15 ° C. or higher. It is preferable, particularly preferably ⁇ 10 ° C. or higher, and further preferably ⁇ 5 ° C. or higher.
  • the glass transition temperature (Tg) is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, particularly preferably 40 ° C. or lower, and further preferably 35 ° C. or lower. ..
  • the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer in the present specification is a value calculated based on the FOX formula.
  • the content of the binder polymer (C) in the adhesive resin composition R is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. Further, it is preferably 4% by mass or more.
  • the content is preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 45% by mass or less, and further preferably 40% by mass or less. ..
  • the adhesive resin composition R in the present embodiment preferably further contains a curing agent (D). Thereby, the adhesive resin composition R can be satisfactorily cured.
  • the curing agent (D) is not particularly limited as long as it can cure the thermosetting component (B) by heating, but phenols, amines, thiols and the like are preferably mentioned, and the above-mentioned thermosetting is preferable. It can be appropriately selected depending on the type of the sex component (B). For example, when an epoxy resin is used as the thermosetting component (B), phenols are preferable from the viewpoint of reactivity with the epoxy resin and the like.
  • thermally conductive filler (A) it is preferable to use a compound having a ⁇ -conjugated mesogen skeleton, and it is particularly preferable to use phenols having a ⁇ -conjugated mesogen skeleton.
  • phenols examples include bisphenol A, tetramethylbisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane type phenol, tetrakisphenol, novolak type phenol resin, cresol novolac resin, and biphenyl type phenol resin. And so on.
  • phenols having a conjugated mesogen skeleton include the above-mentioned biphenyl-type phenols. These can be used alone or in combination of two or more.
  • novolak-type phenol resin or biphenyl-type phenol resin is preferable, and it is particularly preferable to use both novolak-type phenol resin and biphenyl-type phenol resin in combination.
  • the hydroxyl group equivalent of the novolak type phenol resin is preferably 70 g / eq or more, particularly preferably 80 g / eq or more, and further preferably 90 g / eq or more.
  • the hydroxyl group equivalent is preferably 300 g / eq or less, particularly preferably 280 g / eq or less, and more preferably 250 g / eq or less. As a result, the curability of the epoxy resin becomes more excellent.
  • the hydroxyl group equivalent in the present specification is a value measured according to JIS K0070.
  • biphenyl type phenol resin for example, those represented by the following formulas (2) and (3) are preferably mentioned.
  • n is an integer of 1 or more.
  • the hydroxyl group equivalent of the biphenyl-type phenol resin is preferably 80 g / eq or more, particularly preferably 85 g / eq or more, and further preferably 90 g / eq or more.
  • the hydroxyl group equivalent is preferably 300 g / eq or less, particularly preferably 280 g / eq or less, and more preferably 250 g / eq or less. This prevents the inclusion of substances that inhibit the curing reaction that remain as unreactants during synthesis, such as elemental phenol, and makes the epoxy resin more excellent in curability.
  • the softening point of the novolak-type phenol resin and the biphenyl-type phenol resin is preferably 60 ° C. or higher, particularly preferably 80 ° C. or higher, and further preferably 90 ° C. or higher.
  • the softening point is preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower, and further preferably 130 ° C. or lower.
  • its sublimation temperature is preferably 270 ° C. or higher.
  • the sublimation temperature is preferably 330 ° C. or lower.
  • the content of the curing agent (D) in the adhesive resin composition R is preferably 2% by mass or more, more preferably 4% by mass or more, and particularly preferably 5% by mass or more. Further, it is preferably 8% by mass or more.
  • the content is preferably 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less, and further preferably 25% by mass or less. ..
  • the curability of the adhesive resin composition R becomes better.
  • the compounding ratio (mass standard) thereof is preferably 80:20 to 10:90, more preferably 70:30 to 20:80. It is preferable, particularly preferably 65:35 to 25:75, and further preferably 60:40 to 30:70. Thereby, the curability of the adhesive resin composition R and the dispersibility of the heat conductive filler (A) can be well balanced.
  • the adhesive resin composition R in the present embodiment preferably further contains a curing accelerator (E) that promotes or adjusts the reaction between the thermosetting component (B) and the curing agent (D) described above.
  • Examples of the curing accelerator (E) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, and the like.
  • Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like.
  • Organic phosphins such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate can be mentioned. These can be used alone or in admixture of two or more.
  • thermosetting component (B) thermosetting component (B) and phenols are used as the curing agent (D)
  • the content of the curing accelerator (E) in the adhesive resin composition R is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and particularly 0.005% by mass.
  • the above is preferable, and more preferably 0.01% by mass or more.
  • the content is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, and further preferably 0.05% by mass. It is preferably mass% or less.
  • Various additives such as a tackifier, a flame retardant, an antioxidant, a light stabilizer, a softener, and a rust preventive are added to the adhesive resin composition in the present embodiment, if desired. can do.
  • the adhesive resin composition R in the present embodiment contains a heat conductive filler (A) composed of at least one of graphene having a two-dimensional structure and single-layer boron nitride, and a thermosetting component (a thermosetting component (A). It can be obtained by sufficiently mixing B), a binder polymer (C), a curing agent (D), a curing accelerator (E), an additive, and a solvent, if desired. If any of the above components is in the form of a solid, or if precipitation occurs when the components are mixed with other components in an undiluted state, the components may be used alone in advance as a solvent. It may be dissolved or diluted and then mixed with other ingredients.
  • the adhesive resin composition R in the present embodiment is prepared by mixing the thermally conductive filler (A) and the binder polymer (C) in advance in a solvent, and then further adding a thermosetting component (B), if desired. It is preferable to add a curing agent (D), a curing accelerator (E), an additive and the like.
  • a curing agent (D), a curing accelerator (E), an additive and the like By mixing the heat conductive filler (A) and the binder polymer (C) in advance before blending the thermosetting component (B) and the like, the dispersibility of the heat conductive filler (A) becomes better. , Segregation of the thermally conductive filler (A) in the coating film is suppressed. As a result, the heat conductive filler (A) is uniformly dispersed in the obtained adhesive film, and an adhesive film having better heat conductivity can be obtained.
  • the heat conductive filler (A) and the binder polymer (C) are preferably mixed in a solvent at a speed of 500 to 5000 rpm of the disper for 10 minutes or more, preferably at the same speed of 1000 to 40,000 rpm. It is more preferable to stir for 20 minutes or more.
  • the solvent is not particularly limited, and is, for example, an aliphatic hydrocarbon such as hexane, heptane, or cyclohexane, an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as methylene chloride or ethylene chloride, methanol, or the like.
  • Alcohols such as ethanol, propanol, butanol, 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolvent solvents such as ethyl cellosolve, N. , N-Dimethylformamide, trimethyl-2-pyrrolidone, butylcarbitol and the like are used, but methylethylketone is preferable.
  • the viscosity of the coating liquid of the adhesive resin composition R thus prepared is not particularly limited as long as it can be coated, and can be appropriately selected depending on the situation. It should be noted that the addition of the diluting solvent or the like is not a necessary condition, and the diluting solvent may not be added as long as the adhesive resin composition R has a viscosity and the like that can be coated.
  • the adhesive film according to the present embodiment is obtained by forming the adhesive resin composition R obtained above into a film.
  • a release sheet as a coating target.
  • the adhesive film according to the present embodiment can be easily produced by applying the coating liquid of the adhesive resin composition R to the release sheet and removing the diluting solvent by heating and drying.
  • Examples of the release sheet include a resin film, a non-woven fabric, and paper, but a resin film is generally used.
  • Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and polybutylene terephthalate film.
  • Polyurethane film ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Is used. In addition, these crosslinked films are also used. Further, these laminated films may be used.
  • the peeling surface (the surface in contact with the adhesive resin composition R) of the peeling sheet is subjected to a peeling treatment.
  • the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
  • this peeling treatment is not always necessary.
  • the thickness of the release sheet is not particularly limited, but is usually about 20 to 150 ⁇ m.
  • the arithmetic average roughness (Ra) of the peeled surface of the peeled sheet is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and particularly preferably 0.01 ⁇ m or less. Since the arithmetic average roughness (Ra) of the peeling surface of the release sheet is as described above, even if the roughness of the release surface of the release sheet is transferred to the adhesive film, the arithmetic average roughness (Ra) of the adhesive film will be described later. It becomes easy to adjust to a preferable range.
  • the method for measuring the arithmetic mean roughness (Ra) in the present specification is as shown in a test example described later.
  • the coating liquid of the adhesive resin composition R is applied to the peeling surface of the release sheet.
  • the coating method for example, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method and the like can be used.
  • the coating film of the adhesive resin composition R is dried and a diluting solvent or the like is volatilized to obtain an adhesive film.
  • the drying conditions are preferably 90 to 150 ° C. for 0.5 to 30 minutes, and particularly preferably 100 to 120 ° C. for 1 to 10 minutes.
  • the heating temperature of the drying treatment needs to be lower than the thermosetting temperature of the adhesive resin composition R.
  • the protective film the same one as the above-mentioned release sheet mainly composed of the resin film can be used.
  • the protective film may or may not be peeled off as long as it has peelability with respect to the adhesive film.
  • the adhesive film (laminated body) obtained as described above is preferably heat-pressed.
  • the voids existing inside the adhesive film can be reduced, and the thermal conductivity becomes more excellent.
  • the heat press makes it easier for the heat conductive fillers (A) to come into contact with each other, makes it easier for the heat conduction path to be formed, and makes the heat conductivity more excellent.
  • the amount of the heat conductive filler (A) blended in the adhesive film can be further reduced, and the flexibility and adhesiveness of the adhesive film can be further improved.
  • the heating temperature of the hot press shall be lower than the curing reaction temperature of the thermosetting component (B). Specifically, it is preferably 30 to 90 ° C, more preferably 40 to 80 ° C, particularly preferably 45 to 70 ° C, and further preferably 45 to 60 ° C.
  • the pressure of the hot press is preferably 0.5 to 15 MPa, more preferably 1 to 10 MPa, particularly preferably 1.5 to 5 MPa, and further preferably 2 to 4 MPa.
  • the heat pressing time is preferably 0.5 to 60 minutes, more preferably 1 to 50 minutes, particularly preferably 2 to 40 minutes, and further preferably 3 to 30 minutes. ..
  • the thickness of the adhesive film (including the adhesive film that has not been heat-pressed and the adhesive film that has been heat-pressed) according to this embodiment is the thickness (value measured according to JIS K7130).
  • the lower limit is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, particularly preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more. When the lower limit of the thickness of the adhesive film is the above, it is easy to exhibit good adhesive force and adhesive force.
  • the thickness of the adhesive film according to the present embodiment is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, particularly preferably 200 ⁇ m or less, and further preferably 100 ⁇ m or less as an upper limit value. Is preferable. When the upper limit of the thickness of the adhesive film is the above, the thermal conductivity becomes better.
  • the adhesive film may be formed as a single layer, or may be formed by laminating a plurality of layers.
  • the arithmetic mean roughness (Ra) of at least one surface of the adhesive film is preferably 0.5 ⁇ m or less, preferably 0.4 ⁇ m or less. It is more preferably present, particularly preferably 0.35 ⁇ m or less, and further preferably 0.3 ⁇ m or less.
  • the upper limit of the arithmetic average roughness (Ra) of the adhesive film is the above, the adhesiveness to the adherend, that is, the temporary adhesiveness becomes more excellent, and the handleability becomes good. Further, since the contact area with the adherend becomes large, the thermal conductivity with the adherend becomes more excellent.
  • the thermally conductive filler (A) segregates on the surface of the adhesive film, and the resin component is not present on the surface of the adhesive film at all, or even if it is present. It may be in trace amounts. As a result, the temporary adhesiveness may be insufficient when attached to the adherend.
  • the arithmetic mean roughness (Ra) of the adhesive film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, particularly preferably 0.03 ⁇ m or more, and further preferably 0. It is preferably 05 ⁇ m or more.
  • the thermally conductive filler (A) segregates on the surface of the adhesive film, the arithmetic mean roughness (Ra) tends to increase. Since the lower limit of the arithmetic average roughness (Ra) of the adhesive film is as described above, it can be said that the heat conductive filler (A) is present on the surface of the adhesive film, and the heat between the adhesive film and the adherend can be said to be present. The conductivity will be better.
  • Adhesive strength of the adhesive film (including the adhesive film that has not been hot-pressed and the adhesive film that has been hot-pressed) to a silicon wafer is 0.1 mN / It is preferably 25 mm or more, more preferably 0.5 mN / 25 mm or more, particularly preferably 0.8 mN / 25 mm or more, and further preferably 1.0 mN / 25 mm or more. As a result, it adheres well to the adherend and can exhibit excellent temporary adhesiveness.
  • the upper limit of the adhesive strength is not particularly limited, but is usually preferably 5.0 mN / 25 mm or less, more preferably 3.0 mN / 25 mm or less, and particularly preferably 2.5 mN / 25 mm or less. It is preferably 2.0 mN / 25 mm or less. As a result, the reworkability is excellent.
  • the adhesive strength in the present specification basically refers to the adhesive strength measured by the 180-degree peeling method according to JIS Z0237: 2009, and the specific measuring method is as shown in the test example described later. ..
  • the adhesive film with a support sheet is laminated with the above-mentioned adhesive film (including a heat-pressed adhesive film and a heat-pressed adhesive film) on at least one surface side of the adhesive film. It is equipped with a support sheet. The support sheet may be peeled off from the adhesive film in the future.
  • the processability of the adherend can be improved.
  • the adhesive film with a support sheet is attached to one adherend, processed in that state, and then the support sheet is peeled off.
  • a process such as attaching an adhesive film to another adherend can be performed.
  • FIG. 1 shows an adhesive film with a support sheet as an example in this embodiment.
  • the adhesive film 2 with a support sheet shown in FIG. 1 includes an adhesive film 1, a support sheet 11 laminated on one surface of the adhesive film 1 (upper surface in FIG. 1), and the other of the adhesive film 1. It is configured to include a release sheet 12 laminated on a surface (lower surface in FIG. 1).
  • the release sheet 12 is laminated on the adhesive film 1 so that its peelable surface is in contact with the adhesive film 1.
  • the release sheet 12 protects the adhesive film 1 until the adhesive film 1 is used, and may be omitted.
  • a protective film may be laminated instead of the release sheet 12.
  • the support sheet 11 is not particularly limited as long as it can exhibit sufficient mechanical strength to support the adhesive film 1.
  • Examples of the material constituting the support sheet 11 include a resin film, a non-woven fabric, and paper, and a resin film is generally used.
  • the resin film examples include a polyethylene film such as a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, and a high density polyethylene (HDPE) film, a polypropylene film, an ethylene-propylene copolymer film, and a polybutene.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • Polyolefin films such as films, polybutadiene films, polymethylpentene films, ethylene-norbornene copolymer films, norbornene resin films; ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- Ethylene-based copolymer film such as (meth) acrylic acid ester copolymer film; polyvinyl chloride-based film such as polyvinyl chloride film and vinyl chloride copolymer film; polyester-based film such as polyethylene terephthalate film and polybutylene terephthalate film.
  • the support sheet 11 may be a release sheet.
  • the support sheet 11 may be, for example, one in which a known pressure-sensitive adhesive layer is provided on the above-mentioned resin film, non-woven fabric, paper, or the like.
  • the thickness of the support sheet 11 is preferably 20 ⁇ m or more, particularly preferably 40 ⁇ m or more, and further preferably 60 ⁇ m or more.
  • the thickness is preferably 150 ⁇ m or less, particularly preferably 120 ⁇ m or less, and further preferably 110 ⁇ m or less.
  • the support sheet 11 tends to have the desired mechanical strength, and the adherend workability and the like are good.
  • the adhesive film 2 with a support sheet may be a dicing / die bonding sheet used when manufacturing a semiconductor device.
  • the adhesive film 2 with a support sheet can be used in the steps of dicing and dicing the semiconductor element, and the cured product of the adhesive film is for releasing the heat generated when the semiconductor device is driven to the outside world.
  • the support sheet 11 is preferably provided with, for example, a known pressure-sensitive adhesive layer on the surface of the resin film described above on the side of the adhesive film 1.
  • the release sheet may be peeled off from the above-mentioned laminate made of the release sheet / adhesive film / protective film and the support sheet may be laminated, or the above-mentioned release sheet / adhesion may be performed.
  • the protective film may be peeled off from the laminate made of the film / protective film and the support sheet may be laminated, or the support sheet may be used instead of the protective film in the above-mentioned method for producing an adhesive film.
  • the cured product according to the embodiment of the present invention is one in which the above-mentioned adhesive film is cured by heat treatment, and preferably the above-mentioned adhesive film after hot pressing is cured by heat treatment.
  • Area ratio of void portion The area ratio of the void portion in the thickness direction cross section of the cured product in the present embodiment is preferably 10% or less, more preferably 7% or less, and particularly 5%. It is preferably less than or equal to, and more preferably 4% or less. When the area ratio of the void portion is 10% or less, the heat conductive fillers (A) are in more contact with each other, the heat conduction path is formed at a high density, and the heat conductivity becomes more excellent. ..
  • the lower limit of the area ratio is not particularly limited, and the most preferable value is 0%.
  • the method for deriving the area ratio of the void portion is as shown in the test example described later.
  • the maximum area of the void portion in the cross section in the thickness direction of the cured product in the present embodiment is preferably 100 ⁇ m 2 or less, more preferably 80 ⁇ m 2 or less, and particularly 60 ⁇ m 2 or less. It is preferably 50 ⁇ m 2 or less.
  • the heat conductive fillers (A) are in more contact with each other, the heat conduction path is formed at a high density, and the heat conductivity becomes more excellent. ..
  • the lower limit of the maximum area is not particularly limited, and most preferably 0 ⁇ m 2 .
  • the method for deriving the maximum area of the void portion is as shown in a test example described later.
  • the thermal conductivity of the cured product in the present embodiment is preferably 4 W / mK or more, and particularly preferably 5 W / mK or more. As a result, it can be said that the cured product has excellent thermal conductivity.
  • the cured product according to the present embodiment can achieve such a high thermal conductivity because the adhesive film has the above-mentioned structure.
  • the method for measuring the thermal conductivity in the present specification is as shown in a test example described later.
  • an adhesive film (preferably an adhesive film after hot pressing) is heat-treated and finally completely cured.
  • the adhesive film is subjected to thermal weight measurement under the condition that the temperature of the adhesive film before any heat treatment is raised from 40 ° C. to 400 ° C. at a temperature rise rate of 10 ° C./min in an air atmosphere.
  • the adhesive film is completely cured by a rapid heat treatment, the small molecule components in the adhesive film volatilize and foam due to heating, and voids are likely to be formed inside the adhesive film.
  • the heat treatment includes the above steps
  • foaming is suppressed because the small molecule component is taken into the matrix of the thermosetting component (B), the binder polymer (C) and the like and trapped before it volatilizes. This will reduce the voids in the adhesive film.
  • the area ratio and the maximum area of the above-mentioned void portion become preferable numerical values, and the thermal conductivity of the cured product becomes more excellent.
  • the preheating temperature is preferably 1 to 50 ° C. lower than the temperature at which the adhesive film loses weight by 0.5%, particularly preferably 10 to 40 ° C., and further preferably 15 to 30 ° C.
  • the lower limit of the preheating temperature is preferably 80 ° C. or higher, particularly 90 ° C. or higher, and more preferably 100 ° C. or higher.
  • the above preheating step is preferably performed for 30 minutes or more, particularly preferably 30 to 120 minutes, and further preferably 30 to 60 minutes.
  • the heat treatment is performed by performing the preheating step and then performing a complete curing step at a heating temperature at which the adhesive film is completely cured.
  • the heating temperature in the complete curing step needs to be higher than the above-mentioned preheating temperature, preferably 5 to 100 ° C. higher than the preheating temperature, particularly preferably 10 to 70 ° C., and further. It is preferably 20 to 50 ° C. higher.
  • the heating temperature in the complete curing step is preferably 85 to 200 ° C, particularly preferably 100 to 190 ° C, and further preferably 120 to 180 ° C.
  • the above-mentioned complete curing step is preferably performed for 30 to 180 minutes, particularly preferably 45 to 150 minutes, and further preferably 60 to 120 minutes.
  • the cured product according to the present embodiment may exist as a single substance, but usually exists in a state of being in contact with one or more members to be thermally conducted.
  • FIG. 2 shows a structure as an example in this embodiment.
  • the structure 3 shown in FIG. 2 includes a first member 31, a second member 32, and a cured body 1A provided between the first member 31 and the second member 32.
  • the cured product 1A is a product obtained by completely curing the above-mentioned adhesive film (adhesive film 1; including a heat-pressed adhesive film and a heat-pressed adhesive film) by the above-mentioned heat treatment.
  • the first member 31 and the second member 32 are fixed to each other by the adhesiveness of the cured body 1A (adhesive film).
  • the shapes of the first member 31 and the second member 32 in the present embodiment are not particularly limited, but may be a flexible sheet shape, a plate shape, a block shape, or the like. There may be.
  • the first member 31 (or the second member 32) in the present embodiment is not particularly limited, but for example, a member that generates heat as a result of exerting a predetermined function but is required to suppress a temperature rise, or the member generates heat.
  • a member (heat generating member) that is required to control the flow of heat in a specific direction is preferable.
  • the second member 32 (or the first member 31) is not particularly limited, but a member that dissipates heat received or a member that transfers the received heat to another member (heat transfer member) is preferable. .. Since the cured body 1A in the present embodiment has excellent thermal conductivity, for example, heat for conducting heat of the generated first member 31 to the second member 32 and releasing the heat to the outside world. Functions as a conductive material.
  • the heat generating member examples include thermoelectric conversion devices, photoelectric conversion devices, semiconductor devices such as large-scale integrated circuits, electronic devices such as LED light emitting elements, optical pickups, and power transistors, and various electronic devices such as mobile terminals and wearable terminals. Examples include batteries, batteries, motors, engines, etc.
  • the heat transfer member is preferably made of a highly conductive material, for example, a metal such as aluminum, stainless steel or copper, graphite, carbon nanofibers or the like.
  • the form of the heat transfer member may be any of a substrate, a housing, a heat sink, a heat spreader, and the like, and is not particularly limited.
  • one side of the adhesive film described above is attached to the first member 31 (or the second member 32), and then the other side of the adhesive film is attached. It is attached to the second member 32 (or the first member 31).
  • the adhesive film 2 with a support sheet described above is used, the release sheet 12 is peeled off, one surface of the exposed adhesive film 1 is attached to the first member 31 (or the second member 32), and then the exposed adhesive film 1 is attached.
  • the support sheet 11 may be peeled off, and the other surface of the exposed adhesive film 1 may be attached to the second member 32 (or the first member 31).
  • the adhesive film used to manufacture the structure 3 according to the present embodiment may be either a heat-pressed adhesive film or a heat-pressed adhesive film, but a heat-pressed adhesive film is used. Is preferable. Further, after the adhesive film is attached to the first member 31 (or the second member 32) using an adhesive film that has not been heat-pressed, or through the adhesive film, the first member 31 and the first member 31 The adhesive film may be hot-pressed after being bonded to the member 32 of 2. However, if an adhesive film that has been heat-pressed in advance is used, it is possible to prevent the first member 31 and / or the second member 32 from being damaged by the heat press.
  • any method is used when the first member 31 and the second member 32 are attached to each other via the adhesive film, or when the adhesive film is attached to the first member 31 or the second member 32.
  • the temperature is higher than the temperature showing the peak of loss tangent (tan ⁇ ) obtained by measuring the viscoelasticity of the adhesive film before heat treatment (hereinafter sometimes referred to as “tan ⁇ peak temperature”) (hereinafter referred to as “pasting treatment temperature”). There is.), It is preferable to perform the above-mentioned bonding or pasting. By affixing or affixing at such a temperature, the adhesive film becomes flexible, and it is possible to more effectively suppress the entrainment of air between the adhesive film and the adherend. The thermal conductivity between can be made better.
  • the method for measuring the viscoelasticity of the adhesive film is as shown in a test example described later.
  • the first member 31 is a flexible sheet-like member, and when the laminated body of the sheet-like member and the adhesive film is attached to the second member 32, or when the adhesive film 2 with a support sheet is attached to the first member. When it is attached to the member 31 or the second member 32, the above-mentioned air entrainment suppressing effect becomes more excellent. Since the laminated body of the sheet-like member and the adhesive film and the adhesive film 2 with a support sheet are flexible and easy to bend, they can be gradually brought into close contact with the adherend from one direction to the other, and air is pushed out. This is because it can be pasted while.
  • the above-mentioned pasting treatment temperature is preferably 0 to 50 ° C. higher than the tan ⁇ peak temperature, particularly preferably 2 to 30 ° C., and further preferably 5 to 20 ° C.
  • the upper limit of the above-mentioned application processing temperature needs to be lower than the curing temperature of the adhesive film, specifically, it is preferably 120 ° C. or lower, particularly preferably 100 ° C. or lower, and further. It is preferably 90 ° C. or lower.
  • one side of the adhesive film is attached to the first member 31 (or the second member 32), and the other side of the adhesive film is attached to the second member 32 (or the first member 31).
  • the heat treatment for producing the cured body of the adhesive film described above is performed to completely cure the adhesive film to obtain a cured body 1A, and the structure 3 according to the present embodiment is obtained.
  • the release sheet 12 laminated on the adhesive film 1 may be omitted.
  • the shapes of the first member and the first member in the structure are not limited to those shown in FIG. 2, and may be various shapes.
  • Example 1 The following components (a) and (c) are mixed and diluted with methyl ethyl ketone so that the solid content concentration becomes 15% by mass, and the mixture is stirred with a disper at a rotation speed of 3000 rpm for 30 minutes or more to dissolve and disperse. rice field.
  • the following components (b-1), (b-2), (d-1), (d-2) and (e) are added thereto, and the total solid content concentration is 21% by mass.
  • Methyl ethyl ketone was added so as to be.
  • This mixed solution was stirred with a rotating / revolving mixer (manufactured by Shinky Co., Ltd., product name "AR-100”) for 10 minutes to obtain a coating liquid for an adhesive resin composition.
  • each component in this adhesive resin composition is 30.01% by mass for the component (a), 34.95% by mass for the component (c), and 16 for the component (b-1). .56% by mass, (b-2) component is 7.23% by mass, (d-1) component is 5.61% by mass, (d-2) component is 5.61% by mass, and (e) component is 0. It was 0.03% by mass.
  • Thermosetting component Solid epoxy resin having a naphthalene skeleton represented by the following formula (1) (manufactured by Nippon Kayaku Co., Ltd., product name "NC-7000L", epoxy equivalent 223 to 238 g / eq, ICI viscosity (150 ° C.) 0.50 to 1.00 Pa ⁇ s, softening point 83 to 93 ° C.) dissolved in methyl ethyl ketone (solid content concentration 70% by mass) (In the formula, n is an integer greater than or equal to 0.)
  • Thermosetting component Bisphenol F type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "YL983U”, epoxy equivalent 165 to 175 g / eq, viscosity (25 ° C.) 3.0 to 6.0 Pa ⁇ s )
  • Binder polymer Acrylic acid ester polymer (manufactured by Mitsubishi Chemical Co., Ltd., product name "Corponil N-4617", obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate. Copolymer, weight average molecular weight: 300,000, glass transition temperature: 6 ° C) dissolved in a 1: 1 mixed solvent of ethyl acetate and toluene (solid content concentration 36% by mass)
  • (D-2) Hardener A biphenyl-type phenol compound represented by the following formula (3) (manufactured by Honshu Chemical Industry Co., Ltd., product name "BP", hydroxyl group equivalent 93.1 g / eq, sublimation temperature 283 ° C.) with methyl ethyl ketone. Dissolved (solid content concentration 10% by mass)
  • a release sheet (manufactured by Lintec Corporation, product name "SP-PET3811 (S)", peeled off by peeling off one side of a polyethylene terephthalate film with a silicone-based release agent from the coating liquid of the adhesive resin composition obtained in the above step.
  • an adhesive film with a release sheet was attached to the release-treated surface of the protective film (manufactured by Lintec Corporation, product name "SP-PET3811 (S)") in which one side of the polyethylene terephthalate film was peeled off with a silicone-based release agent.
  • SP-PET3811 (S) silicone-based release agent
  • the laminated body obtained above is cut into 4 cm ⁇ 4 cm, and a pressure of 3.0 MPa is applied to the laminated body at 50 ° C. for 30 minutes using a screw type heating press device to heat the adhesive film. Pressed.
  • Example 2 In the hot press, an adhesive film (after hot pressing) was manufactured in the same manner as in Example 1 except that the pressure applied by the screw type hot press device was 2.5 MPa.
  • Example 3 In Test Example 4, which will be described later, the temperature at which the adhesive film after the hot pressing of Example 1 was attached to the silicon wafer was set to 75 ° C. was designated as Example 3.
  • Comparative Example 1 In Test Example 6 to be described later, the adhesive film after the hot pressing of Example 1 was directly heat-treated at 175 ° C. for 3 hours (complete curing step) without performing the preheating step, and was referred to as Comparative Example 1.
  • an adhesive film (also referred to as “adhesive film after hot press” for convenience) was produced in the same manner as in Example 1 except that the pressure applied by the screw type heat press device was 0 MPa.
  • thermoly conductive filler instead of graphene in Example 1, spherical alumina particles (manufactured by Showa Denko KK, product name "CB-P05J", average particle diameter 5.0 ⁇ m, aspect ratio: 1.1, specific gravity). : 3.98 g / cm 3 ) was used, and an adhesive film was produced in the same manner as in Example 1.
  • Comparative Example 5 In Test Example 6 to be described later, the adhesive film after the hot pressing of Comparative Example 3 was directly heat-treated at 175 ° C. for 3 hours (complete curing step) without performing the preheating step, and was designated as Comparative Example 5.
  • Comparative Example 6 In Test Example 4, which will be described later, the temperature at which the adhesive film after hot pressing of Comparative Example 3 was attached to the silicon wafer was set to room temperature (RT) was designated as Comparative Example 6.
  • the temperature of the adhesive film before hot pressing obtained in Examples 1 to 3 and Comparative Examples 1 to 3, 5 to 6 was 147 ° C., and the temperature was 147 ° C. before the hot pressing obtained in Comparative Example 4.
  • the temperature of the adhesive film was 151 ° C.
  • the temperature of the adhesive film before hot pressing obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was 73 ° C.
  • the temperature was 73 ° C. before the hot pressing obtained in Comparative Examples 3 and 5 to 6.
  • the temperature of the adhesive film was 71 ° C.
  • the temperature of the adhesive film before hot pressing obtained in Comparative Example 4 was 75 ° C.
  • OMCL-AC240TS-C3 (resonance frequency; 55-65 kHz, spring constant; about 2 N / m 2 ) manufactured by Olympus was used.
  • the arithmetic average roughness (Ra) of the peeled surface of the peeled sheet was 0.002 ⁇ m.
  • a release-treated surface of a release film manufactured by Lintec Corporation, product name "SP-PET38131", thickness 38 ⁇ m
  • the obtained laminate was cut into 4 cm ⁇ 4 cm together with the release film, and heat-pressed under the conditions of each example. Then, this was cut together with the release film to obtain a sample for measuring adhesive strength having a width of 25 mm and a length of 40 mm.
  • a silicon wafer manufactured by Science and Technology Research Institute, diameter: 150 mm, thickness: 500 ⁇ m
  • the release film of the adhesive force measurement sample was peeled off, and the exposed surface of the adhesive film was attached to the treated surface of the silicon wafer to obtain a laminate composed of the silicon wafer and the adhesive force measurement sample.
  • the temperature at the time of this application was 80 ° C. (Examples 1 to 2 and Comparative Examples 1 to 5), 75 ° C. (Example 3) or room temperature (Comparative Example 6).
  • JIS Z0237: 2000 was used using a universal tensile tester (manufactured by Instron, product name "5581 type tester”).
  • a 180 ° peeling test was conducted at a peeling speed of 300 mm / min. The load at the time of this 180 ° peeling was measured, and the measured value was taken as the adhesive force (N / 25 mm). The results are shown in Table 1.
  • Test Example 5 ⁇ Evaluation of temporary adhesiveness> The laminate obtained in Test Example 4 was observed, and the temporary adhesiveness was evaluated based on the following criteria. The results are shown in Table 1. ⁇ : The sample for measuring the adhesive strength adhered to the adherend, and there was no air entrainment at the interface. ⁇ : A sample for measuring adhesive strength adhered to the adherend, and air entrainment was confirmed at the interface. X: The sample for measuring the adhesive strength did not adhere to the adherend.
  • a film having a thickness of about 30 nm is applied to the cross section of the cured body of the above adhesive film using a sputtering device (manufactured by Vacuum Device Co., Ltd., product name "MSP-20-UM magnetron sputtering"), targeting Pt-Pd. Was coated and antistatic treated.
  • a sputtering device manufactured by Vacuum Device Co., Ltd., product name "MSP-20-UM magnetron sputtering
  • Six images of the cross section of the cured product were taken using a scanning electron microscope (SEM) device (manufactured by KEYENCE, product name "VE-9800"). The imaging conditions were an acceleration voltage of 8 kV and a magnification of 1000 times.
  • SEM scanning electron microscope
  • FIG. 4 shows a binarized SEM image of a cross section of the cured body of the adhesive film of Example 1 shown in FIG.
  • the black part is the void part.
  • the binarized image is used, the total area of the void portion is divided by the area of the entire cross section of the adhesive film obtained from the SEM image, and further, from the average value of the six SEM images. I asked. The results are shown in Table 1.
  • the value was determined by comparing with the actual SEM observation image. Further, the binarized image was compared with the original SEM image, and the portion not corresponding to the void portion was appropriately excluded.
  • FIG. 5 shows an SEM image of a cross section of the cured body of the adhesive film of Comparative Example 2.
  • FIG. 6 shows a binarized SEM image shown in FIG.
  • the cured products of the adhesive films produced in Examples 1 to 3 had excellent thermal conductivity. Further, the adhesive films of Examples 1 to 3 were also excellent in temporary adhesiveness.
  • the adhesive film and the cured product according to the present invention can be suitably used for cooling the electronic device by interposing it between the heat-generating electronic device and the heat-dissipating substrate or heat sink, for example.
  • the structure according to the present invention is useful as, for example, a structure including an electronic device that generates heat and a heat-dissipating substrate or heat sink.
  • Adhesive film 11 ... Support sheet 12 . Release sheet 2 . Adhesive film with support sheet 3 ... Structure 1A ... Cured body of adhesive film 31 ... First member 32 . Second member

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  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un film adhésif 1 qui est formé d'une composition de résine adhésive qui contient (A) une charge thermoconductrice qui est composée d'au moins l'un parmi un graphène ayant une structure bidimensionnelle et un nitrure de bore à paroi unique, (B) un composant thermodurcissable et (C) un polymère liant, et qui est utilisé dans un procédé de chauffage qui comprend une étape de chauffage préliminaire et une étape de durcissement complet dans laquelle le film adhésif 1 est complètement durci après l'étape de chauffage préliminaire. Dans l'étape de chauffage préliminaire, le film adhésif 1 est maintenu à une température qui n'est pas supérieure à la température (T) décrite ci-dessous pendant 30 minutes ou plus.　Température (T) : une température à laquelle le film adhésif 1 présente une perte de poids de 0,5 % si un film adhésif 1 avant un processus de chauffage arbitraire est soumis à une mesure thermogravimétrique, le film adhésif 1 étant chauffé de 40 °C à 400 °C à une vitesse de chauffage de 10 °C/minute dans l'atmosphère ambiante. Ce film adhésif 1 présente une excellente conductivité thermique.
PCT/JP2021/038057 2020-11-04 2021-10-14 Film adhésif, film adhésif avec feuille de support, corps durci et procédé de production de structure WO2022097442A1 (fr)

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CN202180070981.5A CN116348564A (zh) 2020-11-04 2021-10-14 粘合膜、带支撑片的粘合膜、固化体及结构体的制造方法
JP2022560692A JPWO2022097442A1 (fr) 2020-11-04 2021-10-14
KR1020237005868A KR20230098130A (ko) 2020-11-04 2021-10-14 접착필름, 지지시트를 포함하는 접착필름, 경화체, 및 구조체의 제조방법

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