WO2020012978A1 - Composition adhésive, stratifié et feuille adhésive - Google Patents

Composition adhésive, stratifié et feuille adhésive Download PDF

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Publication number
WO2020012978A1
WO2020012978A1 PCT/JP2019/025722 JP2019025722W WO2020012978A1 WO 2020012978 A1 WO2020012978 A1 WO 2020012978A1 JP 2019025722 W JP2019025722 W JP 2019025722W WO 2020012978 A1 WO2020012978 A1 WO 2020012978A1
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WIPO (PCT)
Prior art keywords
adhesive composition
resin
adhesive
laminate
substrate
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PCT/JP2019/025722
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English (en)
Japanese (ja)
Inventor
来 佐藤
武史 中村
正嗣 水野
誌朗 正木
Original Assignee
日立化成株式会社
日立化成テクノサービス株式会社
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Application filed by 日立化成株式会社, 日立化成テクノサービス株式会社 filed Critical 日立化成株式会社
Priority to JP2020530103A priority Critical patent/JPWO2020012978A1/ja
Publication of WO2020012978A1 publication Critical patent/WO2020012978A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present disclosure relates to an adhesive composition, a laminate, and an adhesive sheet. More specifically, the present disclosure relates to an adhesive composition used for bonding a resin substrate and a resin substrate or a metal substrate, and particularly has a low dielectric property such as a liquid crystal polymer (hereinafter abbreviated as “LCP”).
  • LCP liquid crystal polymer
  • the present invention relates to an adhesive composition used for bonding to a substrate.
  • FPC flexible printed wiring boards
  • PI polyimide
  • PPS polyphenylene sulfide
  • the base film having low dielectric properties has low polarity
  • the adhesive strength is weak
  • the FPC member such as a cover lay film and a laminated board is used. Fabrication was difficult.
  • epoxy adhesives and acrylic adhesives have a problem that they are not excellent in low dielectric properties and impair the dielectric properties of FPC.
  • Patent Document 1 proposes a modified polyamide adhesive composition into which an olefin skeleton has been introduced in order to enhance the electrical characteristics of FPC.
  • Patent Literature 2 proposes an adhesive using an aromatic olefin oligomer-type modifier and an epoxy resin, and a coverlay for a flexible printed wiring board.
  • Patent Literatures 1 and 2 have a problem that, although they can obtain adhesiveness with a polyimide film, they cannot easily obtain adhesiveness with a base film having low dielectric properties such as LCP. is there. Further, the adhesive compositions described in Patent Documents 1 and 2 have a problem that the dielectric properties are inferior.
  • the present disclosure has been made in view of the problems of the above prior art, and has an adhesive composition having good adhesion to a substrate such as LCP and also having excellent low dielectric properties.
  • An object is to provide a laminate and an adhesive sheet.
  • the present inventors have conducted intensive studies to solve the above-described problems, and contain a specific bismaleimide resin having a structure derived from dimer acid, and an epoxy resin having a further specific structure, and a curing accelerator.
  • the present inventors have found that an adhesive composition containing the compound exhibits excellent low dielectric properties and has high adhesiveness to a resin substrate having low dielectric properties such as LCP, and has completed the present invention.
  • Adhesion containing (A) a bismaleimide resin represented by the following general formula (1), (B) an epoxy resin represented by the following general formula (2), and (C) a curing accelerator.
  • Composition [In the formula (1), R 1 represents a divalent hydrocarbon group derived from dimer acid, Q represents a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, Alternatively, it represents a substituted or unsubstituted heteroaromatic group, and n represents an integer of 0 to 100.
  • R 2 represents a hydrogen atom or a methyl group
  • n represents an integer of 0 to 30.
  • the content of the component (B) is 10 to 40 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
  • Adhesive composition is 10 to 40 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
  • an adhesive composition having good adhesion to a substrate such as LCP and also having excellent low dielectric properties, and a laminate and an adhesive sheet using the same.
  • the adhesive composition of the present embodiment includes (A) a bismaleimide resin represented by the general formula (1) (hereinafter, also referred to as “component (A)”) and (B) a general formula (2). (Hereinafter, also referred to as “component (B)”) and (C) a curing accelerator (hereinafter, also referred to as “component (C)”). Further, the adhesive composition of the present embodiment may contain (D) an organic solvent (hereinafter, also referred to as “component (D)”).
  • component (D) an organic solvent
  • Bismaleimide resin is a compound represented by the following general formula (1), and is obtained by reacting dimer diamine, which is a diamine derived from dimer acid, with tetracarboxylic dianhydride and maleic anhydride. Obtainable.
  • R 1 represents a divalent hydrocarbon group derived from dimer acid
  • Q represents a substituted or unsubstituted aliphatic group having 1 to 100 carbon atoms, a substituted or unsubstituted aromatic group, or , A substituted or unsubstituted heteroaromatic group
  • n represents an integer of 0 to 100.
  • Q in the formula (1) may be an unsubstituted aromatic group from the viewpoint of obtaining better adhesiveness to a resin base material having low dielectric properties such as LCP and obtaining better low dielectric properties. preferable.
  • n in the formula (1) is an integer of 5 to 30 from the viewpoint of obtaining better adhesiveness to a resin substrate having low dielectric properties such as LCP and obtaining better low dielectric properties. Is preferred.
  • @Dimer diamine is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, as described in, for example, JP-A-9-112712.
  • a known dimer diamine can be used without any particular limitation.
  • a compound represented by the following general formula (3) and / or general formula (4) is preferable.
  • the bond shown by a broken line means a carbon-carbon single bond or a carbon-carbon double bond.
  • the formulas (3) and (4) indicate the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond by the formula The structure is obtained by subtracting one from the numbers shown in (3) and (4).
  • dimer diamines examples include PRIAMINE 1075 and PRIAMINE 1074 (both manufactured by Croda Japan KK).
  • tetracarboxylic dianhydride examples include pyromellitic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 4,9,10-perylenetetracarboxylic dianhydride; bicyclo (2.2.2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; diethylenetriaminepentaacetic dianhydride; Ethylenediaminetetraacetic acid dianhydride; 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride; 3,3', 4,4'-biphenyltetracarboxylic dianhydride; 4,4'-oxydiphthalic acid Anhydride; 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride; 2,2'-bis (3,4-dip
  • the weight average molecular weight of the bismaleimide resin is preferably 3000 to 70000 from the viewpoint of obtaining better adhesiveness to a resin base material having low dielectric properties such as LCP and obtaining better low dielectric properties. It is more preferably from 5,000 to 50,000, even more preferably from 7000 to 30,000.
  • Bismaleimide resin may be a commercially available compound. Specifically, for example, DESIGNERDEMOLECURES Inc. BMI-3000 (synthesized from dimer diamine, pyromellitic dianhydride and maleic anhydride), BMI-1500, BMI-1700, BMI-5000 and the like can be preferably used.
  • the epoxy resin is not particularly limited as long as it is represented by the following general formula (2), and examples thereof include a bisphenol A epoxy resin and a bisphenol F epoxy resin. These can be used alone or in combination of two or more.
  • the epoxy resin (B) it is preferable to use a liquid bisphenol A epoxy resin or a liquid bisphenol F epoxy resin from the viewpoint of compatibility with the (A) bismaleimide resin.
  • R 2 represents a hydrogen atom or a methyl group
  • m represents an integer of 0 to 30.
  • M in the formula (2) is preferably an integer of 0 to 10 from the viewpoint of obtaining better adhesiveness to a resin base material having low dielectric properties such as LCP and obtaining better low dielectric properties. .
  • the content of the epoxy resin (B) is preferably from 10 to 40 parts by mass, more preferably from 10 to 30 parts by mass, where the total amount of the components (A) and (B) is 100 parts by mass. , More preferably from 12 to 25 parts by mass, particularly preferably from 15 to 20 parts by mass.
  • the content of the component (B) is 10 parts by mass or more, excellent adhesive strength to the LCP substrate tends to be easily obtained.
  • the content is 40 parts by mass or less, more excellent low dielectric properties are obtained. Tend to be more likely to be caught.
  • the curing accelerator is not particularly limited, and examples thereof include a phosphine compound, a phosphonium salt compound, an imidazole compound, and an amine compound. These can be used alone or in combination of two or more. Among them, a phosphonium salt compound or an imidazole compound is preferable because it has a particularly excellent function as a catalyst.
  • phosphine compound examples include primary phosphines such as alkyl phosphines such as ethyl phosphine and propyl phosphine and phenyl phosphine; dialkyl phosphines such as dimethyl phosphine and diethyl phosphine; diphenyl phosphine such as diphenyl phosphine; methyl phenyl phosphine; Graded phosphines; trialkyl phosphines such as trimethyl phosphine, triethyl phosphine, tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, alkyl diphenyl phosphine, dialkyl phenyl phosphine, tribenzyl phosphine, tolyl phosphine, tri-p-
  • Examples of the phosphonium salt compound include compounds having tetraphenylphosphonium, alkyltriphenylphosphonium, tetraalkylphosphonium, and the like. Specifically, tetraphenylphosphonium-thiocyanate, tetraphenylphosphonium-tetra-p-methylphenylborate, butyl Triphenylphosphonium-thiocyanate, tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, tetrabutylphosphonium-lauric acid and the like Can be
  • imidazole compound examples include 1- (2-cyanoethyl) -2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, and 2,4- Dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyano Chill-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole,
  • imidazole compounds include 1- (2-cyanoethyl) -2-phenylimidazole, 1,2-dimethylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-imidazole. 4-Methylimidazole is preferred.
  • Examples of the amine compound include triethylamine, dimethylbenzylamine, triethylenediamine, tripropylamine, tributylamine, dimethylethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-amino Examples include pyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine and the like.
  • the content of the curing accelerator is not particularly limited, but from the viewpoint of further improving the adhesiveness to a substrate such as LCP and the heat resistance of the obtained cured product, the bismaleimide resin of the component (A) is used.
  • the total amount is preferably 0.1 to 5.0 parts by mass, more preferably 1.0 to 3.0 parts by mass, based on 100 parts by mass of the total of the component (B) and the epoxy resin.
  • the adhesive composition of the present embodiment can further contain (D) an organic solvent.
  • the organic solvent used in the present embodiment is not particularly limited as long as it dissolves (A) a bismaleimide resin, (B) an epoxy resin, and (C) a curing accelerator.
  • Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; aliphatic hydrocarbons such as hexane, heptane, octane and decane; cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
  • Alicyclic hydrocarbons such as hexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol Solvents; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone and acetophenone; cell solvents such as methyl cellosolve and ethyl cellosolve Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; ethylene glycol mono n-butyl ether, ethylene glycol mono iso-butyl ether, ethylene glycol mono
  • Preparation of the adhesive composition of the present embodiment is performed according to a generally employed method.
  • the preparation method include methods such as melt mixing, powder mixing, and solution mixing.
  • an inorganic filler, a release agent, a flame retardant, an ion trapping agent, an antioxidant, an adhesion imparting agent, a low stress agent, a colorant, a coupling, Agents and the like may be blended within a range that does not impair the effects of the present disclosure.
  • the inorganic filler is added for lowering the coefficient of thermal expansion of the adhesive composition and improving the moisture resistance reliability.
  • the inorganic filler include fused silica, crystalline silica, silica such as cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and magnesium oxide.
  • the average particle size and shape of these inorganic fillers can be selected according to the application. Among them, spherical alumina, spherical fused silica, glass fiber and the like are preferable.
  • the release agent is added to improve the releasability from the mold.
  • the release agent include carnauba wax, rice wax, candelilla wax, polyethylene, polyethylene oxide, polypropylene, montanic acid, montanic acid and saturated alcohol, 2- (2-hydroxyethylamino) ethanol, ethylene glycol, and glycerin. All known compounds such as montan wax, stearic acid, stearic acid ester and stearic acid amide, which are ester compounds with the above, can be used.
  • Flame retardants are added to impart flame retardancy. Any known flame retardant can be used and is not particularly limited. Examples of the flame retardant include a phosphazene compound, a silicone compound, zinc-molybdate-supported talc, zinc-molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, and molybdenum oxide.
  • the ion trapping agent is added in order to capture ionic impurities contained in the liquid adhesive composition and prevent thermal deterioration and moisture absorption deterioration.
  • Any known ion trapping agent can be used and is not particularly limited. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide compounds, and rare earth oxides.
  • the laminate of the present embodiment is obtained by laminating an adhesive composition on a substrate (a two-layer laminate of a substrate / adhesive layer) or further laminating a substrate (substrate / adhesive layer) / Three-layer laminate of base material).
  • the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present embodiment is applied to a substrate and dried.
  • the adhesive composition of the present embodiment can be applied to various substrates and dried according to a conventional method, and further laminated with another substrate to obtain the laminate of the present embodiment.
  • the substrate is not particularly limited as long as the adhesive composition of the present embodiment can be applied and dried to form an adhesive layer.
  • a metal substrate such as a metal plate and a metal foil, and papers.
  • the material of the resin base material examples include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
  • the resin substrate is a film-like resin (hereinafter, also referred to as a “substrate film layer”).
  • the metal substrate any conventionally known conductive material that can be used for a circuit board can be used. Examples of the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, and respective alloys, plated products, metals treated with other metals such as zinc or chromium compounds, and the like. .
  • the metal substrate is preferably a metal foil, more preferably a copper foil.
  • the thickness of the metal foil is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, the thickness of the metal foil is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less.
  • the metal foil is usually provided in the form of a roll, but the form of the metal foil used when manufacturing a printed wiring board as described below is not particularly limited.
  • the form of the metal foil used when manufacturing a printed wiring board as described below is not particularly limited.
  • its length is not particularly limited.
  • the width is not particularly limited, but is preferably about 250 to 500 cm.
  • Examples of papers include high quality paper, kraft paper, roll paper, glassine paper and the like. Further, as the composite material, glass epoxy or the like can be exemplified.
  • polyester resin polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, Fluorine-based resin, SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferred.
  • the adhesive sheet of the present embodiment includes the above-described laminate, and is, for example, a laminate of the above-described laminate and a release substrate via an adhesive composition.
  • base material base material / adhesive layer / base material
  • the release substrate can be released from the adhesive sheet, and the adhesive layer can be transferred to another substrate.
  • the adhesive sheet of the present embodiment can be obtained by applying and drying the adhesive composition of the present embodiment to various laminates according to a conventional method. Also, after drying, when a release substrate is attached to the adhesive layer, it can be wound up without causing set-off to the base material that constitutes the laminate, and excellent operability is achieved, and the adhesive layer is Because it is protected, it has excellent storage properties and is easy to use. Further, if the adhesive composition is applied to the release substrate and dried, and if necessary, another release substrate is attached, the adhesive layer itself can be transferred to another substrate.
  • the release substrate is not particularly limited, for example, a high-quality paper, kraft paper, roll paper, on both sides of paper such as glassine paper, clay, polyethylene, a coating layer of a filler such as polyethylene and polypropylene. And a silicone-based, fluorine-based, or alkyd-based release agent applied on each of the coating layers.
  • various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer and propylene- ⁇ -olefin copolymer alone, and those obtained by applying the above release agent on a film such as polyethylene terephthalate may also be used.
  • alkyd-based release agents on both sides of high-quality paper and polypropylene for the reason that silicone adversely affects the electrical properties
  • the method for coating the adhesive composition on the substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater.
  • an adhesive layer can be provided directly or by a transfer method on a rolled copper foil or a polyimide film which is a constituent material of a printed wiring board.
  • the thickness of the adhesive layer after drying is appropriately changed as necessary, but is preferably in the range of 5 to 200 ⁇ m. If the thickness of the adhesive layer is less than 5 ⁇ m, the adhesive strength may be insufficient. If the thickness is 200 ⁇ m or more, drying may be insufficient and the residual solvent may increase, and there is a problem that blisters may be generated at the time of pressing for manufacturing a printed wiring board.
  • the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% by mass or less. If it exceeds 1% by mass, there is a problem that the residual solvent foams during the press for producing a printed wiring board, and blisters are easily generated.
  • the printed wiring board according to the present embodiment includes, as constituent elements, a laminate formed from a metal foil forming a conductive circuit and a resin base material.
  • the printed wiring board can be manufactured by a conventionally known method such as a subtractive method using a metal-clad laminate.
  • the printed wiring board according to the present embodiment is a so-called flexible circuit board (FPC) in which a conductive circuit formed of a metal foil is partially or entirely covered with a cover film or screen printing ink as necessary.
  • FPC flexible circuit board
  • TAB tape automated bonding
  • the printed wiring board of the present embodiment can have any laminated configuration that can be adopted as a printed wiring board.
  • a printed wiring board including four layers of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer can be provided.
  • a printed wiring board including five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer can be provided.
  • the adhesive composition of the present embodiment can be suitably used for each adhesive layer of a printed wiring board.
  • the adhesive composition when used as an adhesive, the adhesive composition has high adhesiveness not only to conventional polyimide, polyester film, and copper foil constituting a printed wiring board but also to a low-polarity resin base material such as LCP.
  • solder reflow resistance can be obtained, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition used for a coverlay film, a laminate, a copper foil with resin, and a bonding sheet.
  • any resin film conventionally used as a base material of the printed wiring board can be used as the base film.
  • the resin of the base film include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin-based resin, and fluorine-based resin.
  • the adhesive composition of the present embodiment has excellent adhesiveness even to a low-polar substrate such as a liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, and a polyolefin resin.
  • any conventionally known insulating film as an insulating film for a printed wiring board can be used.
  • any conventionally known insulating film as an insulating film for a printed wiring board can be used.
  • manufactured from various polymers such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyimide, polyamide imide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resin.
  • the film to be used is usable. More preferably, it is a polyimide film or a liquid crystal polymer film.
  • the compatibility refers to a composition obtained by mixing (A) a bismaleimide resin, (B) an epoxy resin, (C) a curing accelerator, and (D) an organic solvent, and stirring the mixture under the conditions of Example 1 described below. Refers to the state observed visually. If the compatibility is good, it means that there is no precipitate, etc., and it can be applied to the substrate. If the compatibility is poor, there is a precipitate, etc., which makes it difficult to apply it to the substrate. Point to. For those having poor compatibility, other physical properties were not evaluated because it was difficult to form a film. (Evaluation criteria) ⁇ : No precipitate (transparent) ⁇ : No precipitate (turbidity) ⁇ : with precipitate
  • ⁇ Adhesive strength> A resin film from which Purex A31 was peeled off, a glass plate having a thickness of 0.7 mm, and an LCP film having a thickness of 75 ⁇ m (trade name “Vexter”, manufactured by Kuraray Co., Ltd.) laminated with the resin film in the middle Then, thermocompression bonding was performed with a hot press at 200 ° C. and 2 MPa for 1 hour to obtain a laminate in which a glass plate, a cured resin film, and an LCP film were laminated in this order. The adhesive strength was measured by peeling the LCP film of the obtained laminate.
  • the peeling strength was measured at a normal temperature at a tensile speed of 5 mm / s using a 90 ° peeling measuring device (trade name “RHEONER II CREEMETER RE2-3305B” manufactured by Yamaden Corporation). Further, a peeling position (peeling mode) at the time of peeling was observed.
  • the peeling mode means that “substrate destruction” has higher adhesive strength than “interfacial peeling”.
  • the temperature was raised to 80 ° C., and the temperature was maintained for 0.5 hour, and 201.3 parts by mass of dimer diamine (trade name “PRIAMINE 1075”, manufactured by Crowda Japan Co., Ltd.) was added dropwise. After the dropwise addition, 4.3 parts by mass of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Thereafter, the temperature was raised to 165 ° C., and a dehydration ring-closing reaction was performed at 165 ° C. for 1 hour to remove water and ethanol in the reaction solution to obtain an intermediate polyimide resin.
  • dimer diamine trade name “PRIAMINE 1075”, manufactured by Crowda Japan Co., Ltd.
  • methanesulfonic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the obtained polyimide resin was cooled to 80 ° C., 27.3 parts by mass of maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.) was added, the temperature was raised to 160 ° C., and a dehydration ring closure reaction was performed at 160 ° C. for 2 hours. Then, water in the reaction solution was removed to obtain a bismaleimide resin.
  • maleic anhydride manufactured by Fuso Chemical Industry Co., Ltd.
  • the obtained bismaleimide resin was put into a separating funnel, 1000 parts by mass of pure water was charged, and the separating funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer were separated, and then only the organic layer was recovered.
  • the collected organic layer is poured into a 1-L glass container equipped with a cooler, a nitrogen inlet tube, a thermocouple, a stirrer, and a vacuum pump, heated to 88 to 93 ° C., and water is removed. The temperature was raised and the solvent was removed for 1 hour under reduced pressure of 0.1 MPa from atmospheric pressure to obtain a bismaleimide resin (A-1) (weight average molecular weight of 16,000) as the component (A).
  • Example 1 In a 500 ml four-necked flask equipped with a stirrer, 90 parts by mass of the bismaleimide resin (A-1) obtained in Synthesis Example 1 and an epoxy resin (trade name “jER-825”, manufactured by Mitsubishi Chemical Corporation) And 100 parts by mass of toluene, and stirred for 3 hours. To the obtained solution, 2 parts by mass of a curing accelerator (trade name “TBP-3S”, manufactured by Hokuko Chemical Co., Ltd.) was added, and the mixture was further stirred for 0.5 hour to obtain an adhesive composition.
  • Table 1 shows the amounts of the components and the results of evaluation of the physical properties. In Table 1, the amounts of the components (A) to (D) indicate parts by mass.
  • Examples 2 to 12 and Comparative Examples 1 to 12 were performed in the same manner as in Example 1 except that the kind and the amount of the bismaleimide resin, the epoxy resin, or the curing accelerator were changed to the contents shown in Table 1 or Table 2. Thus, 13 adhesive compositions were obtained.
  • Tables 1 and 2 show the amounts of the components and the results of the physical property evaluation. In Tables 1 and 2, the amounts of the components (A) to (D) indicate parts by mass. Details of the components (A) to (D) are as follows. In the component (B), (B-1) to (B-2) are epoxy resins satisfying the general formula (2), and (B-3) to (B-13) do not satisfy the general formula (2). Epoxy resin.
  • Component (A) Bismaleimide resin (A-1) Bismaleimide resin of Synthesis Example 1 (weight average molecular weight 16,000) (A-2) Bismaleimide resin of Synthesis Example 2 (weight average molecular weight 17000)
  • Component (C): curing accelerator (C-1) tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid (cation type: anion type 1: 1): TBP-3S (manufactured by Hokuko Chemical Co., Ltd.) (C-2) 1- (2-cyanoethyl) -2-phenylimidazole: 2PZCN (manufactured by Shikoku Chemicals Co., Ltd.) (C-3) 1,2-dimethylimidazole: 1,2-DMZ (manufactured by Shikoku Chemicals Co., Ltd.) (C-4) Dimethylbenzylamine: DMBA (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • the adhesive strength “> 2.0 kN / m” indicates the measurement limit of the device. However, even those having an adhesive strength of “> 2.0 kN / m” were at least partially peeled off by pulling by hand or the like, and the breaking mode at that time was evaluated.
  • the adhesive composition (Example) containing the bismaleimide resin, the epoxy resin, and the curing accelerator of the present disclosure shows high adhesive strength with LCP.
  • the adhesive composition (Example) of the present disclosure has low dielectric constant and dielectric loss tangent, and is excellent in low dielectric properties.
  • the mechanism by which the adhesive composition exhibited high adhesive strength with LCP is related to the compatibility between the bismaleimide resin and the epoxy resin.
  • the compatibility between the bismaleimide resin and the epoxy resin is good, the maleimide group and the epoxy group are uniformly copolymerized, and the hydroxy group is dispersed, so that the LCP and the hydroxy group can interact with each other to exhibit high adhesive strength. thinking.
  • the compatibility between the bismaleimide resin and the epoxy resin is poor, the bismaleimide resin and the epoxy resin react with each other, causing microphase separation, and the hydroxy groups do not disperse and interact with each other. It is thought that the adhesive strength will be low because of the inability to interact with.

Abstract

La présente invention concerne une composition adhésive contenant (A) une résine de bismaléimide représentée par la formule générale (1), (B) une résine époxyde représentée par la formule générale (2) et (C) un accélérateur de durcissement. Dans la formule (1), R1 représente un groupe hydrocarboné divalent dérivé d'un acide dimère, Q représente un groupe aliphatique en C1-100 substitué ou non substitué, un groupe aromatique substitué ou non substitué, ou un groupe hétéroaromatique substitué ou non substitué, et n représente un nombre entier de 0 à 100. [Dans La formule (2), R2 représente un atome d'hydrogène ou un groupe méthyle, et m représente un nombre entier de 0 à 30].
PCT/JP2019/025722 2018-07-13 2019-06-27 Composition adhésive, stratifié et feuille adhésive WO2020012978A1 (fr)

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Citations (6)

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JP2013199645A (ja) * 2012-02-24 2013-10-03 Arakawa Chem Ind Co Ltd ポリイミド系接着剤組成物、硬化物、接着シート、積層体、フレキシブルプリント基板
JP2016041797A (ja) * 2014-08-19 2016-03-31 京セラケミカル株式会社 接着剤用樹脂組成物、接着シート、カバーレイフィルム及びフレキシブル配線板
JP2016196549A (ja) * 2015-04-03 2016-11-24 住友ベークライト株式会社 プリント配線基板用樹脂組成物、プリプレグ、樹脂基板、金属張積層板、プリント配線基板、および半導体装置
WO2017027482A1 (fr) * 2015-08-08 2017-02-16 Designer Molecules, Inc. Compositions durcissables anioniques
JP2017119361A (ja) * 2014-12-26 2017-07-06 荒川化学工業株式会社 樹脂付銅箔、銅張積層板、プリント配線板及び多層配線板
JP2019065075A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 熱硬化性樹脂組成物及び繊維強化プリプレグ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013199645A (ja) * 2012-02-24 2013-10-03 Arakawa Chem Ind Co Ltd ポリイミド系接着剤組成物、硬化物、接着シート、積層体、フレキシブルプリント基板
JP2016041797A (ja) * 2014-08-19 2016-03-31 京セラケミカル株式会社 接着剤用樹脂組成物、接着シート、カバーレイフィルム及びフレキシブル配線板
JP2017119361A (ja) * 2014-12-26 2017-07-06 荒川化学工業株式会社 樹脂付銅箔、銅張積層板、プリント配線板及び多層配線板
JP2016196549A (ja) * 2015-04-03 2016-11-24 住友ベークライト株式会社 プリント配線基板用樹脂組成物、プリプレグ、樹脂基板、金属張積層板、プリント配線基板、および半導体装置
WO2017027482A1 (fr) * 2015-08-08 2017-02-16 Designer Molecules, Inc. Compositions durcissables anioniques
JP2019065075A (ja) * 2017-09-28 2019-04-25 日立化成株式会社 熱硬化性樹脂組成物及び繊維強化プリプレグ

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