WO2018030026A1 - Stratifié comprenant une couche adhésive à constante diélectrique faible - Google Patents

Stratifié comprenant une couche adhésive à constante diélectrique faible Download PDF

Info

Publication number
WO2018030026A1
WO2018030026A1 PCT/JP2017/024168 JP2017024168W WO2018030026A1 WO 2018030026 A1 WO2018030026 A1 WO 2018030026A1 JP 2017024168 W JP2017024168 W JP 2017024168W WO 2018030026 A1 WO2018030026 A1 WO 2018030026A1
Authority
WO
WIPO (PCT)
Prior art keywords
laminate
resin
adhesive layer
less
substrate
Prior art date
Application number
PCT/JP2017/024168
Other languages
English (en)
Japanese (ja)
Inventor
忠彦 三上
伊藤　武
遼 薗田
坂田　秀行
Original Assignee
東洋紡株式会社
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 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2018532870A priority Critical patent/JP6984602B2/ja
Priority to KR1020187033852A priority patent/KR102340014B1/ko
Priority to CN201780042592.5A priority patent/CN109476124B/zh
Publication of WO2018030026A1 publication Critical patent/WO2018030026A1/fr

Links

Classifications

    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to a laminate containing an adhesive layer exhibiting a low dielectric constant and a low dielectric loss tangent. More specifically, the present invention relates to a laminate in which a resin substrate and a metal substrate are laminated via an adhesive layer exhibiting a low dielectric constant and a low dielectric loss tangent. In particular, the present invention relates to a laminate for a flexible printed wiring board (hereinafter abbreviated as FPC), and a coverlay film, a laminate, a copper foil with resin, and a bonding sheet including the laminate.
  • FPC flexible printed wiring board
  • the base film having low dielectric properties is low in polarity
  • the adhesive strength is weak when conventional epoxy adhesives or acrylic adhesives are used, so that FPC members such as coverlay films and laminates can be produced. It was difficult.
  • epoxy adhesives and acrylic adhesives are not excellent in low dielectric properties and impair the dielectric properties of FPC.
  • polyolefin resins are known to have low dielectric properties. Therefore, an FPC adhesive composition using a polyolefin resin has been proposed.
  • Patent Document 1 a polyolefin copolymer containing a carboxyl group, a block copolymer of an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and a heat-reactive adhesive using an epoxy resin Compositions have been proposed.
  • Patent Document 2 an adhesive composition using a carboxyl group-containing styrene elastomer and an epoxy resin is proposed.
  • Patent Document 1 describes adhesion between a polyimide film and SUS and solder heat resistance, but does not mention dielectric properties, and adhesion to a substrate film having low dielectric properties such as LCP. Is difficult to obtain.
  • Patent Document 2 describes dielectric properties and adhesiveness between the polyimide film and the copper foil, but does not mention adhesiveness with a base film having low dielectric properties such as LCP.
  • solder heat resistance after drying is described, it cannot be said that the solder heat resistance after humidification is sufficient.
  • the present invention shows that the adhesive layer having specific physical properties is not only a conventional polyimide film but also a resin having a low dielectric property such as LCP which is not assumed in the prior art.
  • the present inventors have found that the substrate and a metal substrate such as a copper foil are excellent in high adhesion, high solder heat resistance, and low dielectric properties, and have completed the present invention.
  • the present invention is a laminate in which an adhesive layer having excellent adhesion to various resin substrates such as polyimide and LCP and a metal substrate, and excellent in heat resistance and low dielectric properties is laminated.
  • the purpose is to provide a body.
  • the laminated body (X) has a relative dielectric constant ( ⁇ c ) at a frequency of 1 MHz of 3.0 or less, and (2) the dielectric body at a frequency of 1 MHz of the laminated body (X) obtained by removing the metal substrate from the laminated body (Z).
  • Tangent (tan ⁇ ) is 0.02 or less
  • Peel strength between resin substrate and metal substrate is 0.5 N / mm or more
  • Humidity solder heat resistance of laminate (Z) Laminated body (Z) characterized by being 240 ° C or higher.
  • the dielectric constant ( ⁇ c ) at a frequency of 1 MHz of the laminate (X) is 3.0 or less, and (2) the dielectric loss tangent (tan ⁇ ) of the laminate (X) at a frequency of 1 MHz.
  • a printed wiring board containing the adhesive sheet as a component.
  • a laminate (Z) in which a resin substrate and a metal substrate are laminated via an adhesive layer containing a carboxyl group-containing polyolefin resin (A) according to the present invention is: (1) the laminate (Z) to the metal substrate.
  • the relative permittivity ( ⁇ c ) at a frequency of 1 MHz of the laminate (X) from which the metal is removed is 3.0 or less, and (2) the frequency of the laminate (X) from which the metal substrate is removed from the laminate (Z)
  • the dielectric loss tangent (tan ⁇ ) at 1 MHz is 0.02 or less, (3) the peel strength between the resin substrate and the metal substrate is 0.5 N / mm or more, and (4) the laminate (Z).
  • the laminate (Z) according to the present invention is obtained by laminating a resin substrate and a metal substrate via an adhesive layer containing a carboxyl group-containing polyolefin resin (A), and the laminate (X) is a carboxyl group. It is a laminated body of the adhesive bond layer containing the containing polyolefin resin (A) and the resin base material.
  • the carboxyl group-containing polyolefin resin (A) used in the present invention (hereinafter also simply referred to as component (A)) is not limited, but the polyolefin resin may be at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydride thereof. It is preferable that it is obtained by grafting.
  • the polyolefin resin is a hydrocarbon such as a homopolymer of an olefin monomer exemplified by ethylene, propylene, butene, butadiene, isoprene or the like, or a copolymer with other monomers, and a hydride or halide of the obtained polymer.
  • the propylene- ⁇ -olefin copolymer is a copolymer in which ⁇ -olefin is copolymerized mainly with propylene.
  • ⁇ -olefin for example, ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate or the like can be used. Of these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the ratio of the propylene component to the ⁇ -olefin component of the propylene- ⁇ -olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • Examples of at least one of ⁇ , ⁇ -unsaturated carboxylic acid and acid anhydrides thereof include maleic acid, itaconic acid, citraconic acid, and acid anhydrides thereof.
  • acid anhydrides are preferable, and maleic anhydride is more preferable.
  • Specific examples include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer, and the like.
  • These acid-modified polyolefins can be used alone or in combination of two or more.
  • a maleic anhydride-modified propylene-butene copolymer is preferable.
  • the propylene component / 1-butene component (molar ratio) of the maleic anhydride-modified propylene-butene copolymer is preferably 90 to 50/10 to 50, more preferably 85 to 60/15 to 40. It is preferably 80 to 55/20 to 45, more preferably 75 to 60/25 to 40.
  • the lower limit of the acid value of the carboxyl group-containing polyolefin resin (A) is preferably 100 equivalents / 10 6 g or more, more preferably 200 from the viewpoints of heat resistance and adhesion to a resin substrate or a metal substrate. Equivalent / 10 6 g or more, more preferably 250 equivalent / 10 6 g. If it is less than the above value, the compatibility with the epoxy resin (D) and the carbodiimide resin (C) is low, and the adhesive strength may not be exhibited. In some cases, the crosslinking density is low and the heat resistance is poor.
  • the upper limit is preferably 1000 equivalents / 10 6 g or less, more preferably 700 equivalents / 10 6 g or less, and even more preferably 500 equivalents / 10 6 g or less.
  • the adhesiveness may decrease.
  • the viscosity and stability of a solution may fall, and pot life property may fall.
  • the weight average molecular weight (Mw) of the carboxyl group-containing polyolefin resin (A) is preferably in the range of 10,000 to 180,000. More preferably, it is in the range of 20,000 to 160,000, more preferably in the range of 30,000 to 150,000, particularly preferably in the range of 40,000 to 140,000, and most preferably 50 , 13,000 to 130,000. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity.
  • the carboxyl group-containing polyolefin resin (A) is preferably a crystalline resin. Since the carboxyl group-containing polyolefin resin (A) is crystalline, it is advantageous because it has a stronger cohesive force and superior adhesion than amorphous.
  • the crystallinity means that a temperature is raised from ⁇ 100 ° C. to 250 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter (DSC) and shows a clear melting peak in the temperature raising process. .
  • the melting point (Tm) of the carboxyl group-containing polyolefin resin (A) is preferably in the range of 50 ° C to 120 ° C. More preferably, it is in the range of 60 ° C to 100 ° C, and most preferably in the range of 70 ° C to 90 ° C. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity.
  • the heat of fusion ( ⁇ H) of the carboxyl group-containing polyolefin resin (A) is preferably in the range of 5 J / g to 60 J / g.
  • the range is more preferably 10 J / g to 50 J / g, and still more preferably 20 J / g to 40 J / g. If it is less than the above value, the cohesive force becomes weak and the adhesiveness may be inferior. On the other hand, when the above value is exceeded, there may be a problem in operability when bonding due to low fluidity.
  • the production method of the carboxyl group-containing polyolefin resin (A) is not particularly limited.
  • a radical graft reaction that is, a radical species is generated with respect to a polymer that becomes a main chain, and the radical species is used as a polymerization initiation point to produce an unsaturated carboxylic acid. Reaction for graft polymerization of acid and acid anhydride), and the like.
  • organic peroxide is not particularly limited, but di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile, etc. Examples thereof include azonitriles.
  • the adhesive layer refers to a layer of the adhesive composition after the adhesive composition is applied to a substrate and dried or cured.
  • Ad refers to a layer of the adhesive composition after the adhesive composition is applied to a substrate and dried or cured.
  • the thickness of an adhesive bond layer is not specifically limited, Preferably it is 5 micrometers or more, More preferably, it is 10 micrometers or more, More preferably, it is 15 micrometers or more. Moreover, it is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and further preferably 50 ⁇ m or less. If the thickness is too thin, sufficient adhesion performance may not be obtained. If the thickness is too thick, drying will be insufficient and residual solvent will tend to increase. There is a problem.
  • 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, which is a printed wiring board constituent material, or a polyimide film.
  • 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 in that the residual solvent is foamed during the printed circuit board press, resulting in blistering.
  • the relative dielectric constant ( ⁇ c ) at 1 MHz of the adhesive layer is preferably 3.0 or less, more preferably 2.6 or less, and even more preferably 2.3 or less.
  • the lower limit is not particularly limited, but is practically 2.0.
  • the relative dielectric constant ( ⁇ c ) in the entire region of the frequency of 1 MHz to 10 GHz is preferably 3.0 or less, more preferably 2.6 or less, and further preferably 2.3 or less.
  • the dielectric loss tangent (tan ⁇ ) at 1 MHz of the adhesive layer is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.005 or less.
  • the lower limit is not particularly limited, but is practically 0.0001.
  • the dielectric loss tangent (tan ⁇ ) in the entire region of the frequency of 1 MHz to 10 GHz is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.005 or less.
  • the relative dielectric constant ( ⁇ c ) and dielectric loss tangent (tan ⁇ ) of the adhesive layer can be measured as follows. That is, the adhesive composition is applied to a release substrate so that the thickness after drying is 25 ⁇ m and dried at about 130 ° C. for about 3 minutes. Next, it is cured by heat treatment at about 140 ° C. for about 4 hours, and the cured adhesive composition layer (adhesive layer) is peeled from the release film.
  • a metal layer is formed on both sides of the adhesive layer by a thin film method such as vapor deposition, sputtering, or application of a conductive paste to form a capacitor, and the capacitance is measured to determine the relative dielectric constant ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) can be calculated.
  • the resin base material is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, but a resin base material such as a film-like resin ( Hereinafter, the substrate film layer is also preferable.
  • a resin base material such as a film-like resin
  • Specific examples include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers (LCP), polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins, and fluorine resins.
  • LCP liquid crystal polymers
  • polyphenylene sulfide polyphenylene sulfide
  • syndiotactic polystyrene polyolefin resins
  • fluorine resins fluorine resins.
  • Bexter registered trademark
  • a polyimide film the Apical (trademark) by Kaneka Corporation is mentioned, for example.
  • the thickness of a resin base material Preferably it is 1 micrometer or more, More preferably, it is 3 micrometers or more, More preferably, it is 10 micrometers or more. Moreover, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit. On the other hand, if the thickness is too thick, the processing efficiency at the time of circuit fabrication may be reduced. Further, the relative dielectric constant ( ⁇ c ) of the resin base material is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.5 or less. The lower limit is not particularly limited, and there is no problem if it is industrially 0.1 or more.
  • Metal base material Any conventionally known conductive material that can be used for the circuit board can be used as the metal substrate.
  • the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, and alloys, plated products, metals treated with other metals such as zinc and chromium compounds, and the like.
  • Metal foil is preferable, and copper foil is more preferable.
  • the thickness of metal foil Preferably it is 1 micrometer or more, More preferably, it is 3 micrometers or more, More preferably, it is 10 micrometers or more.
  • it 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.
  • the form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited.
  • the length is not particularly limited.
  • the width is not particularly limited, but is preferably about 250 to 500 cm.
  • the laminate (Z) of the present invention is a laminate in which a resin substrate and a metal substrate are laminated via an adhesive layer (a three-layer laminate of resin substrate / adhesive layer / metal substrate).
  • (X) is a laminate of a resin substrate and an adhesive layer (resin substrate / adhesive layer).
  • the laminate (X) and the laminate (Z) may be simply referred to as a laminate.
  • the laminate (X) may be obtained by removing the metal substrate from the laminate (Z) by a method such as etching, and the adhesive composition is applied to a resin substrate according to a conventional method and dried. It may be obtained by doing.
  • the laminate (Z) may be obtained by laminating a metal substrate on the laminate (X), or after applying and drying the adhesive composition on the metal substrate according to a conventional method, It may be obtained by laminating.
  • a release substrate can also be laminated on the surface of the adhesive layer of the laminate (X).
  • an adhesive layer is further laminated on the resin substrate or metal substrate of the laminate (Z) (adhesive layer / resin substrate / adhesive layer / metal substrate, resin substrate / adhesive layer / metal substrate). / Adhesive layer, adhesive layer / resin substrate / adhesive layer / metal substrate / adhesive layer).
  • the laminate of the present invention further satisfies the following requirements (1) to (4).
  • the relative permittivity ( ⁇ c ) at a frequency of 1 MHz of the laminate (X) obtained by removing the metal substrate from the laminate (Z) is required to be 3.0 or less. is there.
  • the relative dielectric constant ( ⁇ c ) of the laminate (X) can be measured as follows. That is, the metal substrate of the laminate (Z) is removed cleanly with an etching solution to obtain a laminate (X) having two layers of an adhesive layer and a resin substrate.
  • the etching solution is not particularly limited, and a ferric chloride aqueous solution, a cupric chloride aqueous solution, a mixed solution of sulfuric acid and hydrogen peroxide, an alkali etchant, a nickel etchant, or the like can be used.
  • a capacitor is formed by forming a metal layer on both surfaces of the laminate (X) by a method such as vapor deposition, a thin film method such as sputtering, or application of a conductive paste, and the capacitance is measured to compare the thickness and area.
  • a method for calculating the dielectric constant ( ⁇ c ) can be exemplified.
  • the adhesive composition is applied to a resin substrate so that the thickness after drying is 25 ⁇ m, and dried at about 130 ° C. for about 3 minutes.
  • the laminate (X) can also be produced by curing by heat treatment at about 140 ° C. for about 4 hours.
  • the relative dielectric constant ( ⁇ c ) of the laminate (X) can be measured as described above.
  • the dielectric constant ((epsilon) c ) in frequency 1MHz is 3.0 or less, it is included by this invention.
  • the relative permittivity ( ⁇ c ) at a frequency of 1 MHz of the laminate (X) is 3.0 or less, preferably 2.8 or less, more preferably 2.7 or less, and even more preferably 2.6 or less. It is.
  • the lower limit is not particularly limited, but is practically 2.0.
  • the relative dielectric constant ( ⁇ c ) in the entire region of the frequency of 1 MHz to 10 GHz is preferably 3.0 or less, more preferably 2.8 or less, further preferably 2.7 or less, Particularly preferred is 2.6 or less.
  • the dielectric loss tangent (tan ⁇ ) at a frequency of 1 MHz of the laminate (X) obtained by removing the metal substrate from the laminate (Z) is required to be 0.02 or less.
  • the dielectric loss tangent (tan ⁇ ) of the laminate (X) can be measured as follows. That is, the metal substrate of the laminate (Z) is removed cleanly with an etching solution to obtain a laminate (X) having two layers of an adhesive layer and a resin substrate.
  • the etching solution is not particularly limited, and a ferric chloride aqueous solution, a cupric chloride aqueous solution, a mixed solution of sulfuric acid and hydrogen peroxide, an alkali etchant, a nickel etchant, or the like can be used.
  • a metal layer is formed on both surfaces of the laminate (X) by a thin film method such as vapor deposition, sputtering, or application of a conductive paste to form a capacitor, and the capacitance is measured to determine the dielectric from the thickness and area.
  • a method for calculating the tangent (tan ⁇ ) can be exemplified.
  • the adhesive composition is applied to a resin substrate so that the thickness after drying is 25 ⁇ m, and dried at about 130 ° C. for about 3 minutes.
  • the laminate (X) can also be produced by curing by heat treatment at about 140 ° C. for about 4 hours.
  • the dielectric loss tangent (tan ⁇ ) of the laminate (X) can be measured as described above.
  • the dielectric loss tangent (tan-delta) in frequency 1MHz is 0.02 or less, it is included by this invention.
  • the dielectric loss tangent (tan ⁇ ) at a frequency of 1 MHz of the laminate (X) is 0.02 or less, preferably 0.01 or less, more preferably 0.005 or less.
  • the lower limit is not particularly limited, but is practically 0.0001.
  • the dielectric loss tangent (tan ⁇ ) in the entire region of the frequency of 1 MHz to 10 GHz is preferably 0.02 or less, more preferably 0.01 or less, and further preferably 0.005 or less.
  • the peel strength between the resin base material and the metal base material needs to be 0.5 N / mm or more.
  • the laminate (Z) resin base material is peeled 90 ° at a tensile rate of 50 mm / min at room temperature (about 25 ° C.), and the peel strength is measured.
  • the 90 ° peel strength needs to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more.
  • the laminate (Z) can be produced as follows. Specifically, the adhesive composition is applied to a resin substrate so that the thickness after drying is about 25 ⁇ m, and dried at about 130 ° C. for about 3 minutes. Next, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). Bonding is performed by vacuum pressing at a pressure of about 40 kgf / cm 2 at about 160 ° C. for about 30 seconds so that the glossy surface of the metal substrate is in contact with the adhesive composition layer. Next, it is cured by heat treatment at about 140 ° C. for about 4 hours to produce a three-layer laminate (Z) of resin substrate / adhesive layer / metal substrate. In addition, even if it is a laminated body (Z) produced by methods other than the said method, if 90 degree peel strength is 0.5 N / mm or more, it is included by this invention.
  • the laminate (Z) of the present invention can be obtained by laminating a metal substrate on the surface of the adhesive composition layer (adhesive layer) of the laminate (X). Bonding is performed by vacuum pressing at a pressure of about 40 kgf / cm 2 at about 160 ° C. for about 30 seconds so that the glossy surface of the metal substrate is in contact with the adhesive composition layer. Next, it is cured by heat treatment at about 140 ° C. for about 4 hours to produce a three-layer laminate (Z) of resin substrate / adhesive layer / metal substrate. At normal temperature (about 25 ° C.), the resin substrate of the laminate (Z) is peeled 90 ° at a tensile speed of 50 mm / min, and the peel strength is measured. The 90 ° peel strength needs to be 0.5 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more.
  • the laminate (Z) according to the present invention is required to have a humidified solder heat resistance of 240 ° C. or higher. Specifically, the laminate (Z) is treated for about 72 hours under conditions of about 40 ° C. and about 80 RH%, and then flows into a solder bath melted at each temperature for 1 minute, so that there is no change in appearance such as swelling. Measure the temperature.
  • the humidified solder heat resistance needs to be 240 ° C. or higher, preferably 250 ° C. or higher, more preferably 260 ° C. or higher.
  • the laminate (Z) can be produced as follows. Specifically, the adhesive composition is applied to a resin substrate so that the thickness after drying is 25 ⁇ m, and dried at about 130 ° C. for about 3 minutes. Next, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). Bonding is performed by vacuum pressing for about 30 seconds under a pressure of about 40 kgf / cm 2 at about 160 ° C. so that the glossy surface of the metal substrate is in contact with the adhesive composition layer. Next, it is cured by heat treatment at about 140 ° C. for about 4 hours to produce a three-layer laminate (Z) of resin substrate / adhesive layer / metal substrate. In addition, even if it is a laminated body (Z) produced by methods other than the said method, if humidification solder heat resistance is 240 degreeC or more, it is included by this invention.
  • the laminate (Z) of the present invention can be obtained by laminating a metal substrate on the surface of the adhesive composition layer (adhesive layer) of the laminate (X). Bonding is performed by vacuum pressing at a pressure of about 40 kgf / cm 2 at about 160 ° C. for about 30 seconds so that the glossy surface of the metal substrate is in contact with the adhesive composition layer. Next, it is cured by heat treatment at about 140 ° C. for about 4 hours to produce a three-layer laminate (Z) of resin substrate / adhesive layer / metal substrate. The laminate (Z) is treated for about 72 hours under conditions of about 40 ° C.
  • the humidified solder heat resistance needs to be 240 ° C. or higher, preferably 250 ° C. or higher, more preferably 260 ° C. or higher.
  • the adhesive composition used in the present invention contains at least a carboxyl group-containing polyolefin resin (A).
  • A carboxyl group-containing polyolefin resin
  • the adhesive composition of the present invention includes a carboxyl group-containing styrene resin (B) (hereinafter also simply referred to as component (B)), a carbodiimide resin (C) (hereinafter simply referred to as (C). ) And / or epoxy resin (D) (hereinafter also simply referred to as component (D)).
  • component (B) carboxyl group-containing styrene resin
  • C carbodiimide resin
  • D epoxy resin
  • the carboxyl group-containing styrene resin (B) that can be used in the present invention is not limited.
  • the aromatic vinyl compound is not particularly limited.
  • styrene for example, styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethyl
  • conjugated diene compound examples include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
  • copolymers of these aromatic vinyl compounds and conjugated diene compounds include styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), Examples thereof include styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS).
  • SEBS styrene-ethylene-butylene-styrene block copolymers
  • SEPS styrene-ethylene-propylene-styrene block copolymers
  • SEEPS styrene-ethylene-ethylene / propylene-styrene block copolymer
  • the modification of the carboxyl group-containing styrene resin (B) can be performed, for example, by copolymerizing an unsaturated carboxylic acid during the polymerization of the styrene resin. Moreover, it can also carry out by heating and kneading
  • the unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, and fumaric anhydride.
  • the lower limit of the acid value of the carboxyl group-containing styrene resin (B) is preferably 10 equivalents / 10 6 g or more, more preferably 100 from the viewpoints of heat resistance and adhesion to a resin substrate or a metal substrate. Equivalent / 10 6 g or more, more preferably 150 equivalent / 10 6 g. If it is less than the above value, the compatibility with the epoxy resin (D) and the carbodiimide resin (C) is low, and the adhesive strength may not be exhibited. In some cases, the crosslinking density is low and the heat resistance is poor.
  • the upper limit is preferably 1000 equivalents / 10 6 g or less, more preferably 700 equivalents / 10 6 g or less, and even more preferably 500 equivalents / 10 6 g or less. When the above value is exceeded, adhesiveness and low dielectric properties may be deteriorated.
  • the content of the carboxyl group-containing styrene resin (B) is from 95 to 95 parts by mass of the carboxyl group-containing polyolefin resin (A) and from 95 to 95 parts by weight of the carboxyl group-containing styrene resin (B).
  • the amount of component (A) When the amount of component (A) is less than the above value, the crosslinking density may decrease, and the humidified solder heat resistance may decrease. When the amount of the component (A) exceeds the above value, the wettability to the substrate is lowered, and the adhesive strength may be lowered.
  • the carbodiimide resin (C) is not particularly limited as long as it has a carbodiimide group in the molecule. Preferably, it is polycarbodiimide having two or more carbodiimide groups in the molecule.
  • the carboxyl group of the carboxyl group-containing polyolefin resin (A) or the carboxyl group-containing styrene resin (B) reacts with the carbodiimide, and the interaction between the adhesive composition and the substrate is caused. Can be improved and adhesion can be improved.
  • the content of the carbodiimide resin (C) is 0.1 to about 100 parts by mass in total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B).
  • the range is preferably 30 parts by mass.
  • the range is more preferably 1 to 25 parts by mass, and most preferably 2 to 20 parts by mass. If it is less than the above value, there is a problem that the interaction with the substrate does not appear and the adhesiveness is lowered. When the above value is exceeded, there is a problem that the pot life of the adhesive is lowered and the low dielectric properties are lowered.
  • Epoxy resin (D) Although it will not specifically limit as an epoxy resin (D) if it has a glycidyl group in a molecule
  • biphenyl type epoxy resin naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, At least one selected from the group consisting of tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine can be used.
  • Bisphenol A type epoxy resin, novolak type epoxy resin or dicyclopentadiene type epoxy resin is preferable.
  • the content of the epoxy resin (D) is 1 to 30 masses with respect to 100 mass parts in total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B).
  • the range is preferably 2 to 15 parts by mass, and most preferably 3 to 10 parts by mass. If it is less than the said range, sufficient hardening effect cannot be acquired but adhesiveness and heat resistance may fall. Further, if the amount is within the above range, there are problems that the pot life of the adhesive is lowered and the low dielectric properties are lowered.
  • the adhesive composition used in the present invention can further contain an organic solvent.
  • the organic solvent used in the present invention is not particularly limited as long as it dissolves the carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C), and the epoxy resin (D).
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane, heptane, octane and decane
  • alicyclic carbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane
  • Halogenated hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene, chloroform, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone, methyl isobutyl ketone, Ketone solvents such as methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, cellsolves such as methyl cellosolv
  • the organic solvent is preferably in the range of 100 to 1000 parts by mass, and in the range of 200 to 900 parts by mass with respect to 100 parts by mass in total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B). More preferably, the range is 300 to 800 parts by mass. If it is less than the said range, liquid state and pot life property may fall. Moreover, when the said range is exceeded, there exists a problem which becomes disadvantageous from the surface of manufacturing cost and transport cost.
  • the adhesive composition used in the present invention may further contain other components as necessary.
  • specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
  • ⁇ Flame Retardant> You may mix
  • the flame retardant include bromine, phosphorus, nitrogen, and metal hydroxide compounds.
  • phosphorus-based flame retardants are preferable, and phosphoric acid esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphates such as aluminum phosphinate, phosphazenes, and other known phosphorus flame retardants can be used. . These may be used alone or in any combination of two or more.
  • the flame retardant is preferably contained in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass with respect to 100 parts by mass of the total of the components (A) to (D).
  • the range of 10 to 100 parts by mass is most preferable. If it is less than the said range, a flame retardance may be low.
  • the above range is exceeded, there is a problem that the adhesiveness, heat resistance, electrical characteristics and the like deteriorate.
  • ⁇ Tackifier> You may mix
  • tackifiers include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins, which improve adhesive strength. Used for purposes. These may be used alone or in any combination of two or more.
  • ⁇ Filler> You may mix
  • the compounding amount of silica is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass in total of the components (A) to (D). If it is less than 0.05 parts by mass, the effect of improving the heat resistance may not be exhibited. On the other hand, when the amount exceeds 30 parts by mass, there may be a case where poor dispersion of silica occurs, the solution viscosity becomes too high, and the workability is deteriorated or the adhesiveness is lowered.
  • ⁇ Silane coupling agent> You may mix
  • glycidyl such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane from the viewpoint of heat resistance.
  • a silane coupling agent having a group is more preferable.
  • the compounding amount of the silane coupling agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) to (D). If it is less than 0.5 parts by mass, heat resistance may be deteriorated. On the other hand, if it exceeds 20 parts by mass, heat resistance failure and adhesiveness may decrease.
  • the adhesive sheet is obtained by laminating the laminate (Z) and the release substrate via an adhesive composition, or laminating a release substrate on the adhesive layer surface of the laminate (X). Or a release substrate laminated on at least one surface of the adhesive layer.
  • Specific configuration modes include a release substrate / adhesive layer, a release substrate / adhesive layer / release substrate, a resin substrate / adhesive layer / release substrate, a metal substrate / adhesive.
  • the adhesive composition of the present invention can be obtained by applying and drying the adhesive composition used in the present invention on various laminates according to a conventional method.
  • a release substrate is pasted to the adhesive layer after drying, it can be rolled up without causing any back-off to the substrate, and it is excellent in operability and the adhesive layer is protected so that it can be stored. Excellent and easy to use.
  • the adhesive layer itself can be transferred to another substrate.
  • the release substrate is not particularly limited.
  • a coating layer of a sealant such as clay, polyethylene, or polypropylene is formed on both surfaces of paper such as fine paper, kraft paper, roll paper, and glassine paper.
  • a silicone-type, fluorine-type, or alkyd-type release agent is further applied on each coating layer.
  • various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, and those obtained by applying the release agent on a film such as polyethylene terephthalate are also included.
  • polypropylene seal treatment is applied to both sides of the fine paper and an alkyd release agent is used on it. Or what uses an alkyd type mold release agent on polyethylene terephthalate is preferred.
  • the “printed wiring board” in the present invention includes a laminate formed from a metal foil forming a conductor circuit and a resin base material as a constituent element.
  • a printed wiring board is manufactured by conventionally well-known methods, such as a subtractive method, using a metal-clad laminated body, for example. If necessary, a so-called flexible circuit board (FPC), flat cable, tape automated bonding (covered by using a cover film or screen printing ink, etc., partially or entirely covered with a conductor circuit formed of metal foil (tape automated bonding) TAB) circuit board and the like.
  • FPC flexible circuit board
  • TAB tape automated bonding
  • the printed wiring board of the present invention can have any laminated structure that can be employed as a printed wiring board.
  • it can be set as the printed wiring board comprised from four layers, a base film layer, a metal foil layer, an adhesive bond layer, and a cover film layer.
  • it can be set as the printed wiring board comprised from five layers, a base film layer, an adhesive bond layer, a metal foil layer, an adhesive bond layer, and a cover film layer.
  • the adhesive composition used in the present invention can be suitably used for each adhesive layer of a printed wiring board.
  • the adhesive composition used in the present invention is used as an adhesive, not only conventional polyimide, polyester film and copper foil constituting a printed wiring board but also high adhesiveness with a low-polarity resin substrate such as LCP.
  • solder reflow resistance can be obtained, and the adhesive layer confidence is excellent in low dielectric properties. Therefore, it is suitable as an adhesive composition used for a coverlay film, a laminate, a resin-coated copper foil, and a bonding sheet.
  • any resin film conventionally used as a substrate for printed wiring boards can be used as the substrate film.
  • the resin for the base film include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
  • it has excellent adhesion to low-polar substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.
  • any conventionally known insulating film can be used as an insulating film for a printed wiring board.
  • any conventionally known insulating film can be used as an insulating film for a printed wiring board.
  • manufactured from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyimide, polyamideimide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, etc.
  • Film can be used. More preferably, it is a polyimide film or a liquid crystal polymer film.
  • the printed wiring board of the present invention can be manufactured using any conventionally known process except that the material of each layer described above is used.
  • a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter referred to as “cover film-side semi-finished product”) is manufactured.
  • an adhesive layer is laminated on a semi-finished product (hereinafter referred to as “base film side two-layer semi-product”) or a base film layer in which a desired circuit pattern is formed by laminating a metal foil layer on the base film layer.
  • base film side three-layer semi-product having a desired circuit pattern formed by laminating a metal foil layer thereon
  • base film side two-layer semi-product The base film side three-layer semi-finished product is collectively referred to as “base film side semi-finished product”.
  • a four-layer or five-layer printed wiring board can be obtained by laminating the cover film side semi-finished product and the base film side semi-finished product thus obtained.
  • the base film side semi-finished product is, for example, (A) a step of applying a resin solution to be a base film to the metal foil, and initial drying of the coating film (B) (A) and the metal foil obtained in the initial stage It can be obtained by a production method including a step of heat-treating and drying the laminate with the dried coating film (hereinafter referred to as “heat treatment / solvent removal step”).
  • a conventionally known method can be used to form a circuit in the metal foil layer.
  • An active method may be used and a subtractive method may be used.
  • the subtractive method is preferable.
  • the obtained base film side semi-finished product may be used as it is for pasting with the cover film side semi-finished product. May be used.
  • the cover film side semi-finished product is manufactured, for example, by applying an adhesive to the cover film. If necessary, a crosslinking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.
  • the obtained cover film-side semi-finished product may be used as it is for pasting with the base-side semi-finished product, or after being laminated and stored with the release film for pasting with the base-film-side semi-finished product. May be used.
  • the base film side semi-finished product and the cover film side semi-finished product are each stored, for example, in the form of a roll, and then bonded together to produce a printed wiring board.
  • Arbitrary methods can be used as a method of bonding, for example, it can bond using a press or a roll. Further, the two can be bonded together while heating by a method such as using a heating press or a heating roll device.
  • the reinforcing material-side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material.
  • a reinforcing plate that cannot be rolled up hard such as a metal plate such as SUS or aluminum, or a plate in which glass fibers are cured with an epoxy resin, by transferring and applying an adhesive previously applied to a release substrate. It is preferred to be manufactured.
  • coated adhesive agent can be performed as needed.
  • the adhesive layer is semi-cured.
  • the obtained reinforcing material-side semi-finished product may be used as it is for pasting with the back side of the printed wiring board, and after being used for pasting with the base film-side semi-finished product after storing the release film. May be.
  • the base film side semi-finished product, the cover film side semi-finished product, and the reinforcing agent side semi-finished product are all laminated bodies for printed wiring boards in the present invention.
  • the acid value (equivalent / 10 6 g) in the present invention is FT-IR (manufactured by Shimadzu Corporation, FT-IR8200PC) using maleic anhydride carbonyl (The absorbance (I) of the stretching peak (1780 cm ⁇ 1 ) of the C ⁇ O) bond, the absorbance (II) of the isotactic peculiar peak (840 cm ⁇ 1 ), and a maleic anhydride (manufactured by Tokyo Kasei) chloroform solution.
  • Acid value (B) component carboxyl group-containing styrene resin
  • the acid value (equivalent / 10 6 g) in the present invention is obtained by dissolving a carboxyl group-containing styrene resin in toluene and using phenolphthalein as an indicator in a methanol solution of sodium methoxide. Titration. Expressed as equivalents (equivalent / 10 6 g) in 1 ton of resin.
  • Weight average molecular weight (Mw) The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran).
  • the melting point and heat of fusion in the present invention are increased at a rate of 20 ° C./minute using a differential scanning calorimeter (hereinafter DSC, manufactured by TA Instruments Japan, Q-2000). It is a value measured from the top temperature and area of the melting peak when heated and melted into a cooled resin and then heated and melted again.
  • DSC differential scanning calorimeter
  • peel strength (adhesiveness) An adhesive composition to be described later is dried on a polyimide film having a thickness of 12.5 ⁇ m (manufactured by Kaneka Corporation, Apical) or an LCP film having a thickness of 25 ⁇ m (manufactured by Kuraray Co., Ltd., Bexter), and the thickness after drying is 25 ⁇ m. And then dried at 130 ° C. for 3 minutes.
  • the adhesive film (B stage product) thus obtained was bonded to 18 ⁇ m rolled copper foil. Bonding was performed by pressing for 30 seconds under a pressure of 40 kgf / cm 2 at 160 ° C. so that the glossy surface of the rolled copper foil was in contact with the adhesive.
  • Humidity solder heat resistance A sample is prepared by the same method as described above, and a 2.0 cm ⁇ 2.0 cm sample piece is treated at 40 ° C. ⁇ 80 RH% ⁇ 72 hours, and then melted at each temperature in a solder bath for 1 minute. The temperature at which flow occurred and no change in appearance such as blistering occurred was measured.
  • an evaporation-drying type conductive silver paste was applied to a circle with a diameter of 50 mm by screen printing, dried and cured at 120 ° C. for 30 minutes, and further with the conductive silver paste.
  • a lead wire having a length of 30 mm was adhered to the center of the circle with a conductive adhesive to obtain a parallel plate capacitor.
  • the capacitance Cap and loss factor D (dielectric loss tangent) of the obtained parallel plate capacitor were measured using a PRECISION LCR meter HP-4284A under a condition of a frequency of 1 MHz at 22 ° C., and a relative dielectric constant ( ⁇ c ) was calculated.
  • ⁇ c (Cap ⁇ d) / (S ⁇ ⁇ 0 )
  • Cap Capacitance [F]
  • S: measured dielectric area ⁇ ⁇ (25 ⁇ 10 ⁇ 3 ) 2 ⁇ 0 : Dielectric constant of vacuum 8.854 ⁇ 10 ⁇ 12 It is.
  • the relative dielectric constant and dielectric loss tangent obtained were evaluated as follows.
  • the liquid containing the resin was centrifuged to separate and purify an acid-modified propylene-butene copolymer grafted with maleic anhydride, (poly) maleic anhydride and a low molecular weight product. Thereafter, by drying at 70 ° C. under reduced pressure for 5 hours, a maleic anhydride-modified propylene-butene copolymer (CO-1, acid value 410 equivalents / 10 6 g, weight average molecular weight 60,000, Tm 80 ° C., ⁇ H35J / G).
  • Production Example 2 A maleic anhydride-modified propylene-butene copolymer (CO-2, acid value of 290 equivalents / 10 6 g, weight) except that the amount of maleic anhydride charged was changed to 13 parts by mass. Average molecular weight 68,000, Tm 79 ° C., ⁇ H 32 J / g).
  • Production Example 3 A maleic anhydride-modified propylene-butene copolymer (CO-3, acid equivalent of 220 equivalents / 10 6 g, weight was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged was changed to 8 parts by mass. Average molecular weight 74,000, Tm 78 ° C., ⁇ H 29 J / g).
  • Production Example 4 Production Example 1 except that the propylene-butene copolymer (“Tuffmer (registered trademark) XM7080” manufactured by Mitsui Chemicals) was changed to a propylene-butene copolymer (“Tuffmer (registered trademark) XM7070” manufactured by Mitsui Chemicals). In the same manner, a maleic anhydride-modified propylene-butene copolymer (CO-4, acid value 400 equivalent / 10 6 g, weight average molecular weight 57,000, Tm 68 ° C., ⁇ H 15 J / g) was obtained.
  • CO-4 acid value 400 equivalent / 10 6 g, weight average molecular weight 57,000, Tm 68 ° C., ⁇ H 15 J / g
  • Production Example 5 A maleic anhydride-modified propylene-butene copolymer (CO-5, acid value of 300 equivalents / 10 6 g, weight) except that the amount of maleic anhydride charged was changed to 15 parts by mass. Average molecular weight 65,000, Tm 70 ° C., ⁇ H21 J / g).
  • Example 1 In a 500 ml four-necked flask equipped with a water-cooled reflux condenser and a stirrer, 80 parts by mass of the maleic anhydride-modified propylene-butene copolymer (CO-1) obtained in Production Example 1 and a carboxyl group-containing styrene resin 20 parts by mass (Tuftec (registered trademark) M1943) and 500 parts by mass of toluene were charged, and the mixture was heated to 80 ° C. with stirring and dissolved by continuing stirring for 1 hour. The solution obtained by cooling was mixed with 5 parts by mass of carbodiimide resin V-05 and 10 parts by mass of epoxy resin HP-7200 to obtain an adhesive composition.
  • CO-1 maleic anhydride-modified propylene-butene copolymer
  • a carboxyl group-containing styrene resin 20 parts by mass (Tuftec (registered trademark) M1943) and 500 parts by mass of toluene were charged,
  • Table 1 shows the blending amount, adhesive strength, solder heat resistance, and electrical characteristics.
  • the relative dielectric constant of the adhesive layer is 2.27 and the dielectric loss tangent is 0.0031.
  • the relative dielectric constant of the laminate 1 (adhesive layer / polyimide film) is 2.51 and the dielectric loss tangent is 0.0042.
  • the laminate 2 (adhesive layer / LCP film) had a relative dielectric constant of 2.68 and a dielectric loss tangent of 0.0122.
  • Examples 2 to 17 The carboxyl group-containing polyolefin resin (A), carboxyl group-containing styrene resin (B), carbodiimide resin (C), and epoxy resin (D) were changed to those shown in Table 1, and the same method as in Example 1 was used. Examples 2 to 17 were carried out by changing the blending amounts to those shown in FIG. Table 1 shows the adhesive strength, solder heat resistance, and electrical characteristics.
  • Comparative Examples 1-7 Carboxyl group-containing polyolefin resin (A), carboxyl group-containing styrene resin (B), carbodiimide resin (C), and epoxy resin (D) were changed to those shown in Table 2, and the same method as in Example 1 was used. Comparative Examples 1 to 7 were carried out by changing the blending amounts shown in FIG. Table 2 shows the blending amount, adhesive strength, solder heat resistance, and electrical characteristics.
  • the polyolefin resin, carboxyl group-containing styrene resin (B), carbodiimide resin (C), and epoxy resin (D) used in Tables 1 and 2 are as follows.
  • Carboxyl group-containing styrene resin Tuftec (registered trademark) M1911 (Asahi Kasei Chemicals)
  • Carboxyl group-containing styrene resin Tuftec (registered trademark) M1913 (Asahi Kasei Chemicals)
  • Comparative Example 3 since the polyolefin resin does not contain a carboxyl group, the crosslinking density is low and the humidified solder heat resistance is poor. In Comparative Example 4, since the styrene resin does not contain a carboxyl group, the crosslinking density is low and the humidified solder heat resistance is poor. In Comparative Example 5, since no carbodiimide resin is blended, there is little interaction with the LCP interface, and the adhesive strength is low. In Comparative Example 6, since no epoxy resin is blended, the crosslinking density is low and the solder heat resistance is poor. In Comparative Example 7, since the polyolefin resin and the styrene resin are not blended, the low dielectric property of the adhesive composition is inferior.
  • the laminate of the present invention can also be suitably used for electromagnetic shielding applications.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un stratifié qui présente une adhérence élevée, non seulement à des films de polyimide et de polyester conventionnels, mais également à des matériaux de base de résine à faible polarité tels que des matériaux de base de LCP et métalliques, et qui permet d'obtenir une résistance élevée à la chaleur de soudure, tout en ayant d'excellentes caractéristiques de constante diélectrique faible. L'invention concerne en outre un stratifié (Z) qui est obtenu par stratification d'un matériau de base en résine et d'un matériau de base métallique avec une couche adhésive intercalée entre ceux-ci, ladite couche adhésive contenant une résine de polyoléfine contenant un groupe carboxyle (A). Ce stratifié (Z) est caractérisé en ce que : (1) la constante diélectrique relative (εc) à la fréquence de 1 MHz d'un stratifié (X) qui est obtenu par élimination du matériau de base métallique du stratifié (Z) est de 3,0 ou moins ; (2) la tangente de perte diélectrique (tanδ) à la fréquence de 1 MHz du stratifié (X), qui est obtenue par élimination du matériau de base métallique du stratifié (Z), est de 0,02 ou moins ; (3) la résistance au pelage entre le matériau de base de résine et le matériau de base métallique est de 0,5 N/mm ou plus ; et (4) la résistance à la chaleur de soudure humide du stratifié (Z) est de 240 °C ou plus.
PCT/JP2017/024168 2016-08-09 2017-06-30 Stratifié comprenant une couche adhésive à constante diélectrique faible WO2018030026A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018532870A JP6984602B2 (ja) 2016-08-09 2017-06-30 低誘電接着剤層を含有する積層体
KR1020187033852A KR102340014B1 (ko) 2016-08-09 2017-06-30 저유전 접착제층을 함유하는 적층체
CN201780042592.5A CN109476124B (zh) 2016-08-09 2017-06-30 含有低介电粘合剂层的层叠体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-156204 2016-08-09
JP2016156204 2016-08-09

Publications (1)

Publication Number Publication Date
WO2018030026A1 true WO2018030026A1 (fr) 2018-02-15

Family

ID=61161946

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/024168 WO2018030026A1 (fr) 2016-08-09 2017-06-30 Stratifié comprenant une couche adhésive à constante diélectrique faible

Country Status (5)

Country Link
JP (1) JP6984602B2 (fr)
KR (1) KR102340014B1 (fr)
CN (1) CN109476124B (fr)
TW (1) TWI749038B (fr)
WO (1) WO2018030026A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019188284A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Composition adhésive à base de polyoléfines
JP2021077716A (ja) * 2019-11-06 2021-05-20 古河電気工業株式会社 プリント基板およびプリント基板の製造方法
WO2021132058A1 (fr) * 2019-12-23 2021-07-01 三井化学株式会社 Adhésif pour étiquette électronique, et étiquette électronique
WO2021200713A1 (fr) * 2020-03-30 2021-10-07 東洋紡株式会社 Composition adhésive et feuille adhésive, stratifié et carte de circuit imprimé
WO2022091960A1 (fr) * 2020-10-29 2022-05-05 株式会社カネカ Film stratifié et feuille stratifiée plaquée de cuivre
WO2023127890A1 (fr) * 2021-12-28 2023-07-06 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive
JP7335559B2 (ja) 2016-12-22 2023-08-30 東亞合成株式会社 接着剤組成物並びにこれを用いたカバーレイフィルム、ボンディングシート、銅張積層板及び電磁波シールド材

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112440532A (zh) * 2019-08-27 2021-03-05 康宁股份有限公司 用于高频印刷电路板应用的有机/无机层叠体
WO2021045125A1 (fr) * 2019-09-06 2021-03-11 東洋紡株式会社 Composition d'adhésif à base de polyoléfine
TWI724563B (zh) * 2019-09-26 2021-04-11 盟鑫金屬股份有限公司 金屬材料的膠合方法
WO2021106847A1 (fr) * 2019-11-28 2021-06-03 東洋紡株式会社 Film adhésif, stratifié, et carte de circuit imprimé
KR102254212B1 (ko) 2019-12-20 2021-05-21 율촌화학 주식회사 저유전 특성이 우수한 폴리올레핀계 접착제 조성물, 이를 이용한 본딩 시트, 인쇄회로기판 및 그 제조 방법
KR102259097B1 (ko) * 2020-02-28 2021-06-02 (주)이녹스첨단소재 접착 필름, 이를 포함하는 접착 필름 부착 적층체 및 이를 포함하는 금속박 적층체
CN113355032B (zh) * 2020-03-03 2023-02-28 利诺士尖端材料有限公司 粘结膜、包括其的粘结膜附着层叠体及金属箔层叠体
KR20240103489A (ko) 2022-12-27 2024-07-04 율촌화학 주식회사 금속 이온 마이그레이션 방지용 접착제 조성물, 이를 포함하는 본딩 시트 및 인쇄회로기판

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1060401A (ja) * 1996-08-20 1998-03-03 Mitsui Petrochem Ind Ltd 接着剤組成物
JP2000104025A (ja) * 1998-09-29 2000-04-11 Nisshinbo Ind Inc フレキシブルプリント配線板用フィルム
JP2000345132A (ja) * 1999-06-01 2000-12-12 Nisshinbo Ind Inc Ｌｃｐ接合方法
JP2002235061A (ja) * 2001-02-08 2002-08-23 Nitto Denko Corp 熱反応性接着剤組成物および熱反応性接着フィルム
WO2016185956A1 (fr) * 2015-05-15 2016-11-24 東洋紡株式会社 Stratifié comprenant une couche adhésive à faible constante diélectrique
WO2017077912A1 (fr) * 2015-11-02 2017-05-11 東洋紡株式会社 Composition adhésive ignifuge à faible valeur diélectrique

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639353A (en) * 1970-03-20 1972-02-01 Goodrich Co B F Polymers crosslinked with polycarbodiimides
JP5141071B2 (ja) * 2007-03-29 2013-02-13 住友電気工業株式会社 フレキシブルフラットケーブル用絶縁テープおよびその製法
JP4911252B1 (ja) * 2010-11-30 2012-04-04 東洋インキＳｃホールディングス株式会社 カルボキシル基含有変性エステル樹脂を含む熱硬化性樹脂組成物
JPWO2014147903A1 (ja) * 2013-03-22 2017-02-16 東亞合成株式会社 接着剤組成物並びにこれを用いたカバーレイフィルム及びフレキシブル銅張積層板
JP6522993B2 (ja) * 2014-03-05 2019-05-29 デクセリアルズ株式会社 両面黒色粘着テープ
US10544305B2 (en) * 2015-01-16 2020-01-28 Hitachi Chemical Company, Ltd. Thermosetting resin composition, resin film for interlayer insulation, composite film, printed wiring board, and method for producing same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1060401A (ja) * 1996-08-20 1998-03-03 Mitsui Petrochem Ind Ltd 接着剤組成物
JP2000104025A (ja) * 1998-09-29 2000-04-11 Nisshinbo Ind Inc フレキシブルプリント配線板用フィルム
JP2000345132A (ja) * 1999-06-01 2000-12-12 Nisshinbo Ind Inc Ｌｃｐ接合方法
JP2002235061A (ja) * 2001-02-08 2002-08-23 Nitto Denko Corp 熱反応性接着剤組成物および熱反応性接着フィルム
WO2016185956A1 (fr) * 2015-05-15 2016-11-24 東洋紡株式会社 Stratifié comprenant une couche adhésive à faible constante diélectrique
WO2017077912A1 (fr) * 2015-11-02 2017-05-11 東洋紡株式会社 Composition adhésive ignifuge à faible valeur diélectrique

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7335559B2 (ja) 2016-12-22 2023-08-30 東亞合成株式会社 接着剤組成物並びにこれを用いたカバーレイフィルム、ボンディングシート、銅張積層板及び電磁波シールド材
TWI786280B (zh) * 2018-03-30 2022-12-11 日商東洋紡股份有限公司 聚烯烴系黏接劑組成物
CN115558442A (zh) * 2018-03-30 2023-01-03 东洋纺株式会社 聚烯烃类粘接剂组合物
JPWO2019188284A1 (ja) * 2018-03-30 2021-04-08 東洋紡株式会社 ポリオレフィン系接着剤組成物
EP3778818A4 (fr) * 2018-03-30 2021-12-01 Toyobo Co., Ltd. Composition adhésive à base de polyoléfines
KR20200135861A (ko) * 2018-03-30 2020-12-03 도요보 가부시키가이샤 폴리올레핀계 접착제 조성물
JP7484707B2 (ja) 2018-03-30 2024-05-16 東洋紡エムシー株式会社 ポリオレフィン系接着剤組成物
CN111918944A (zh) * 2018-03-30 2020-11-10 东洋纺株式会社 聚烯烃类粘接剂组合物
KR102438894B1 (ko) * 2018-03-30 2022-08-31 도요보 가부시키가이샤 폴리올레핀계 접착제 조성물
WO2019188284A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Composition adhésive à base de polyoléfines
JP2021077716A (ja) * 2019-11-06 2021-05-20 古河電気工業株式会社 プリント基板およびプリント基板の製造方法
JPWO2021132058A1 (fr) * 2019-12-23 2021-07-01
WO2021132058A1 (fr) * 2019-12-23 2021-07-01 三井化学株式会社 Adhésif pour étiquette électronique, et étiquette électronique
JP6981581B1 (ja) * 2020-03-30 2021-12-15 東洋紡株式会社 接着剤組成物、ならびに接着シート、積層体およびプリント配線板
WO2021200713A1 (fr) * 2020-03-30 2021-10-07 東洋紡株式会社 Composition adhésive et feuille adhésive, stratifié et carte de circuit imprimé
WO2022091960A1 (fr) * 2020-10-29 2022-05-05 株式会社カネカ Film stratifié et feuille stratifiée plaquée de cuivre
WO2023127890A1 (fr) * 2021-12-28 2023-07-06 東亞合成株式会社 Composition adhésive et stratifié doté d'une couche adhésive

Also Published As

Publication number Publication date
CN109476124A (zh) 2019-03-15
JPWO2018030026A1 (ja) 2019-06-06
TW201829176A (zh) 2018-08-16
CN109476124B (zh) 2021-06-22
TWI749038B (zh) 2021-12-11
JP6984602B2 (ja) 2021-12-22
KR20190039392A (ko) 2019-04-11
KR102340014B1 (ko) 2021-12-16

Similar Documents

Publication Publication Date Title
JP6984701B2 (ja) 低誘電接着剤層を含有する積層体
JP6984602B2 (ja) 低誘電接着剤層を含有する積層体
JP6761588B2 (ja) 低誘電接着剤組成物
JP6874896B2 (ja) 低誘電難燃性接着剤組成物
JP6705456B2 (ja) 低誘電接着剤組成物
JP6941308B2 (ja) 低誘電接着剤組成物
WO2021075367A1 (fr) Composition adhésive à base de polyoléfine
TW202242060A (zh) 黏接劑組成物、及含有此黏接劑之黏接片、疊層體及印刷配線板

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018532870

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187033852

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17839100

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17839100

Country of ref document: EP

Kind code of ref document: A1