WO2023054676A1 - Feuille adhésive durcissable - Google Patents

Feuille adhésive durcissable Download PDF

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Publication number
WO2023054676A1
WO2023054676A1 PCT/JP2022/036714 JP2022036714W WO2023054676A1 WO 2023054676 A1 WO2023054676 A1 WO 2023054676A1 JP 2022036714 W JP2022036714 W JP 2022036714W WO 2023054676 A1 WO2023054676 A1 WO 2023054676A1
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Prior art keywords
curable adhesive
mass
group
less
film
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PCT/JP2022/036714
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English (en)
Japanese (ja)
Inventor
健太 西嶋
幹広 樫尾
直史 泉
Original Assignee
リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020247009258A priority Critical patent/KR20240070533A/ko
Priority to CN202280063976.6A priority patent/CN118043416A/zh
Priority to JP2023551900A priority patent/JPWO2023054676A1/ja
Publication of WO2023054676A1 publication Critical patent/WO2023054676A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • 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
    • 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 curable adhesive sheet.
  • An FPC can be manufactured by, for example, etching the copper foil of a copper-clad laminate in which a copper foil is bonded to an insulating resin film such as polyimide to form an electric circuit.
  • a coverlay sheet having an insulating resin base material and an adhesive layer is attached to a copper foil on which an electric circuit is formed to protect the electric circuit. ing.
  • Patent Document 1 discloses an adhesive composition containing predetermined amounts of a styrene-based elastomer, a modified polyphenylene ether resin having a polymerizable group at the end, an epoxy resin, and an epoxy resin curing agent.
  • An invention relating to a thermosetting adhesive sheet having a thermosetting adhesive layer formed on a substrate is disclosed.
  • the thermosetting adhesive sheet as described in Patent Document 1 above has a layer made of a silicone-based release agent on the thermosetting adhesive layer for the purpose of protecting the surface of the thermosetting adhesive layer.
  • a silicone-based release sheet is laminated. Silicone-based release sheets are widely used because they are easy to separate from the thermosetting adhesive layer during use and are excellent in handleability.
  • the silicon (Si) component of the layer made of the silicone-based release agent migrates to the curable adhesive layer over time, and the silicon component in the curable adhesive layer is transferred to the adherend. There is a problem that it may migrate to the surface of a certain FPC and cause malfunction of electronic equipment. Therefore, there is a demand for a curable adhesive sheet that suppresses contamination of adherends and has excellent handleability.
  • the present invention provides a curable adhesive layer capable of forming a cured product having a dielectric loss tangent of a predetermined value or less, and a curable adhesive having a first release film and a second release film sandwiching both sides of the curable adhesive layer.
  • a curable adhesive sheet in which the peel force when peeling the film from the curable adhesive layer is adjusted to a predetermined value or less.
  • one aspect provided by the present invention is as follows.
  • a curable adhesive layer capable of forming a cured product having a dielectric loss tangent of 0.01 or less at 23° C. and 1 GHz, and a first release film and a second release film sandwiching both sides of the curable adhesive layer
  • a curable adhesive sheet having The first release film and the second release film comprise a resin film and a release layer formed from a non-silicone release agent on one surface of the resin film and in contact with the surface of the curable adhesive layer. have A curable adhesive sheet that satisfies the following requirements (I).
  • Any one of [1] to [4] above, wherein the non-silicone release agent used to form the release layer of at least one of the first release film and the second release film is an alkyd release agent.
  • the curable adhesive sheet according to item 1 is a layer formed from a curable adhesive composition containing a binder resin (A), the curable according to any one of the above [1] to [5] adhesive sheet.
  • the curable adhesive sheet of a preferred embodiment of the present invention suppresses contamination of adherends, and can easily remove the release film at the time of use and has excellent handleability.
  • it is suitably applied as a coverlay sheet. can.
  • FIG. 1 is a schematic cross-sectional view in the thickness direction of the adhesive sheet, showing an example of the configuration of the curable adhesive sheet of the present invention
  • the term "active ingredient" of the curable adhesive composition means a component excluding water and a diluent such as an organic solvent among the components contained in the curable adhesive composition.
  • the number average molecular weight (Mn) is a value converted to standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in Examples. is.
  • each layer constituting the curable adhesive sheet is a value measured in accordance with JIS K7130 (1999). name "PG-02J").
  • FIG. 1 is a schematic cross-sectional view in the thickness direction of the adhesive sheet, showing an example of the configuration of the curable adhesive sheet of the present invention.
  • the curable adhesive sheet 1 of the present invention comprises a curable adhesive layer 10, and a first release film 21 and a second release film 22 sandwiching both sides of the curable adhesive layer 10. have.
  • the curable adhesive layer 10 can be cured to form a cured product having a dielectric loss tangent of 0.01 or less at 23° C. and 1 GHz.
  • the first release film 21 also has a resin film 212 and a release layer 211 on one surface of the resin film 212 that contacts the surface 10 a of the curable adhesive layer 10 .
  • the second release film 22 also has a resin film 222 and a release layer 221 on one surface of the resin film 222 that contacts the surface 10 b of the curable adhesive layer 10 .
  • the release layers 211 and 221 of the first release film 21 and the second release film 22 are layers formed from a non-silicone release agent. Since the release layers 211 and 221 are layers formed from a non-silicone release agent, the silicon (Si) component does not migrate to the surfaces 10a and 10b of the curable adhesive layer 10 that come into contact with them. None. Therefore, the curable adhesive sheet of the present invention can suppress contamination due to transfer of the silicon component to the adherend.
  • the curable adhesive layer of the curable adhesive sheet of the present invention has a low dielectric loss tangent of 0.01 or less.
  • a curable adhesive layer with a low dielectric loss tangent is often composed of a component that does not have a polar group or a component with a low polarity, and the polarity of the surface of the curable adhesive layer tends to be low. be.
  • peelability from the surface of the curable adhesive layer is rarely a problem. do not have.
  • the curable adhesive sheet of the present invention is adjusted so as to satisfy the following requirement (I) in order to deal with the handling problem that the release film is difficult to peel off from the surface of the curable adhesive layer.
  • the peel force (R1) when peeling the first peel film from the curable adhesive layer at a peel angle of 180° and a peel speed of 300 mm/min is 250 mN/50 mm or less.
  • the peel force (R1) defined in the requirement (I) is 250 mN/50 mm or less, preferably 200 mN/50 mm or less, more preferably 150 mN from the above viewpoint. /50 mm or less, more preferably 110 mN/50 mm or less, still more preferably 90 mN/50 mm or less, preferably 5 mN/50 mm or more, more preferably 10 mN/50 mm or more, still more preferably 20 mN/50 mm or more.
  • the resin film constituting the first release film, the type of release agent forming the release agent layer, and the formation of the curable adhesive layer It can be adjusted by appropriately setting the type and content of each component contained in the curable adhesive composition. A specific adjustment method will be described in detail in the description of each configuration.
  • the curable adhesive sheet of one aspect of the present invention preferably satisfies the following requirement (II) in addition to the above requirement (I).
  • the first release film can be more easily peeled off from the surface of the curable adhesive layer, and a curable adhesive sheet with excellent handleability can be obtained.
  • the curable adhesive sheet of one embodiment of the present invention more preferably satisfies the following requirement (IIa) in addition to the above requirement (I).
  • the ratio [(R1)/(R2)] of the peel force (R1) and the peel force (R2) defined in the above requirement (IIa) makes it easier to peel the first release film from the surface of the curable adhesive layer. From the viewpoint of obtaining a curable adhesive sheet with excellent handleability, it is 0.97 or less, preferably 0.95 or less, more preferably 0.88 or less, and still more preferably 0.80 or less. be.
  • the lower limit of the ratio [(R1)/(R2)] between the peel strength (R1) and the peel strength (R2) defined in the requirement (IIa) is not particularly limited, but is preferably 0.2 or more, preferably 0.35 or more.
  • the curable adhesive sheet of one aspect of the present invention preferably satisfies the following requirement (III) together with the above requirement (I), and further satisfies the following requirement (III) along with the above requirements (I) and (II). More preferably, it satisfies the requirements (I) and (IIa) as well as the requirement (III) below.
  • the peel strength (R2) is 300 mN/50 mm or less.
  • the peel force (R1) defined in the requirement (I) is 300 mN/50 mm or less, preferably 250 mN/50 mm or less, more preferably 220 mN from the above viewpoint. /50 mm or less, more preferably 150 mN/50 mm or less, still more preferably 110 mN/50 mm or less, preferably 20 mN/50 mm or more, more preferably 30 mN/50 mm or more, still more preferably 40 mN/50 mm or more.
  • the release force (R2) is also included in the type of release agent forming the resin film and the release agent layer constituting the second release film, and the curable adhesive composition forming the curable adhesive layer. It can be adjusted by appropriately setting the type and content of each component. A specific adjustment method will be described in detail in the description of each configuration.
  • peel strengths (R1) and (R2) mean values measured based on the method described in Examples below.
  • Each layer constituting the curable adhesive sheet of one embodiment of the present invention and the material forming the layer will be described below.
  • the first release film and the second release film included in the curable adhesive sheet of one embodiment of the present invention may have a structure including a resin film and a release layer formed from a non-silicone release agent.
  • resin components contained in the resin film include polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin; polyolefin resins such as polypropylene resin and polyethylene resin; Examples include mixed resins in which more than one species are used in combination.
  • the resin film contains additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, and colorants (pigments, dyes, etc.). good too.
  • the resin film may be a colored resin film.
  • the colored resin film may be a foamed resin film in which a resin layer is foamed for coloring.
  • the foamed resin film is usually a white opaque colored resin film.
  • a resin film formed from a resin composition containing a filler together with a resin component also becomes a colored resin film due to a decrease in transparency due to light scattering. Furthermore, in order to color it in a desired color, it may be a colored resin film formed from a resin composition containing a desired colorant together with the resin component.
  • the resin film (1) constituting the first release film is preferably a colored resin film from the viewpoint of making the curable adhesive sheet superior in handleability.
  • the first release film made of a colored resin film the distinction from the second release film becomes clear. For example, it is possible to prevent the misuse of peeling off the second peeling film when the first peeling film should be peeled off at the time of use.
  • a colored resin film also includes a white resin film.
  • the resin film (2) constituting the second release film is visually distinguishable from the resin film (1) constituting the first release film.
  • the resin film (2) is a colorless and transparent resin film, or the resin film (2) is a resin film.
  • a method of forming a transparent or opaque colored resin film having a different color from (1) may be used, and a method of attaching a visible mark to the surface of the resin film (2) may be used.
  • the state of the surface of the adherend is visually observed through the second release film, or observed by other optical means.
  • the method of making the resin film (2) transparent and colorless when the resin film (1) is a colored resin film or a method of making the resin film (2) a colorless and transparent resin film.
  • a method of forming a transparent or opaque colored resin film having a color different from that of the film (1) is preferred, and a method of forming a colorless and transparent resin film as the resin film (2) is more preferred.
  • a release agent, a fluorine-based release agent, and the like are included.
  • the non-silicone release agent is preferably an alkyd release agent, and the non-silicone release agent used to form the release layers of both the first release film and the second release film is an alkyd release agent. It is more preferable to have
  • the thickness (T1) of the first release film is preferably 10 ⁇ m or more, from the viewpoint of adjusting the peel force (R1) to a range satisfying the above requirement (I).
  • the thickness is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 70 ⁇ m or less, and even more preferably 45 ⁇ m or less.
  • the thickness (T2) of the second release film is preferably 30 ⁇ m or more, from the viewpoint of adjusting the peel force (R2) to a range that satisfies the above requirement (III). It is preferably 35 ⁇ m or more, and preferably 270 ⁇ m or less, more preferably 210 ⁇ m or less, and still more preferably 140 ⁇ m or less. Furthermore, from the viewpoint of obtaining a curable adhesive sheet that satisfies the above requirements (II) and (IIa), the thickness (T2) of the second release film is preferably 47 ⁇ m or more, more preferably 55 ⁇ m or more, and still more preferably 65 ⁇ m or more. be.
  • the thickness (T1) of the first release film and the thickness of the second release film is preferably 0.15 or more, more preferably 0.20 or more, still more preferably 0.25 or more, and is preferably 1.5. 00 or less, more preferably 0.90 or less, and still more preferably 0.80 or less.
  • the curable adhesive layer of the curable adhesive sheet of one embodiment of the present invention can form a cured product having a dielectric loss tangent of 0.01 or less at 23° C. and 1 GHz.
  • the dielectric loss tangent of the cured product that can be formed at 23° C. and 1 GHz is 0.01 or less, preferably 0.005 or less, more preferably 0.002 or less.
  • the dielectric loss tangent of the cured product at 23° C. and 1 GHz is not particularly limited to a lower limit, but is preferably 0.00005 or more, more preferably 0.0001 or more. In this specification, the dielectric loss tangent of the cured product means a value measured based on the method described in Examples below.
  • the method for curing the curable adhesive layer may be a thermosetting method or a photo-curing method, and can be appropriately selected according to the application.
  • a thermosetting method is preferable.
  • the thickness of the curable adhesive layer is preferably 3.0 ⁇ m or more, more It is preferably 5.0 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, and preferably 60 ⁇ m or less, more preferably 45 ⁇ m or less.
  • the curable adhesive layer of the curable adhesive sheet of one aspect of the present invention can be formed from a curable adhesive composition containing a binder resin (A) (hereinafter also referred to as "component (A)"). .
  • the curable adhesive composition used in one aspect of the present invention is a curable adhesive sheet adjusted to satisfy the above requirements (I) or (III), and has improved adhesive strength and low dielectric properties.
  • the curable adhesive composition used in one aspect of the present invention includes a cationic polymerization initiator (D) (hereinafter also referred to as “component (D)”), which reacts with the reactive functional group of component (A).
  • the curable adhesive composition used in one aspect of the present invention may contain additives other than these components (A) to (F) within a range that does not impair the effects of the present invention.
  • the total content of components (A) and (B) is the total amount of active ingredients in the curable adhesive composition (100 mass %), preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 100% by mass or less, more It may be preferably 99.90% by mass or less, more preferably 99.00% by mass or less, still more preferably 95.00% by mass or less.
  • the total content of component (A), component (B), component (C), and component (D) is It is preferably 60% by mass or more, more preferably 75% by mass or more, still more preferably 90% by mass or more, and usually 100% by mass or less, relative to the total amount (100% by mass) of the active ingredients of the composition. , 99.70% by mass or less, or 90% by mass or less.
  • component (A), component (B), component (C), component (D), component (E), and component (F) The total content is preferably 60% by mass or more, more preferably 75% by mass or more, and still more preferably 90% by mass or more with respect to the total amount (100% by mass) of the active ingredients of the curable adhesive composition. Also, it is usually 100% by mass or less, and may be 99.70% by mass or less, or 90% by mass or less. Details of each component contained in the curable adhesive composition used in one embodiment of the present invention are described below.
  • the curable adhesive composition used in one aspect of the present invention preferably contains a binder resin (A). By containing the binder resin (A), it becomes a composition capable of forming a curable adhesive layer having excellent adhesive strength when cured and good shape stability.
  • the binder resin (A) may be used alone or in combination of two or more.
  • the content of component (A) is preferably 35% by mass with respect to the total amount (100% by mass) of the active ingredients in the curable adhesive composition. Above, more preferably 45% by mass or more, still more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.
  • the number average molecular weight (Mn) of the binder resin (A) used in one embodiment of the present invention is from the viewpoint of improving film-forming properties and forming a curable adhesive layer with good shape stability. , preferably 10,000 or more, more preferably 25,000 or more, and still more preferably 35,000 or more, and when the composition is in the form of a solution, the solubility of the component (A) with a dilution solvent is preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less, from the viewpoint of making the composition excellent in coating properties.
  • binder resin (A) examples include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamide-imide-based resins, polyvinyl butyral-based resins, polycarbonate-based resins, and styrene-based resins.
  • the binder resin (A) used in one embodiment of the present invention contains a polyolefin resin from the viewpoint of being a composition capable of forming a cured product having excellent dielectric properties in a high frequency region (eg, 1 GHz or higher). is preferred.
  • the polyolefin-based resin may be a polymer having structural units derived from an olefin-based monomer, and may be a polymer consisting only of structural units derived from an olefin-based monomer. It may be a copolymer having a structural unit derived from and a structural unit derived from a monomer copolymerizable with an olefinic monomer.
  • the olefinic monomers constituting the polyolefinic resin include ⁇ -olefins having 2 or more carbon atoms, preferably ⁇ -olefins having 2 to 8 carbon atoms, ethylene, propylene, 1-butene, isobutylene, and 1- At least one selected from hexene is more preferred, and at least one selected from ethylene and propylene is even more preferred. These olefinic monomers may be used alone or in combination of two or more.
  • Examples of monomers copolymerizable with olefinic monomers that constitute the polyolefinic resin include vinyl acetate, (meth)acrylic acid esters, and styrene. These monomers may be used alone or in combination of two or more.
  • the polyolefin resin used in one aspect of the present invention includes very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low Density polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefinic elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic Examples include acid ester copolymers.
  • VLDPE very low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • PP ethylene-propylene copolymer
  • TPO olefinic elastomer
  • EVA ethylene-vinyl acetate copolymer
  • ethylene-(meth)acrylic acid copolymer ethylene-(meth)acrylic
  • the binder resin (A) used in one aspect of the present invention is a composition capable of forming a curable adhesive layer with improved film-forming properties and good shape stability, and improved low dielectric properties. From the viewpoint of making the composition capable of forming a cured product and reducing the peeling force when peeling the first release film or the second release film from the curable adhesive layer, a binder resin having a reactive functional group is added. It preferably contains one or more selected from a polyolefin resin having a reactive functional group and a styrene resin having a reactive functional group, and more preferably contains a polyolefin resin having a reactive functional group (A1 ) is further preferred.
  • the content of the polyolefin-based resin (A1) is, from the viewpoint of making the composition capable of forming a cured product having excellent low dielectric properties, the curable adhesive composition It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, based on the total amount (100% by mass) of component (A) contained in the product.
  • the reactive functional groups of the binder resin (A) include, for example, a carboxy group, a group having a carboxylic anhydride structure, a group having a carboxylic acid ester structure, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, Amino group, imide group, isocyanate group, acetyl group, thiol group, sulfone group, phosphon group, nitro group, halogen atom, alkoxysilyl group and the like.
  • the reactive functional groups possessed by the binder resin (A) may be composed of one type alone, or may be composed of a combination of two or more types.
  • the reactive functional groups possessed by the binder resin (A) include a carboxy group, a group having a carboxylic anhydride structure, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, an isocyanate group, A composition that is preferably a group selected from an acetyl group, a thiol group, an ether group, a thioether group, a sulfone group, a phosphonic group, a nitro group, a urethane group, a halogen atom, and an alkoxysilyl group, and which can form a cured product with excellent adhesive strength.
  • a group selected from a group having a carboxyl group and a carboxylic anhydride structure is more preferable, and a group having a carboxylic anhydride structure is more preferable from the viewpoint of obtaining a composition capable of forming a cured product having excellent adhesive strength and low dielectric properties.
  • the binder resin (A) used in one aspect of the present invention may be a modified resin obtained by modifying a main chain resin using a modifying agent to introduce the reactive functional groups described above.
  • specific modified resins include acid-modified resins into which acid groups have been introduced and resins into which hydroxyl groups have been introduced.
  • an acid-modified resin into which an acid group is introduced is preferable, and is more excellent in adhesive strength and low dielectric properties.
  • an acid anhydride-modified resin into which an acid anhydride structure is introduced is more preferable.
  • Acid-modified resins or acid anhydride-modified resins are produced, for example, by reacting unsaturated carboxylic acids or the like with resins that serve as the main chain to form carboxy groups or carboxylic acid anhydrides. It is obtained by introducing a structure and graft-denaturing it.
  • the method of introducing the unsaturated carboxylic acid or the like into the resin is not particularly limited. A method of heating and melting the reaction as described above, or a method of dissolving the resin and the unsaturated carboxylic acid or the like in an organic solvent, followed by heating and stirring in the presence of a radical generator, and the like.
  • Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid.
  • Examples of unsaturated carboxylic anhydrides include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride. These may be used alone or in combination of two or more.
  • maleic anhydride is preferable from the viewpoint of forming a composition capable of forming a cured product having excellent adhesive strength and low dielectric properties.
  • the amount of unsaturated carboxylic acid or the like to be reacted with the resin is preferably 0.1 to 5 parts per 100 parts by mass of the resin, from the viewpoint of making the composition capable of forming a cured product having excellent adhesive strength and low dielectric properties. parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.2 to 1 part by mass.
  • the curable adhesive composition used in one aspect of the present invention is a curable adhesive sheet adjusted to satisfy the above requirements (I) or (III), and has improved adhesive strength and low dielectric properties. From the viewpoint of making the composition capable of forming a cured product, it is preferable to contain a polyphenylene ether resin (B). In addition, polyphenylene ether resin (B) may be used independently and may use 2 or more types together.
  • the content of component (B) is preferably 5 parts by mass or more, more preferably 12 parts by mass, with respect to 100 parts by mass of the total amount of component (A). Above, more preferably 17 parts by mass or more, preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the number average molecular weight (Mn) of the polyphenylene ether resin (B) used in one embodiment is preferably 1500 or more, more preferably 1700 or more, still more preferably 1900 or more, and when the composition is in the form of a solution In addition, it is preferably 7,000 or less, more preferably 5,500 or less, and still more preferably 4,000 or less from the viewpoint of improving the solubility of the component (B) in the diluent solvent and making the composition excellent in coatability.
  • the polyphenylene ether resin (B) used in one aspect of the present invention may be a resin having a structural unit represented by at least one of the following general formulas (bi) and (b-ii) in the main chain.
  • R a1 and R a2 each independently represent a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom) having 1 to 6 alkyl group or phenyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, methyl groups or ethyl groups are even more preferred, and methyl groups are particularly preferred.
  • halogen atom fluorine atom, chlorine atom, bromine atom, or iodine atom
  • alkyl groups having 1 to 6 carbon atoms that can be selected as R a1 and R a2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s -butyl group, isobutyl group, n-pentyl group, n-hexyl group and the like.
  • m1 and m2 are each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 2.
  • the polyphenylene ether resin (B) used in one aspect of the present invention is preferably a resin having a skeleton represented by the following formula (b-1) as a main chain.
  • R a1 and R a2 , and m1 and m2 are the same as defined in general formula (bi) or formula (b-ii) above; The same applies to types and numerical ranges.
  • X is a divalent organic group, and at least one hydrogen atom of the organic group may be substituted with a substituent.
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater. * indicates the bonding position with the terminal group.
  • Examples of divalent hydrocarbon groups that can be selected as X include an alkylene group having 1 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, and a ring-forming carbon atom number of 3. to 10 cycloalkylene groups, cycloalkenylene groups having 3 to 10 ring-forming carbon atoms, phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, groups formed by combining two or more of these groups, and the like.
  • the alkylene group, oxyalkylene group, and alkenylene group described above may be linear or branched.
  • the alkylene group, oxyalkylene group, and alkenylene group have a substituent selected from a halogen atom, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, and a cycloalkyl group having 3 to 10 carbon atoms.
  • cycloalkylene group, cycloalkenylene group, phenylene group, biphenylene group, terphenylene group, and naphthylene group are halogen atoms, alkyl groups having 1 to 6 carbon atoms, oxyalkyl groups having 1 to 6 carbon atoms, and may have a substituent selected from alkenyl groups having 1 to 6 carbon atoms.
  • X is the following: A group represented by formula (b-2) is preferred.
  • R b1 and R b2 each independently represent a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), an alkyl group having 1 to 6 carbon atoms, and an oxyalkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and 1 to 6 carbon atoms;
  • An alkyl group of 3 is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred.
  • alkyl groups having 1 to 6 carbon atoms that can be selected as R b1 and R b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s -butyl group, isobutyl group, n-pentyl group, n-hexyl group and the like.
  • n1 and n2 are each independently an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 3.
  • A is a single bond or a divalent hydrocarbon group.
  • the divalent hydrocarbon group that can be selected as A includes, for example, an alkylene group having 1 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, and a ring-forming carbon atom number of 3. to 10 cycloalkylene groups and 3 to 10 ring-forming carbon atoms cycloalkenylene groups.
  • the alkylene group, oxyalkylene group, and alkenylene group may be linear or branched.
  • the hydrocarbon group that can be selected as A includes a substituent selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, and an alkenyl group having 1 to 6 carbon atoms. may have.
  • A is a single A bond or an alkylene group having 1 to 20 carbon atoms is preferable, and a single bond is more preferable.
  • the ether resin (B) is more preferably a resin having a skeleton represented by the following formula (b-3) as the main chain.
  • R a1 and R a2 are the same as defined in general formula (bi) or formula (b-ii) above. are the same. Further, R b1 and R b2 are the same as defined in the general formula (b-2) above, and the types and numerical ranges of suitable groups are also the same.
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater. * indicates the bonding position with the terminal group.
  • R a1 , R a2 , R b1 , and R b2 in the general formula (b-3) are each independently preferably an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms. is more preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred.
  • the polyphenylene ether resin (B) used in one aspect of the present invention is a curable adhesive sheet adjusted to satisfy the above requirements (I) or (III), and further improves low dielectric properties, crosslinkability, and heat resistance.
  • Polyphenylene ether resins having a vinyl group are preferable from the viewpoint of forming a composition capable of forming a cured product.
  • the vinyl group that the polyphenylene ether resin (B) has may be one that constitutes a part of the hydrocarbon substituent, such as vinylbenzyl group and vinylnaphthyl group. That is, the polyphenylene ether resin (B) is formed by bonding a vinyl group or a vinyl group-containing hydrocarbon group to a polyphenylene ether skeleton.
  • the polyphenylene ether resin (B) used in one aspect of (1) is preferably a resin having a vinyl group or a vinyl group-containing hydrocarbon group at both ends of the main chain.
  • a polyphenylene ether resin (B) having a vinyl group or a vinyl group-containing hydrocarbon group at both ends of the main chain forms a polyphenylene ether skeleton to be the main chain, and then has a vinyl group or a vinyl group-containing hydrocarbon group at both ends.
  • a bifunctional phenol compound and a monofunctional phenol compound are reacted to obtain a polymer having phenolic hydroxyl groups at both ends, and then 4-(chloromethyl)styrene is used to convert the terminal phenolic hydroxyl groups to vinyl.
  • 4-(chloromethyl)styrene is used to convert the terminal phenolic hydroxyl groups to vinyl.
  • benzyl etherifying a polyphenylene ether resin (B) having vinylbenzyl groups at both ends of the polyphenylene ether skeleton can be obtained.
  • the polyphenylene ether resin (B) used in one aspect of the present invention is preferably a compound represented by the following general formula (b-4).
  • p1 and p2 are each independently an integer of 0 or greater, and p1+p2 is an integer of 1 or greater.
  • a commercially available product can also be used as the polyphenylene ether resin (B) used in one aspect of the present invention.
  • Examples of commercially available products include OPE-2St (compound represented by the above general formula (b-4)) manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.
  • the curable adhesive composition used in one aspect of the present invention preferably contains a polyfunctional compound (C) having two or more unsaturated hydrocarbon groups with double bonds at their terminals.
  • the polyfunctional compound (C) in the present invention excludes compounds corresponding to the components (A) and (B).
  • a composition containing a polyfunctional compound (C) together with the polyphenylene ether resin (B) described above a cured product having improved low dielectric properties and adhesive strength in a well-balanced manner can be formed.
  • the polyfunctional compound (C) has two or more unsaturated hydrocarbon groups, a crosslinked structure is formed in the obtained cured product, thereby forming a cured product with further improved adhesive strength.
  • polyfunctional compound (C) may be used independently and may use 2 or more types together.
  • the content of the component (C) is a composition capable of forming a cured product excellent in low dielectric properties with respect to 100 parts by mass of the total amount of the component (A). It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more, from the viewpoint of obtaining a curable adhesive sheet with improved sticking properties while maintaining a product, and component (C) Since the release force (R1) and the release force (R2) tend to increase as the content of It is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the component (B) and the component (C) are preferably 15/85 or more, more preferably 30/70 or more, and preferably 85/15 or less, in terms of mass ratio. Preferably it is 70/30 or less.
  • the total content of component (B) and component (C) is the above requirement (I) or ( From the viewpoint of making a curable adhesive sheet adjusted to satisfy III) and having excellent sticking properties, and from the viewpoint of making a composition capable of forming a cured product having excellent adhesive strength, it is preferable It is 85 parts by mass or less, more preferably 75 parts by mass or less, still more preferably 65 parts by mass or less, and preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and still more preferably 35 parts by mass or more.
  • the number of carbon atoms in the unsaturated hydrocarbon group per one of the polyfunctional compound (C) used in one aspect of the present invention is preferably 2 to 7, more preferably 2 to 4, and still more preferably 2 to 3.
  • the unsaturated hydrocarbon group include vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, 1-methyl-2-propenyl group and vinylbenzyl group. , a vinyl naphthyl group, and the like.
  • the unsaturated hydrocarbon group possessed by the polyfunctional compound (C) is preferably an allyl group.
  • the number of the unsaturated hydrocarbon groups possessed by the polyfunctional compound (C) used in one aspect of the present invention is 2 or more, but the crosslinked structure is moderately sparse, and a cured product in which the generation of cracks is suppressed is obtained.
  • the polyfunctional compound (C) used in one embodiment of the present invention has two unsaturated hydrocarbon groups.
  • a polyfunctional compound having the above and further having a saturated hydrocarbon group is preferred.
  • the polyfunctional compound (C) used in one embodiment of the present invention preferably has 1 to 4 saturated hydrocarbon groups, more preferably 1 to 2, and still more preferably 1.
  • Examples of the saturated hydrocarbon group include an alkyl group and an alkyl group substituted with an alkoxy group.
  • alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group and the like.
  • the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 4-18, even more preferably 6-16, and even more preferably 8-15.
  • alkyl group substituted with the alkoxy group examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethoxymethyl group, benzyloxymethyl group and the like.
  • the number of carbon atoms in the alkyl group substituted with the alkoxy group is preferably 2-15, more preferably 2-12, and still more preferably 3-10.
  • the polyfunctional compound (C) used in one aspect of the present invention preferably contains the polyfunctional compound (C1) having two unsaturated hydrocarbon groups.
  • the composition containing such a polyfunctional compound (C1) having two unsaturated hydrocarbon groups suppresses the occurrence of cracks and causes warping of a plate-like member such as a circuit board as an adherend.
  • the polyfunctional compound (C1) is more preferably a polyfunctional compound having two unsaturated hydrocarbon groups and at least one saturated hydrocarbon group.
  • the content of the polyfunctional compound (C1) is the total amount of the component (C) contained in the curable adhesive composition (100 mass %), preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
  • the polyfunctional compound (C) used in one aspect of the present invention is preferably a polyfunctional compound having a heterocyclic skeleton.
  • a polyfunctional compound having a heterocyclic skeleton By including a polyfunctional compound having a heterocyclic skeleton, it is possible to obtain a composition capable of forming a cured product with improved low dielectric properties and adhesive strength.
  • Specific heterocyclic skeletons include an isocyanurate skeleton and a glycoluril skeleton.
  • Examples of the polyfunctional compound (C) used in one embodiment of the present invention include compounds having an isocyanurate skeleton represented by the following general formula (c-1), glycoluril represented by the following general formula (c-2) A compound having a skeleton can be mentioned.
  • R 11 to R 13 are each independently an unsaturated hydrocarbon group having a double bond at the end or a saturated hydrocarbon group, are the unsaturated hydrocarbon groups.
  • R 21 to R 26 are each independently a hydrogen atom, an unsaturated hydrocarbon group having a double bond at the end, or a saturated hydrocarbon group, At least two of R 21 to R 26 are the unsaturated hydrocarbon groups.
  • Specific examples of unsaturated hydrocarbon groups and saturated hydrocarbon groups that can be selected as R 11 to R 13 and R 21 to R 26 are as described above, and the preferred carbon number ranges are also as described above. .
  • the polyfunctional compound (C) used in one embodiment of the present invention preferably contains a compound having an isocyanurate skeleton represented by the general formula (c-1), It more preferably contains a compound (C11) having an isocyanurate skeleton represented by the following general formula (c-11).
  • R a is a saturated hydrocarbon group, and specific examples thereof are as described above. Among these, R a is preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 4-18, even more preferably 6-16, and even more preferably 8-15.
  • the content of the compound (C11) is based on the total amount (100% by mass) of the component (C) contained in the curable adhesive composition. , preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
  • a commercially available product may be used as the polyfunctional compound (C) used in one embodiment of the present invention.
  • Specific commercial products include, for example, L-DAIC (product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., compound represented by the general formula (c-11)), TAIC (registered trademark) (product name, Mitsubishi Chemical Co., Ltd., a compound in which R 11 to R 13 in the general formula (c-1) are allyl groups), TA-G (product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., in the general formula (c-2) compounds represented) and the like.
  • L-DAIC product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., compound represented by the general formula (c-11)
  • TAIC registered trademark
  • TA-G product name, manufactured by Shikoku Kasei Kogyo Co., Ltd., in the general formula (c-2) compounds represented
  • the molecular weight (formula weight) of the polyfunctional compound (C) used in one aspect of the present invention is the viewpoint of making the composition easy to form a cured product having desired physical properties, and the smaller the molecular weight of the component (C), the , Since the peel strength (R1) and peel strength (R2) tend to increase, from the viewpoint of adjusting the curable adhesive sheet so as to satisfy the above requirement (I) or (III), it is preferably 200 or more, more It is preferably 230 or more, more preferably 270 or more, and preferably 1000 or less, more preferably 800 or less, still more preferably 800 or less, from the viewpoint of making the composition easy to form a curable adhesive layer that can be easily applied at room temperature. 500 or less.
  • the boiling point of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175 to 350°C, more preferably 200 to 300°C.
  • the 5% weight loss temperature of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175 to 350°C, more preferably 200 to 300°C.
  • the liquid compound (C) is preferably a compound that is liquid at 25°C.
  • a compound that is liquid at 25°C refers to a compound that has fluidity at 25°C. means a compound having a viscosity of 2 to 10,000 mPa ⁇ s as measured by
  • the curable adhesive composition used in one aspect of the present invention preferably further contains a cationic polymerization initiator (D).
  • a cationic polymerization initiator (D) By making the curable adhesive composition containing the cationic polymerization initiator (D), the polymerization reaction of the component (B) and the component (C) is sufficiently advanced, and the curable adhesive layer formed is preserved. Stability can be improved.
  • a cationic polymerization initiator (D) may be used independently and may use 2 or more types together.
  • the content of component (D) is such that component (B) and component ( From the viewpoint of making the composition capable of sufficiently advancing the polymerization reaction of component C and forming a curable adhesive layer with improved storage stability, the amount is preferably 0.01 parts by mass or more, more preferably 0.05. parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.15 parts by mass or more, still more preferably 0.20 parts by mass or more, even more preferably 0.25 parts by mass or more, and particularly preferably 0.25 parts by mass or more.
  • 30 parts by mass or more preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, still more preferably is 1.5 parts by mass or less, more preferably 1.0 parts by mass or less, and particularly preferably 0.70 parts by mass or less.
  • the cationic polymerization initiator (D) used in one aspect of the present invention may be a thermal cationic polymerization initiator or a photocationic polymerization initiator, and the polymerization can be carried out in a simple process. From this point of view, a thermal cationic polymerization initiator is preferred.
  • the thermal cationic polymerization initiator used in one aspect of the present invention is a compound capable of generating a cationic species that initiates polymerization by heating. is mentioned. These thermal cationic polymerization initiators may be used alone or in combination of two or more.
  • Sulfonium salts include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris(4-methoxyphenyl)sulfonium hexafluoroalcinate, diphenyl(4-phenylthiophenyl ) sulfonium hexafluoroalcinate and the like.
  • commercially available sulfonium salts can also be used.
  • SI-80L, San-Aid SI-100L, San-Aid SI-B2A, San-Aid SI-B3 manufactured by Sanshin Chemical Industry Co., Ltd.
  • CYRACURE UVI-6974 CYRACURE UVI-6990 (manufactured by Union Carbide)
  • UVI -508, UVI-509 manufactured by General Electric Co.
  • FC-508, FC-509 manufactured by Minnesota Mining and Manufacturing Co.
  • CD-1010, CD-1011 manufactured by Thurstomer (manufactured by Nippon Soda Co., Ltd.), CI series products (manufactured by Nippon Soda Co., Ltd.), and the like.
  • quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N,N-dimethyl- N-benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyltrifluoro romethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
  • Phosphonium salts include, for example, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.
  • diazonium salts examples include AMERICURE (manufactured by American Can) and ULTRASET (manufactured by ADEKA).
  • iodonium salts examples include diphenyliodonium hexafluoroarcinate, bis(4-chlorophenyl)iodonium hexafluoroarcinate, bis(4-bromophenyl)iodonium hexafluoroarcinate, phenyl(4-methoxyphenyl)iodonium hexafluoroalkinate, and the like.
  • Commercially available iodonium salts can also be used, such as UV-9310C (manufactured by Toshiba Silicone Co., Ltd.), Photoinitiator 2074 (manufactured by Rhone-Poulenc), UVE series products (manufactured by General Electric), FC series. (manufactured by Minnesota Mining and Manufacturing Co.).
  • the curable adhesive composition of one aspect of the present invention contains the cationic polymerization initiator (D), at least part of the cationic polymerization initiator (D) is subjected to differential scanning calorimetry under the following conditions.
  • It may be a high-temperature reactive thermal cationic polymerization initiator that gives a peak top temperature of an exothermic peak exceeding 120°C.
  • Differential scanning calorimetry conditions A mixture containing 0.1 part by mass of a cationic polymerization initiator to be measured, 100 parts by mass of bisphenol A diglycidyl ether, and 0.1 part by mass of ⁇ -butyrolactone was used as a measurement sample, and the temperature was changed from 30°C to 300°C. Differential scanning calorimetry is performed at a heating rate of 10° C./min to measure the peak temperature of the exothermic peak.
  • Examples of commercially available high-temperature reactive thermal cationic polymerization initiators include San-Aid SI-B3, San-Aid SI-B4, San-Aid SI-B5, and San-Aid SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.). .
  • ⁇ Reactive curing agent other than cationic polymerization initiator (D)> The curable adhesive composition used in one aspect of the present invention, in place of the cationic polymerization initiator (D), or together with the cationic polymerization initiator (D), in a range that does not impair the effects of the present invention, cationic polymerization initiation Other reactive curing agents than the agent (D) may be contained.
  • the content of the other reactive curing agent is 0 to 90 parts by mass and 0 to 50 parts by mass with respect to 100 parts by mass of the total amount of component (D).
  • 0 to 40 parts by weight 0 to 30 parts by weight, 0 to 20 parts by weight, 0 to 10 parts by weight, 0 to 5.0 parts by weight, 0 to 2.0 parts by weight, 0 to 1.0 parts by weight, 0 It may be up to 0.10 parts by mass, 0 to 0.010 parts by mass, or 0 to 0.0010 parts by mass.
  • the content of the other reactive curing agent is the total of component (B) and component (C) 0.01 parts by mass or more, 0.05 parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more with respect to the amount of 100 parts by mass, Alternatively, it may be 0.30 parts by mass or more, and 6.0 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.5 parts by mass or less, 1. It may be 0 parts by mass or less, or 0.70 parts by mass or less.
  • Examples of reactive curing agents (D) other than cationic polymerization initiators include amine compounds such as benzylmethylamine and 2,4,6-trisdimethylaminomethylphenol; 2-methylimidazole, 2-ethyl-4-methyl imidazole compounds such as imidazole and 2-heptadecyl imidazole; Lewis acids such as boron trifluoride/monoethylamine complex and boron trifluoride/piperazine complex; peroxides such as di(t-butylperoxy)diisopropylbenzene; are mentioned.
  • amine compounds such as benzylmethylamine and 2,4,6-trisdimethylaminomethylphenol
  • 2-methylimidazole, 2-ethyl-4-methyl imidazole compounds such as imidazole and 2-heptadecyl imidazole
  • Lewis acids such as boron trifluoride/monoethylamine complex and boron trifluoride/piperazine
  • the curable adhesive composition used in one aspect of the present invention contains a binder resin having a reactive functional group as component (A), it further contains a cross-linking agent (E) capable of reacting with the reactive functional group. is preferred.
  • a composition that further contains the cross-linking agent (E) together with the component (A) it is possible to form a curable adhesive layer that is highly effective in suppressing the exudation of the adhesive component. That is, in the process of forming a curable adhesive layer from a coating film formed from a curable adhesive composition, the reactive functional groups of the crosslinking agent (E) and the binder resin (A) react with each other to form a coating film.
  • a crosslinked structure is formed inside, and a curable adhesive layer that is difficult to fluidize even when heated can be formed.
  • the formed curable adhesive layer is adhered to an adherend such as a circuit board, cured, and adhered to the adherend. become more difficult to occur.
  • an adherend such as a circuit board, cured, and adhered to the adherend. become more difficult to occur.
  • a composition containing a cross-linking agent (E) may be used alone or in combination of two or more.
  • the content of component (E) is preferably 0.01 parts by mass or more, more preferably 0 parts by mass, relative to 100 parts by mass of the total amount of component (A). 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, more preferably 0.07 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.15 parts by mass or more, still more preferably 0 .20 parts by mass or more, more preferably 0.25 parts by mass or more, particularly preferably 0.30 parts by mass or more, and preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, more preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 4.0 parts by mass or less, still more preferably 3.0 parts by mass or less, and even more preferably 2.5 parts by mass or less; More preferably 2.0 parts by mass or less, particularly preferably 1.5 parts by mass or less.
  • the molecular weight of the cross-linking agent (E) used in one aspect of the present invention increases the probability of reaction with the component (A), facilitates the formation of a cross-linked structure, and has a higher effect of suppressing the exudation of the adhesive component. It is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, still more preferably 600 or less, and particularly preferably 500 or less, from the viewpoint of a composition capable of forming an agent layer.
  • the cross-linking agent (E) used in one aspect of the present invention is appropriately selected according to the type of reactive functional group possessed by the component (A). , aziridine-based cross-linking agents, and the like.
  • the cross-linking agent (E) used in one embodiment of the present invention is preferably at least one selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents.
  • the cross-linking agent (E) used in one embodiment of the present invention is preferably a cross-linking agent having an isocyanurate skeleton.
  • the isocyanate-based cross-linking agent is preferably a compound having two or more isocyanate groups in the molecule.
  • Examples include triphenylmethane triisocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and the like.
  • the epoxy-based cross-linking agent is preferably a compound having two or more epoxy groups in the molecule. -m-xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
  • Metal chelate-based cross-linking agents include chelate compounds having metal ions functioning as cross-linking points. Examples of such metal ions include aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, and tin ions. Among these, the metal chelate-based cross-linking agent is preferably an aluminum chelate compound. aluminum bisoleyl acetoacetate and the like.
  • the cross-linking agent (E) used in one aspect of the present invention is preferably an isocyanate-based cross-linking agent, more preferably an isocyanurate of a polyisocyanate compound, and an isocyanurate of 1,5-pentamethylene diisocyanate [1,3,5 -tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione] and the isocyanurate of 1,6-hexamethylene diisocyanate [1,3,5-tris(6-isocyanate hexyl)-1,3,5-triazine-2,4,6-trione] is more preferable.
  • the curable adhesive composition used in one aspect of the present invention preferably further contains a silane coupling agent (F).
  • a silane coupling agent (F) By using a composition containing a silane coupling agent, a cured product with improved adhesive strength can be formed.
  • the silane coupling agent (F) may be used alone or in combination of two or more.
  • the content of component (F) is preferably 0.001 parts by mass or more, more preferably 0 parts by mass, relative to 100 parts by mass of the total amount of component (A).
  • 0.005 parts by mass or more more preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, still more preferably 0.05 parts by mass or more, still more preferably 0.07 parts by mass or more, still more preferably 0 .10 parts by mass or more, more preferably 0.12 parts by mass or more, particularly preferably 0.15 parts by mass or more, and preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.5 parts by mass or less, and even more preferably 1.0 parts by mass or less; More preferably 0.80 parts by mass or less, particularly preferably 0.60 parts by mass or less.
  • the silane coupling agent (E) used in one aspect of the present invention is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule.
  • Specific silane coupling agents include, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 - Silane coupling agents having a (meth)acryloyl group such as acryloxypropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy) Silane coupling agents having a vinyl group such as silane; 2-(3,4-epoxycyclohexyl)ethy
  • the curable adhesive composition used in one aspect of the present invention may also be a composition containing a cyclic ether compound.
  • Any compound having a cyclic ether group can be used as the cyclic ether compound.
  • the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, a tetrahydropyranyl group and the like.
  • the oxirane group includes groups having an oxirane structure such as glycidyl group, glycidyl ether group and epoxycyclohexyl group.
  • a cyclic ether compound may be used independently and may use 2 or more types together.
  • a composition containing a cyclic ether compound has the property of being able to form a cured product having excellent adhesive strength, but the cured product has a large relative dielectric constant and dielectric loss tangent value, and the above-mentioned component (B) and ( The low dielectric properties tend to be inferior to compositions containing component C) and not containing a cyclic ether compound.
  • the content of the cyclic ether compound is less than 5.0% by mass with respect to the total amount (100% by mass) of the active ingredients of the curable adhesive composition. , less than 3.0% by weight, less than 1.0% by weight, less than 0.50% by weight, less than 0.10% by weight, less than 0.010% by weight, less than 0.0010% by weight, less than 0.00010% by weight, Alternatively, it may be less than 0.000010% by mass. Further, in the curable adhesive composition used in one aspect of the present invention, the content of the cyclic ether compound is less than 100 parts by mass of the total amount of components (A) to (C) contained in the curable adhesive composition.
  • the curable adhesive composition used in one aspect of the present invention may be a composition containing an inorganic filler or a composition containing no inorganic filler.
  • inorganic fillers include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide, calcium carbonate, and the like. is mentioned. These inorganic fillers may be used alone or in combination of two or more.
  • the content of the inorganic filler in the curable adhesive composition used in one aspect of the present invention is preferably as low as possible.
  • the content of the inorganic filler is 0 to 30% by mass with respect to the total amount (100% by mass) of the active ingredients of the curable adhesive composition, 0-20% by mass, 0-10% by mass, 0-5.0% by mass, 0-2.0% by mass, 0-1.0% by mass, 0-0.1% by mass, 0-0.01% by mass %, or 0 to 0.001% by mass.
  • the content of the inorganic filler is 100 parts by mass of the total amount of components (A) to (C) contained in the curable adhesive composition.
  • the curable adhesive composition used in one aspect of the present invention may contain additives other than the above-described components within a range that does not impair the effects of the present invention.
  • additives include, for example, ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, pigments, extenders, softeners, and the like. These additives may be used alone or in combination of two or more.
  • the content of these additives can be appropriately set according to the type of additive. For example, the content of each additive is 0.001 to 30 parts by mass, 0.005 to 20 parts by mass, 0.005 to 20 parts by mass, and 0 0.01 to 10 parts by mass, or 0.03 to 5 parts by mass.
  • the curable adhesive composition used in one aspect of the present invention preferably contains an active ingredient that is liquid at 25°C.
  • an active ingredient that is liquid at 25°C By using a composition containing a liquid active ingredient, it is possible to improve the sticking property of the formed curable adhesive layer.
  • the content of the active ingredient that is liquid at 25° C. is based on the total amount (100% by mass) of the active ingredient in the curable adhesive composition.
  • the peel strength (R1) and peel strength (R2) tend to increase, so the curable adhesive sheet is adjusted to satisfy the above requirement (I) or (III).
  • the content is preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less.
  • one aspect of the present invention is At least one active ingredient that is liquid at 25° C. contained in the curable adhesive composition used in the embodiment is preferably a polyfunctional compound (C).
  • the content of the polyfunctional compound (C) with respect to the total amount (100% by mass) of the active ingredients that are liquid at 25°C is preferably 70% by mass or more, It is more preferably 80% by mass or more, still more preferably 85% by mass or more, and may be usually 100% by mass or less, preferably 99.0% by mass or less, more preferably 98.0% by mass or less.
  • the curable adhesive composition used in one aspect of the present invention may be in the form of a solution by further adding a diluent solvent.
  • diluent solvents used in one aspect of the present invention include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like.
  • These diluent solvents may be used alone or in combination of two or more. These diluent solvents may be the solvents used during the synthesis of the components (A) and (B) as they are, or the solvents other than the solvents used during the synthesis of the components (A) and (B). More than one solvent may be added.
  • the concentration of the active ingredient in the curable adhesive composition is appropriately set so as to have a desired viscosity in consideration of applicability and the like.
  • the total amount (100% by mass) of the curable adhesive composition it may be preferably 3.0% by mass or more, more preferably 10% by mass or more, and preferably 70% by mass or less. , and more preferably 50% by mass or less.
  • the curable adhesive composition described above is coated on the release layer of the first release film or the second release film by a known coating method. be able to. From the viewpoint of improving the applicability to the release film, it is preferable to dilute the curable adhesive composition with a diluting solvent to form a solution.
  • Examples of methods for applying the curable adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the drying treatment method include hot air drying, hot roll drying, and infrared irradiation.
  • the drying conditions for the formed coating film are preferably 80° C. to 150° C. and heating for 30 seconds to 5 minutes (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes) to dry.
  • a curable adhesive layer can be formed on the release layer of the first release film or the second release film.
  • the curable adhesive sheet of one embodiment of the present invention can be obtained.
  • the curable adhesive composition is applied to the second release film, and the exposed surface of the formed curable adhesive layer is It is preferable to laminate the first release film on.
  • the curable adhesive composition used for forming the curable adhesive layer contains a cross-linking agent (E), a certain period of time (for example, 1 to 14 days) is required to complete the cross-linking reaction. It is preferable to go through a seasoning process to retain the degree of flavor).
  • a cross-linking agent for example, 1 to 14 days
  • a cured product obtained by curing the curable adhesive layer of the curable adhesive sheet of one embodiment of the present invention has high adhesive strength and excellent low dielectric properties in a high frequency region. Therefore, the curable adhesive sheet of one aspect of the present invention is suitably used when forming a member in a device that requires low dielectric properties, and is particularly used as a cover lay sheet for protecting a circuit board. is preferred.
  • circuit boards include flexible printed circuit boards (FPC).
  • the present invention can also provide the following [1] and [2].
  • [1] The curable adhesive layer of the curable adhesive sheet of one aspect of the present invention is laminated to a circuit board, the curable adhesive layer is cured to obtain a cured product, and the cured product is obtained as described above.
  • [2] The curable adhesive layer of the curable adhesive sheet of one aspect of the present invention is laminated to a circuit board, the curable adhesive layer is cured to obtain a cured product, and the cured product is obtained as described above.
  • the method of curing the curable adhesive layer to obtain a cured product can be adjusted depending on the type of the reactive curing agent such as the component (D), and is a heat curing method.
  • it may be a photo-curing method, which is selected according to the type of components contained in the curable adhesive composition, which is the material for forming the curable adhesive layer.
  • a thermosetting method is preferred.
  • the heating temperature for heat curing is preferably 80 to 200° C., more preferably 90 to 190° C., still more preferably 100 to 180° C.
  • the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 6 hours, more preferably 40 minutes to 3 hours.
  • the pressure for hot pressing is preferably 0.1 to 10 MPa, more preferably 0.5 to 8.0 MPa, still more preferably 1.0 to 5.0 MPa.
  • a cured product when the curable adhesive layer is cured by a photo-curing method, a cured product can be obtained by irradiating the curable adhesive layer with energy rays such as ultraviolet rays.
  • each physical property value is a value measured by the method shown below.
  • the first release film is removed from the curable adhesive sheet to be measured, and the exposed adhesive surface is placed on the surface of a 25 ⁇ m thick polyimide film (manufactured by Toray DuPont Co., Ltd., Kapton 100H), and a heat laminator is used. and pressed at 100°C.
  • the curable adhesive sheet was cut together with the polyimide film into a size of 150 mm long ⁇ 50 mm wide to prepare a test sample.
  • One adhesive surface of the double-sided tape is attached to the surface of the polyimide film of the test sample opposite to the surface on which the curable adhesive layer is laminated, and the other adhesive surface of the double-sided tape is attached to the surface of the metal plate. stacked and pressed.
  • peel force (R2) This test sample was subjected to a peel test in the same manner as the peel force (R1) measurement described above. That is, in an environment with a temperature of 23 ° C. and a relative humidity of 50%, the second release film to be measured for peel force is peeled from the test sample fixed to the metal plate using the precision universal tester. The value measured when peeled under conditions of an angle of 180° and a peeling speed of 300 mm/min was defined as "peeling force (R2)".
  • ⁇ Component (E): Crosslinking agent> ⁇ “Isocyanate-based cross-linking agent”: 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione (manufactured by Mitsui Chemicals, Inc., product name “Stabio D- 370N”), molecular weight 462, liquid at 25°C.
  • Examples 1-2, Comparative Examples 1-2 The curable adhesive compositions used in the following Examples and Comparative Examples, which are materials for forming the release film and the curable adhesive layer, are as follows. ⁇ First release film> - Non-silicone release film (1): Product name "PC38 AL-5", manufactured by Lintec Corporation, a non-silicone having a release layer formed from an alkyd release agent on a polyethylene terephthalate (PET) film that has been foamed and made white Silicone-based release film, thickness: 38 ⁇ m.
  • PET polyethylene terephthalate
  • Non-silicone release film (2) product name “SP-PET50 AL-5”, manufactured by Lintec Corporation, a non-silicone release film having a release layer formed from an alkyd release agent on a colorless PET film, thick Thickness: 50 ⁇ m.
  • Non-silicone release film (3) product name “SP-PET75 AL-5”, manufactured by Lintec Corporation, a non-silicone release film having a release layer formed from an alkyd release agent on a colorless PET film, thick Thickness: 75 ⁇ m.
  • Curable adhesive composition (1) Curable adhesive composition (1) prepared according to the composition shown in Table 1 in Production Example 1.
  • Curable adhesive composition (2) Curable adhesive composition (2) prepared according to the composition shown in Table 1 in Production Example 2.
  • the curable adhesive composition shown in Table 1 is applied onto the release layer of the second release film shown in Table 2 to form a coating film, the coating film is dried, and the curable adhesive composition having a thickness of 25 ⁇ m is applied. A layer was formed. Further, the exposed surface of the formed curable adhesive layer and the release layer of the first release film shown in Table 2 were laminated to prepare a curable adhesive sheet.
  • a plurality of prepared curable adhesive sheets are prepared, a plurality of curable adhesive layers are superimposed to form a curable adhesive layer having a thickness of about 1 mm, and a second release film/a curable adhesive having a thickness of about 1 mm
  • a laminate was obtained by laminating the agent layer/first release film in this order. Then, this laminate is heated at 160° C. for 1 hour to cure the curable adhesive layer to obtain a cured product, and the cured product obtained by removing the first release film and the second release film is measured. was used as a sample.
  • the dielectric loss tangent of the cured product was measured at 23° C. and 1 GHz using an RF impedance material analyzer (manufactured by Keysight Technologies, product name “E4991A”) for the obtained measurement sample.
  • 1 GHz is adopted as an example of a high frequency region.
  • the curable adhesive sheets produced in Examples 1 and 2 were easier to peel off of the first release film than Comparative Examples 1 and 2, and had excellent handleability.
  • the curable adhesive sheets prepared in Examples 1 and 2 use a non-silicone release agent, the silicone component does not migrate to the adherend, thus preventing contamination of the adherend. can be suppressed.
  • curable adhesive sheet 10 curable adhesive layer 10a, 10b surface 21 first release film 211 release layer 212 resin film 22 second release film 221 release layer 222 resin film

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne une feuille adhésive durcissable comprenant une couche adhésive durcissable, avec laquelle un produit durci ayant une tangente de perte diélectrique de 0,01 ou moins à 23 °C et à 1 GHz peut être formé, et des premier et second films anti-adhésifs entre lesquels les deux côtés de la couche adhésive durcissable sont maintenus. Les premier et second films anti-adhésifs comportent un film de résine et une couche anti-adhésive qui est disposée sur une surface du film de résine, est formée à partir d'un agent anti-adhésif non siliconé et est en contact avec une surface de la couche adhésive durcissable ; et l'exigence suivante (I) est satisfaite. Exigence (I) : la force de pelage (R1) au moment où le premier film anti-adhésif est décollé de la couche adhésive durcissable à l'angle de pelage de 180° et à la vitesse de pelage de 300 mm/min n'est pas supérieure à 250 mN/50 mm.
PCT/JP2022/036714 2021-09-30 2022-09-30 Feuille adhésive durcissable WO2023054676A1 (fr)

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KR1020247009258A KR20240070533A (ko) 2021-09-30 2022-09-30 경화성 접착 시트
CN202280063976.6A CN118043416A (zh) 2021-09-30 2022-09-30 固化性粘接片
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005332516A (ja) * 2004-05-21 2005-12-02 Sony Disc & Digital Solutions Inc ディスクの製造装置および製造方法
WO2010038697A1 (fr) * 2008-09-30 2010-04-08 リンテック株式会社 Procédé de décollement de film, processus de production de film optique, mécanisme de décollement de film et appareil de production de film optique
JP2013067743A (ja) * 2011-09-26 2013-04-18 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2013091785A (ja) * 2011-10-08 2013-05-16 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2015004009A (ja) * 2013-06-21 2015-01-08 味の素株式会社 樹脂組成物
WO2021106847A1 (fr) * 2019-11-28 2021-06-03 東洋紡株式会社 Film adhésif, stratifié, et carte de circuit imprimé

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7090428B2 (ja) 2018-02-05 2022-06-24 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005332516A (ja) * 2004-05-21 2005-12-02 Sony Disc & Digital Solutions Inc ディスクの製造装置および製造方法
WO2010038697A1 (fr) * 2008-09-30 2010-04-08 リンテック株式会社 Procédé de décollement de film, processus de production de film optique, mécanisme de décollement de film et appareil de production de film optique
JP2013067743A (ja) * 2011-09-26 2013-04-18 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2013091785A (ja) * 2011-10-08 2013-05-16 Mitsubishi Plastics Inc 基材レス両面粘着シート
JP2015004009A (ja) * 2013-06-21 2015-01-08 味の素株式会社 樹脂組成物
WO2021106847A1 (fr) * 2019-11-28 2021-06-03 東洋紡株式会社 Film adhésif, stratifié, et carte de circuit imprimé

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TW202332749A (zh) 2023-08-16
CN118043416A (zh) 2024-05-14
KR20240070533A (ko) 2024-05-21

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