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WO2024143121A1 - Composition adhésive, stratifié avec couche adhésive, stratifié revêtu de cuivre flexible, et câble plat flexible - Google Patents

Composition adhésive, stratifié avec couche adhésive, stratifié revêtu de cuivre flexible, et câble plat flexible Download PDF

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Publication number
WO2024143121A1
WO2024143121A1 PCT/JP2023/045751 JP2023045751W WO2024143121A1 WO 2024143121 A1 WO2024143121 A1 WO 2024143121A1 JP 2023045751 W JP2023045751 W JP 2023045751W WO 2024143121 A1 WO2024143121 A1 WO 2024143121A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
adhesive layer
mass
silica filler
resin
Prior art date
Application number
PCT/JP2023/045751
Other languages
English (en)
Japanese (ja)
Inventor
健人 大村
晋次 北
真 平川
Original Assignee
東亞合成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東亞合成株式会社 filed Critical 東亞合成株式会社
Publication of WO2024143121A1 publication Critical patent/WO2024143121A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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

Definitions

  • the present disclosure relates to an adhesive composition, a laminate with an adhesive layer, a flexible copper-clad laminate, and a flexible flat cable. More specifically, the present disclosure relates to an adhesive composition suitable for bonding electronic components and the like, particularly for the manufacture of products related to flexible printed wiring boards, a laminate with an adhesive layer using the same, and a flexible copper-clad laminate and a flexible flat cable using the same.
  • FPCs Flexible printed circuit boards
  • Products related to such FPCs include, for example, flexible copper-clad laminates made by bonding polyimide film and copper foil together, flexible printed wiring boards in which electronic circuits are formed on flexible copper-clad laminates, flexible printed wiring boards with reinforcement plates made by bonding flexible printed wiring boards and reinforcement plates together, multilayer boards made by stacking and bonding flexible copper-clad laminates or flexible printed wiring boards, and flexible flat cables (hereinafter also referred to as "FFCs") in which copper wiring is bonded to a base film, and adhesives are usually used when manufacturing these.
  • FFCs flexible flat cables
  • coverlay film When manufacturing the FPC, a laminate with an adhesive layer, called a "coverlay film,” is usually used to protect the wiring portion.
  • This coverlay film comprises an insulating base film and an adhesive layer formed on its surface, with polyimide resin being widely used as the material for the base film.
  • a flexible printed wiring board is then manufactured by attaching the coverlay film via the adhesive layer to the surface having the wiring portion, for example, using a heat press or the like. At this time, the adhesive layer of the coverlay film needs to have strong adhesion to both the wiring portion and the base film.
  • a build-up type multilayer printed wiring board in which conductor layers and organic insulating layers are alternately laminated on the surface of a substrate.
  • an insulating adhesive layer forming material called a "bonding sheet” is used to bond the conductor layers and the organic insulating layers.
  • the insulating adhesive layer must be embeddable in the wiring portion and have strong adhesion to both the constituent material of the conductor part that forms the circuit (copper, etc.) and the organic insulating layer (polyimide resin, etc.).
  • the adhesive compositions used in such FPC-related products are generally epoxy-based adhesive compositions that contain an epoxy resin and a thermoplastic resin that is reactive with the epoxy resin.
  • Patent Document 1 discloses an adhesive composition that contains an olefin resin having at least one reactive functional group, an epoxy resin, and an inorganic filler such as silica to control thixotropy.
  • the adhesive composition, adhesive layer-attached laminate, flexible copper-clad laminate, and flexible flat cable disclosed herein are as follows:
  • the content of the silica filler (C) is 10 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the modified polyolefin resin (A).
  • the modified polyolefin resin (A) is an acid-modified polyolefin resin.
  • the modified polyolefin resin (A) is a resin obtained by graft-modifying an unmodified polyolefin resin with a modifying agent containing an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof.
  • a cured product of the adhesive composition has a relative dielectric constant of 2.5 or less and a dielectric dissipation factor of 0.01 or less, measured at a frequency of 10 GHz;
  • the adhesive composition according to any one of the above [1] to [8].
  • a laminate with an adhesive layer comprising an adhesive layer made of the adhesive composition according to any one of [1] to [9] above, and a base film in contact with at least one surface of the adhesive layer.
  • a flexible copper-clad laminate comprising the adhesive layer-attached laminate according to the above-mentioned [10], the base film being provided on one side of the adhesive layer, and a copper foil being provided on the other side of the adhesive layer.
  • a flexible flat cable comprising the base film on one side of the adhesive layer in the laminate with an adhesive layer according to [10] above, and a copper wiring on the other side of the adhesive layer.
  • the adhesive composition has the above-mentioned configuration. Therefore, the adhesive composition can improve the dispersibility of the silica filler without adversely affecting the dielectric properties of the cured product of the adhesive composition.
  • the flexible flat cable has the above-mentioned configuration. Therefore, even if the adhesive composition constituting the adhesive layer in the laminate with the adhesive layer contains silica filler, the flexible flat cable does not adversely affect the dielectric properties of the adhesive layer after the adhesive composition is cured. Furthermore, since the silica filler in the adhesive composition constituting the adhesive layer in the laminate with the adhesive layer has good dispersibility, the flexible flat cable suppresses agglomerations of the silica filler, and the adhesive layer can be made into a smooth and homogeneous thin film.
  • the modified polyolefin resin (A) can be produced by a known method through graft modification (graft polymerization), and a radical initiator may be used during production.
  • methods for producing the modified polyolefin resin (A) include a solution method in which an unmodified polyolefin resin is heated and dissolved in a solvent such as toluene, and the modifying agent and radical initiator are added, and a melting method in which the unmodified polyolefin resin, the modifying agent, and the radical initiator are melt-kneaded using a Banbury mixer, kneader, extruder, or the like.
  • the method for using the unmodified polyolefin resin, the modifying agent, and the radical initiator is not particularly limited, and they may be added to the reaction system all at once or successively.
  • a modifying auxiliary for improving the grafting efficiency by a modifying agent such as ⁇ , ⁇ -unsaturated carboxylic acid, a stabilizer for adjusting the resin stability, and the like may be further used.
  • the content ratio of the structural units in the unmodified polyolefin resin and the unmodified polypropylene resin can be selected arbitrarily.
  • the modified polyolefin resin (A) is preferably a modified resin of an unmodified polypropylene resin which is at least one selected from the group consisting of ethylene-propylene, propylene-butene, and ethylene-propylene-butene copolymers. From the viewpoint of obtaining particularly excellent adhesiveness, it is preferable to use an unmodified polypropylene resin in which the content ratio of propylene units is 50% by mass or more and 98% by mass or less.
  • the modifier may include ⁇ , ⁇ -unsaturated carboxylic acids and their derivatives.
  • ⁇ , ⁇ -unsaturated carboxylic acids include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, aconitic acid, and norbornene dicarboxylic acid.
  • derivatives of unsaturated carboxylic acids include acid anhydrides, acid halides, amides, imides, and esters.
  • itaconic anhydride, maleic anhydride, aconitic anhydride, and citraconic anhydride are preferred, and itaconic anhydride and maleic anhydride are particularly preferred in terms of adhesiveness.
  • Examples of (meth)acrylic acid derivatives other than (meth)acrylic acid esters include hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and isocyanate-containing (meth)acrylic acid.
  • Examples of aromatic vinyl compounds include styrene, o-methylstyrene, p-methylstyrene, and ⁇ -methylstyrene.
  • the graft mass derived from ⁇ , ⁇ -unsaturated carboxylic acid or its derivative in modified polyolefin resin (A) can be determined by alkali titration, but if the derivative of ⁇ , ⁇ -unsaturated carboxylic acid is an imide or the like that does not have an acid group, the graft mass can be determined by Fourier transform infrared spectroscopy.
  • the graft mass is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.3% by mass or more and 25% by mass or less, relative to 100% by mass of the modified polyolefin resin (A).
  • the resin has excellent solubility in solvents and excellent compatibility with other resins or elastomers described below when they are contained, and the adhesion to the adherend can be further improved.
  • the acid value of the modified polyolefin resin (A) is preferably 0.1 mgKOH/g or more and 50 mgKOH/g or less, more preferably 0.5 mgKOH/g or more and 40 mgKOH/g or less, and even more preferably 1.0 mgKOH/g or more and 30 mgKOH/g or less.
  • the adhesive composition is sufficiently cured, and good adhesion, heat resistance, and resin flow properties are obtained.
  • the epoxy resin (B) is preferably one having two or more epoxy groups in one molecule. This is because it forms a crosslinked structure by reaction with the modified polyolefin resin (A), and can exhibit high heat resistance. Furthermore, when an epoxy resin with two or more epoxy groups is used, the degree of crosslinking with the modified polyolefin resin (A) is sufficient, and sufficient heat resistance can be obtained.
  • the dispersibility of the silica filler can be improved by suppressing the silanol group concentration to a low concentration range of 0.5 mmol/g or less.
  • the silica filler (C) can be specifically composed of an aggregate of silica particles having silanol groups on the surface (silica powder having silanol groups on the surface).
  • the silica filler (C) can be obtained, for example, by surface treating silica powder with a surface treatment agent capable of introducing silanol groups.
  • the surface treatment agent include alkoxysilanes such as methyltrimethoxysilane, and organosilazanes such as hexamethyldisilazane (HMDS). These can be used alone or in combination of two or more.
  • HMDS hexamethyldisilazane
  • commercially available silica fillers can be used as the silica filler (C).
  • the BET specific surface area of the silica filler (C) is preferably 1 m2/g or more and 10 m2/g or less, more preferably 2 m2/g or more and 8 m2/g or less, and even more preferably 3 m2/g or more and 7 m2 /g or less.
  • thermoplastic resin examples include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene-based resins, polypropylene-based resins, and polyvinyl-based resins, etc. These thermoplastic resins may be used alone or in combination of two or more kinds.
  • the content of the curing agent is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 70 parts by mass or less, per 100 parts by mass of the epoxy resin (B).
  • inorganic filler examples include powders of titanium oxide, aluminum oxide, zinc oxide, carbon black, talc, copper, silver, etc. These may be used alone or in combination of two or more.
  • the adhesive composition contains a solvent and is a solution or dispersion (resin varnish) in which the modified polyolefin resin (A), epoxy resin (B), and silica filler (C) are dissolved or dispersed in the solvent, application to the substrate film and formation of the adhesive layer can be carried out smoothly, and an adhesive layer of the desired thickness can be easily obtained.
  • a solvent is a solution or dispersion (resin varnish) in which the modified polyolefin resin (A), epoxy resin (B), and silica filler (C) are dissolved or dispersed in the solvent
  • the solvent used in the adhesive composition of this embodiment preferably contains, among the above-mentioned examples, an alicyclic hydrocarbon solvent such as methylcyclohexane and/or cyclohexane, and an alcohol-based solvent.
  • an alicyclic hydrocarbon solvent such as methylcyclohexane and/or cyclohexane
  • an alcohol-based solvent such as methylcyclohexane and/or cyclohexane
  • the content of the alicyclic hydrocarbon relative to 100 parts by mass of the solvent is preferably 20 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
  • the content of the alcohol-based solvent relative to 100 parts by mass of the solvent is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass or less.
  • the solvent used in the adhesive composition of this embodiment preferably contains toluene.
  • the toluene content per 100 parts by mass of the adhesive composition is preferably 10 parts by mass or more and 60 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.
  • the bonding sheet also has the above-mentioned adhesive layer formed on the surface of a base film, but the base film functions as a release film.
  • the bonding sheet may also have an adhesive layer between two release films. The release films are peeled off when the bonding sheet is used.
  • the release films that can be used are similar to those described above.
  • sample 1C had a relatively high resin flow because the adhesive composition did not contain silica filler (C).
  • sample 1C was an adhesive composition that did not contain silica filler (C) and had a cured product with a relative dielectric constant of 2.3 (Dk) and a dielectric dissipation factor of 0.0017 (Df).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

Cette composition adhésive comprend : une résine de polyoléfine modifiée (A) ayant un groupe fonctionnel réactif qui réagit avec un groupe époxy ; une résine époxy (B) ; et une charge de silice (C). La concentration en groupe silanol de la charge de silice (C) est de 0,5 mmol/g ou moins. Ce stratifié avec une couche adhésive est pourvu d'un film de base sur au moins une surface de la couche adhésive, la couche adhésive étant constituée de la composition adhésive. Ce stratifié revêtu de cuivre flexible ou câble plat flexible est pourvu d'un film de base sur une surface de la couche adhésive du stratifié avec la couche adhésive, et est également pourvu d'une feuille de cuivre ou d'un câblage de cuivre sur l'autre surface de la couche adhésive.
PCT/JP2023/045751 2022-12-27 2023-12-20 Composition adhésive, stratifié avec couche adhésive, stratifié revêtu de cuivre flexible, et câble plat flexible WO2024143121A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022209966 2022-12-27
JP2022-209966 2022-12-27

Publications (1)

Publication Number Publication Date
WO2024143121A1 true WO2024143121A1 (fr) 2024-07-04

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PCT/JP2023/045751 WO2024143121A1 (fr) 2022-12-27 2023-12-20 Composition adhésive, stratifié avec couche adhésive, stratifié revêtu de cuivre flexible, et câble plat flexible

Country Status (1)

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WO (1) WO2024143121A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016047289A1 (fr) * 2014-09-24 2016-03-31 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive l'utilisant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016047289A1 (fr) * 2014-09-24 2016-03-31 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive l'utilisant

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