TW201702341A - Laminate comprising low dielectric constant adhesive layer - Google Patents

Laminate comprising low dielectric constant adhesive layer Download PDF

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Publication number
TW201702341A
TW201702341A TW105114487A TW105114487A TW201702341A TW 201702341 A TW201702341 A TW 201702341A TW 105114487 A TW105114487 A TW 105114487A TW 105114487 A TW105114487 A TW 105114487A TW 201702341 A TW201702341 A TW 201702341A
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laminate
resin
adhesive layer
substrate
layer
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TW105114487A
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Chinese (zh)
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TWI697532B (en
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Tadahiko Mikami
Takeshi Ito
Ryo Sonoda
Hideyuki Sakata
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Toyo Boseki
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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
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Adhesive Tapes (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

Provided is a laminate which has superior low dielectric constant characteristics, which exhibits excellent adhesion between metal substrates and not only conventional polyimide and polyester film substrates, but also low polarity resin substrates such as LCP, and which enables high solder heat resistance. This laminate (Z), in which a resin substrate and a metal substrate are layered via an adhesive layer comprising a carboxyl group-containing polyolefin resin (A), is characterized in that: 1.) the dielectric constant ([epsilon]c) of the adhesive layer is at most 3.0 at a frequency of 1MHz; 2.) the dielectric loss tangent (tan[delta]) of the adhesive layer is at most 0.02 at a frequency of 1MHz; 3.) the peel strength of the resin substrate and the metal substrate is at least 0.5N/mm; and 4.) the moist solder heat resistance of the laminate (Z) is at least 240 DEG C.

Description

包含低介電性接著劑層的疊層體Laminate comprising a low dielectric adhesive layer

本發明關於一種包含顯現低介電常數、低介電正切之接著劑層的疊層體。更詳細言之，係關於一種樹脂基材與金屬基材介由顯現低介電常數、低介電正切之接著劑層疊層而成的疊層體。特別是關於可撓性印刷電路板(以下簡稱為FPC)用之疊層體、及含有該疊層體之表覆層膜、疊層板、附樹脂之銅箔及黏合片。The present invention relates to a laminate comprising an adhesive layer exhibiting a low dielectric constant and a low dielectric tangent. More specifically, the present invention relates to a laminate in which a resin substrate and a metal substrate are laminated via an adhesive exhibiting a low dielectric constant and a low dielectric tangent. In particular, a laminate for a flexible printed circuit board (hereinafter abbreviated as FPC), a surface coating film containing the laminate, a laminate, a copper foil with a resin, and an adhesive sheet.

近年，伴隨印刷電路板中之傳輸信號的高速化，信號的高頻化正發展中。與此同時，對於FPC在高頻區域之低介電特性(低介電常數、低介電正切)的要求正日益增長。因應該等要求，作為FPC所使用之基材膜，有人提案以具有低介電特性之液晶聚合物(LCP)、對排聚苯乙烯(SPS)、聚苯硫醚(PPS)等基材膜替換以往的聚醯亞胺(PI)、聚對苯二甲酸乙二酯膜。 但，具有低介電特性之基材膜由於低極性的緣故，使用以往的環氧系接著劑或丙烯酸系接著劑時接著力弱，表覆層膜、疊層板等FPC用構件的製作困難。又，環氧系接著劑或丙烯酸系接著劑，低介電特性並不優異，會損害FPC的介電特性。 另一方面，聚烯烴樹脂已知具有低介電特性。因此，有人提出使用聚烯烴樹脂的FPC用接著劑組成物。例如，專利文獻1中提出了使用含有羧基之聚烯烴系共聚物、芳香族乙烯基化合物聚合物嵌段與共軛二烯系化合物聚合物嵌段之嵌段共聚物、及環氧樹脂的熱反應性接著劑組成物。又，專利文獻2中提出了使用含有羧基之苯乙烯彈性體與環氧樹脂的接著劑組成物。 [先前技術文獻] [專利文獻]In recent years, with the increase in the speed of transmission signals in printed circuit boards, high frequency signals are being developed. At the same time, there is an increasing demand for low dielectric properties (low dielectric constant, low dielectric tangent) of the FPC in the high frequency region. As a substrate film used for FPC, a substrate film such as liquid crystal polymer (LCP), aligned polystyrene (SPS), or polyphenylene sulfide (PPS) having low dielectric properties has been proposed. It replaces the conventional polyimide (PI) and polyethylene terephthalate film. However, the base film having a low dielectric property has a low polarity, and it is difficult to produce a FPC member such as a cover film or a laminate when a conventional epoxy-based adhesive or an acrylic adhesive is used. . Further, the epoxy-based adhesive or the acrylic-based adhesive is not excellent in low dielectric properties, and impairs the dielectric properties of the FPC. On the other hand, polyolefin resins are known to have low dielectric properties. Therefore, an adhesive composition for FPC using a polyolefin resin has been proposed. For example, Patent Document 1 proposes the use of a polyolefin-based copolymer containing a carboxyl group, a block copolymer of an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and heat of an epoxy resin. Reactive adhesive composition. Further, Patent Document 2 proposes an adhesive composition using a styrene elastomer containing a carboxyl group and an epoxy resin. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利3621351號公報 [專利文獻2]WO2014/147903A1公報[Patent Document 1] Japanese Patent No. 3,621,351 [Patent Document 2] WO2014/147903A1

[發明所欲解決之課題] 但，專利文獻1中雖有記述聚醯亞胺膜與SUS之接著性、焊料耐熱性，但並未提及介電特性，難以獲得與LCP等具有低介電特性之基材膜的接著性。又，專利文獻2中雖有記述介電特性、聚醯亞胺膜與銅箔之接著性，但並未提及與LCP等具有低介電特性之基材膜的接著性。又，雖有記述乾燥後之焊料耐熱性，但加濕後之焊料耐熱性不能說是充分。[Problems to be Solved by the Invention] However, in Patent Document 1, although the adhesion between the polyimide film and SUS and the solder heat resistance are described, dielectric properties are not mentioned, and it is difficult to obtain a low dielectric with LCP or the like. The adhesion of the substrate film of the characteristics. Further, in Patent Document 2, although the dielectric properties and the adhesion between the polyimide film and the copper foil are described, the adhesion to the substrate film having low dielectric properties such as LCP is not mentioned. Moreover, although the heat resistance of the solder after drying is described, the heat resistance of the solder after humidification cannot be said to be sufficient.

本發明為了解決上述課題而進行深入研究的結果，發現具有特定物性之接著劑層，不僅是與以往的聚醯亞胺膜，與習知技術所未預想之LCP等具有低介電特性之樹脂基材、銅箔等金屬基材的高接著性、高焊料耐熱性、及低介電特性優異，而完成了本發明。As a result of intensive studies to solve the above problems, the present inventors have found that a binder layer having a specific physical property is not only a resin having a low dielectric property such as a conventional polyimide film and a conventionally unpredictable LCP. The metal substrate such as a substrate or a copper foil has excellent adhesion, high solder heat resistance, and low dielectric properties, and has completed the present invention.

亦即，本發明旨在提供一種疊層體，係利用對於聚醯亞胺、LCP等各種樹脂基材與金屬基材兩者具有良好接著性，且耐熱性、低介電特性亦優異之接著劑層進行疊層而成。 [解決課題之手段]In other words, the present invention has been made to provide a laminate which has excellent adhesion to various resin substrates such as polyimide and LCP and a metal substrate, and is excellent in heat resistance and low dielectric properties. The layers are laminated. [Means for solving the problem]

一種疊層體(Z)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成；其特徵為：(1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下，(2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下，(3)樹脂基材與金屬基材間的剝離強度為0.5N/mm以上，(4)疊層體(Z)之加濕焊料耐熱性為240℃以上。A laminate (Z) comprising a resin substrate and a metal substrate laminated via an adhesive comprising a carboxyl group-containing polyolefin resin (A); characterized by: (1) an adhesive layer at a frequency of 1 MHz The relative dielectric constant (ε c ) is 3.0 or less, (2) the dielectric tangent (tan δ) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, and (3) the peel strength between the resin substrate and the metal substrate is 0.5. N/mm or more, (4) The heat resistance of the solder of the laminate (Z) is 240 ° C or higher.

一種疊層體(X)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層與該樹脂基材的疊層體；其特徵為：(1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下，(2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下，(3)於疊層體(X)之接著劑層面疊層金屬基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上，(4)於疊層體(X)之接著劑層面疊層金屬基材時，該疊層體之加濕焊料耐熱性為240℃以上。A laminate (X), which is a laminate of a resin substrate and a metal substrate, which is formed by laminating a layer of an adhesive including a carboxyl group-containing polyolefin resin (A). a laminate of the resin substrate; characterized in that: (1) the dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) dielectric tangent of the adhesive layer at a frequency of 1 MHz (tan δ) is 0.02 or less, and (3) when a metal substrate is laminated on the adhesive layer of the laminate (X), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm. As described above, (4) when the metal substrate is laminated on the adhesive layer of the laminate (X), the heat resistance of the solder of the laminate is 240 ° C or higher.

一種疊層體(Y)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層與該金屬基材的疊層體；其特徵為：(1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下，(2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下，(3)於疊層體(Y)之接著劑層面疊層樹脂基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上，(4)於疊層體(Y)之接著劑層面疊層樹脂基材時，該疊層體之加濕焊料耐熱性為240℃以上。A laminate (Y) which is a laminate of a resin substrate and a metal substrate which is formed by laminating a layer of an adhesive including a carboxyl group-containing polyolefin resin (A). a laminate of the metal substrate; characterized in that: (1) the dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) dielectric tangent of the adhesive layer at a frequency of 1 MHz (tan δ) is 0.02 or less, and (3) when a resin substrate is laminated on the adhesive layer of the laminate (Y), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm. As described above, (4) when the resin substrate is laminated on the adhesive layer of the laminate (Y), the heat resistance of the solder of the laminate is 240 ° C or higher.

一種接著劑層，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層；其特徵為：(1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下，(2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下，(3)於接著劑層之其中一面疊層樹脂基材，於另一面疊層金屬基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上，(4)於接著劑層之其中一面疊層樹脂基材，於另一面疊層金屬基材時，該疊層體之加濕焊料耐熱性為240℃以上。An adhesive layer used for a laminate (Z) comprising a resin substrate and a metal substrate via an adhesive layer layer comprising a carboxyl group-containing polyolefin resin (A); (1) The relative dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) the dielectric tangent (tan δ) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, and (3) When the resin substrate is laminated on one surface of the agent layer and the metal substrate is laminated on the other surface, the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm or more, and (4) When the resin substrate is laminated on one surface of the agent layer and the metal substrate is laminated on the other surface, the heat resistance of the solder of the laminate is 240 ° C or higher.

一種接著片，含有上述疊層體(Z)、疊層體(X)、疊層體(Y)或接著劑層。A back sheet comprising the above laminate (Z), laminate (X), laminate (Y) or an adhesive layer.

一種印刷電路板，包含上述接著片作為構成要素。 [發明之效果]A printed circuit board comprising the above-described succeeding film as a constituent element. [Effects of the Invention]

本發明之係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體，由於滿足(1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下，(2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下，(3)樹脂基材與金屬基材間的剝離強度為0.5N/mm以上，(4)疊層體之加濕焊料耐熱性為240℃以上，故不僅是與以往的聚醯亞胺、聚酯膜，與習知技術所未預想之LCP膜等低極性樹脂基材或金屬基材亦具有高接著性，可獲得高焊料耐熱性，且低介電特性優異。The resin substrate and the metal substrate of the present invention are laminated on each other via an adhesive layer comprising a carboxyl group-containing polyolefin resin (A), and the relative interlayer of the (1) adhesive layer at a frequency of 1 MHz is satisfied. The electric constant (ε c ) is 3.0 or less, (2) the dielectric tangent (tan δ) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, and (3) the peel strength between the resin substrate and the metal substrate is 0.5 N/mm. As described above, (4) the moisture-absorbing solder of the laminate has a heat resistance of 240 ° C or higher, and therefore is not only a low-polarity resin substrate such as a conventional polyimide or a polyester film or an LCP film which is not expected by a conventional technique. Or the metal substrate also has high adhesion, high solder heat resistance, and excellent low dielectric properties.

以下，對本發明之實施形態進行詳細說明。本案發明之疊層體(Z)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成者。Hereinafter, embodiments of the present invention will be described in detail. The laminate (Z) of the present invention is a resin substrate and a metal substrate which are laminated via an adhesive including a carboxyl group-containing polyolefin resin (A).

＜含有羧基之聚烯烴樹脂(A)＞ 本發明所使用之含有羧基之聚烯烴樹脂(A)(以下亦簡稱為(A)成分)並無限定，宜為藉由將α,β－不飽和羧酸及其酸酐中之至少1種接枝於聚烯烴樹脂而得者較佳。聚烯烴樹脂係指例示為乙烯、丙烯、丁烯、丁二烯、異戊二烯等之烯烴單體的均聚物、或與其他單體的共聚物、及所獲得之聚合物的氫化物或鹵化物等以烴骨架為主體的聚合物。亦即，含有羧基之聚烯烴，宜為藉由將α,β－不飽和羧酸及其酸酐中之至少1種接枝於聚乙烯、聚丙烯及丙烯－α－烯烴共聚物中之至少1種而得者較佳。<Polyolefin-containing polyolefin resin (A)> The carboxyl group-containing polyolefin resin (A) (hereinafter also referred to simply as (A) component) used in the present invention is not limited, and it is preferable to make α,β-unsaturated It is preferred that at least one of the carboxylic acid and its anhydride is grafted to the polyolefin resin. The polyolefin resin refers to a homopolymer of an olefin monomer exemplified as ethylene, propylene, butylene, butadiene, isoprene or the like, or a copolymer with other monomers, and a hydride of the obtained polymer. Or a polymer such as a halide which is mainly composed of a hydrocarbon skeleton. That is, the carboxyl group-containing polyolefin is preferably at least 1 by grafting at least one of the α,β-unsaturated carboxylic acid and its anhydride to the polyethylene, the polypropylene, and the propylene-α-olefin copolymer. The kind is better.

丙烯－α－烯烴共聚物係以丙烯為主體並與α－烯烴共聚而得者。就α－烯烴而言，例如，可使用乙烯、1－丁烯、1－庚烯、1－辛烯、4－甲基－1－戊烯、乙酸乙烯酯等之1種或多種。該等α－烯烴中，乙烯、1－丁烯為較佳。丙烯－α－烯烴共聚物之丙烯成分與α－烯烴成分的比率並無限定，丙烯成分宜為50莫耳%以上較佳，70莫耳%以上更佳。The propylene-α-olefin copolymer is mainly obtained by copolymerizing propylene with an α-olefin. As the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate can be used. Among these α-olefins, ethylene and 1-butene are preferred. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, and the propylene component is preferably 50 mol% or more, more preferably 70 mol% or more.

作為α,β－不飽和羧酸及其酸酐中之至少1種，例如，可列舉馬來酸、衣康酸、檸康酸及該等之酸酐。該等中酸酐為較佳，馬來酸酐更佳。具體而言，可列舉馬來酸酐改性聚丙烯、馬來酸酐改性丙烯－乙烯共聚物、馬來酸酐改性丙烯－丁烯共聚物、馬來酸酐改性丙烯－乙烯－丁烯共聚物等，可使用該等酸改性聚烯烴之1種或2種以上組合使用。Examples of at least one of the α,β-unsaturated carboxylic acid and the acid anhydride thereof include maleic acid, itaconic acid, citraconic acid, and the like. These anhydrides are preferred, and maleic anhydride is preferred. Specific examples thereof include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene copolymer. One or a combination of two or more kinds of these acid-modified polyolefins can be used in combination.

含有羧基之聚烯烴樹脂(A)的酸值，以耐熱性及與樹脂基材或金屬基材的接著性的觀點觀之，下限宜為100當量/106 g以上較佳，200當量/106 g以上更佳，250當量/106 g尤佳。未達上述值的話，與環氧樹脂(D)、碳二亞胺樹脂(C)的相容性低，會有無法顯現接著強度的情況。又，會有交聯密度低、欠缺耐熱性的情況。上限宜為1000當量/106 g以下較佳，700當量/106 g以下更佳，500當量/106 g以下尤佳。超過上述值的話，會有接著性降低的情況。又，溶液的黏度、穩定性降低，會有適用期(pot life)縮短的情況。進一步製造效率亦降低故不佳。The acid value of the carboxyl group-containing polyolefin resin (A) is preferably 100 equivalents to 10 6 g or more, and 200 equivalents or less, in view of heat resistance and adhesion to a resin substrate or a metal substrate. More preferably 6 g or more, and 250 equivalents/10 6 g is particularly preferred. When the above value is not reached, the compatibility with the epoxy resin (D) or the carbodiimide resin (C) is low, and the bonding strength may not be exhibited. Further, there is a case where the crosslinking density is low and heat resistance is lacking. The upper limit is preferably 1000 equivalents/10 6 g or less, more preferably 700 equivalents/10 6 g or less, and particularly preferably 500 equivalents/10 6 g or less. If the value exceeds the above value, there is a case where the adhesion is lowered. Further, the viscosity and stability of the solution are lowered, and the pot life may be shortened. Further manufacturing efficiency is also reduced, which is not good.

含有羧基之聚烯烴樹脂(A)之重量平均分子量(Mw)宜為10,000～180,000之範圍較佳。20,000～160,000之範圍更佳，30,000～150,000之範圍尤佳，40,000～140,000之範圍特佳，50,000～130,000之範圍最佳。未達上述值的話，內聚力變弱，會有接著性差的情況。另一方面，超過上述值的話，流動性低，會有接著時的操作性產生問題的情況。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. The range of 20,000 to 160,000 is better, the range of 30,000 to 150,000 is particularly good, the range of 40,000 to 140,000 is particularly good, and the range of 50,000 to 130,000 is the best. If the above value is not reached, the cohesive force is weak and there is a case where the adhesion is poor. On the other hand, when the value is exceeded, the fluidity is low, and there is a case where the operability at the time of the problem arises.

含有羧基之聚烯烴樹脂(A)之製造方法並無特別限定，例如可列舉自由基接枝反應(亦即，對成為主鏈之聚合物生成自由基物種，以該自由基物種作為聚合起始點而使不飽和羧酸及酸酐進行接枝聚合反應)等。The method for producing the carboxyl group-containing polyolefin resin (A) is not particularly limited, and examples thereof include a radical graft reaction (that is, a radical species are generated for a polymer which becomes a main chain, and the radical species is used as a polymerization starting point). The unsaturated carboxylic acid and the acid anhydride are subjected to graft polymerization (such as graft polymerization).

自由基產生劑並無特別限定，宜使用有機過氧化物較佳。有機過氧化物並無特別限定，可列舉過氧化苯二甲酸二－第三丁酯、第三丁基過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化苯甲酸第三丁酯、過氧化－2－乙基己酸第三丁酯、過氧化新戊酸第三丁酯、過氧化甲乙酮、二－第三丁基過氧化物、過氧化月桂醯等過氧化物；偶氮雙異丁腈、偶氮雙異丙腈等偶氮腈類等。The radical generator is not particularly limited, and an organic peroxide is preferably used. The organic peroxide is not particularly limited, and examples thereof include di-tert-butyl peroxybenzeneate, t-butyl hydroperoxide, dicumyl peroxide, benzammonium peroxide, and benzoic acid peroxide. a butyl ester, a third butyl peroxy-2-ethylhexanoate, a third butyl peroxypivalate, a methyl ethyl ketone peroxide, a di-tert-butyl peroxide, a peroxide such as laurel; Azonitrile such as azobisisobutyronitrile or azobisisopropionitrile.

＜接著劑層＞ 本發明中，接著劑層係指將接著劑組成物塗布於基材，並使其乾燥後的接著劑組成物之層。接著劑層之厚度並無特別限定，宜為5μm以上較佳，10μm以上更佳，15μm以上尤佳。又，宜為200μm以下較佳，100μm以下更佳，50μm以下尤佳。厚度過薄時，有時會難以獲得充分的接著性能，過厚時，可列舉由於乾燥不充分，殘留溶劑容易變多，印刷電路板製造時之壓製時產生膨起的問題。<Adhesive Layer> In the present invention, the adhesive layer refers to a layer of an adhesive composition obtained by applying an adhesive composition to a substrate and drying the composition. The thickness of the layer is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more. Further, it is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less. When the thickness is too small, it may be difficult to obtain sufficient adhesion performance. When the thickness is too large, the residual solvent may be insufficient due to insufficient drying, and the film may be swollen during pressing during the production of the printed circuit board.

將接著劑組成物塗覆於基材上的方法並無特別限定，可列舉逗點式塗布機、逆轉輥式塗布機等。或必要時亦可在係印刷電路板構成材料之壓延銅箔、或聚醯亞胺膜上，直接或利用轉印法設置接著劑層。乾燥條件並無特別限定，乾燥後之殘留溶劑率宜為1質量%以下較佳。超過1質量%的話，可列舉印刷電路板壓製時殘留溶劑起泡而產生膨起的問題。The method of applying the adhesive composition to the substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater. Alternatively, the adhesive layer may be provided directly or by a transfer method on a rolled copper foil or a polyimide film which is a constituent material of the printed circuit board. The drying conditions are not particularly limited, and the residual solvent ratio after drying is preferably 1% by mass or less. When the amount is more than 1% by mass, there is a problem that the residual solvent is foamed during the pressing of the printed circuit board to cause swelling.

＜樹脂基材＞ 本發明中之樹脂基材，只要是可塗布本發明之接著劑組成物，並乾燥形成接著劑層者即可，並無特別限定，宜為膜狀樹脂等樹脂基材(以下亦稱為基材膜層)較佳。具體而言，可例示聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、液晶聚合物(LCP)、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂、及氟系樹脂等。作為LCP膜之市售品，例如，可列舉KURARAY股份有限公司製的Vecstar(註冊商標)。又，作為聚醯亞胺膜之市售品，例如，可列舉Kaneka股份有限公司製的Apical(註冊商標)。<Resin base material> The resin base material in the present invention is not particularly limited as long as it can be applied to the adhesive composition of the present invention and dried to form an adhesive layer, and is preferably a resin substrate such as a film-like resin ( Hereinafter, it is also referred to as a base film layer). Specifically, a polyester resin, a polyamide resin, a polyimide resin, a polyamidimide resin, a liquid crystal polymer (LCP), a polyphenylene sulfide, a para-polystyrene, a polyolefin system can be exemplified. Resin, fluorine resin, etc. As a commercial item of the LCP film, for example, Vecstar (registered trademark) manufactured by KURARAY Co., Ltd. can be cited. In addition, as a commercial item of a polyimine film, Apical (registered trademark) by Kaneka Co., Ltd. is mentioned, for example.

樹脂基材之厚度並無特別限定，宜為1μm以上較佳，3μm以上更佳，10μm以上尤佳。又，宜為50μm以下較佳，30μm以下更佳，20μm以下尤佳。厚度過薄時，會有電路難以獲得充分的電氣性能的情況，另一方面，厚度過厚時，會有電路製作時的加工能率等降低的情況。又，樹脂基材之相對介電常數(εc )宜為5.0以下較佳，4.0以下更佳，3.5以下尤佳。下限值並無特別限定，在工業上只要為0.1以上則無問題。The thickness of the resin substrate is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more. Further, it is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. When the thickness is too small, it may be difficult to obtain sufficient electrical performance in the circuit. On the other hand, when the thickness is too thick, the processing energy rate at the time of circuit production may be lowered. Further, the relative dielectric constant (? c ) of the resin substrate is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.5 or less. The lower limit value is not particularly limited, and it is not problematic if it is industrially 0.1 or more.

＜金屬基材＞ 就金屬基材而言，可使用能用於電路基板之任意以往公知的導電性材料。作為素材，可例示SUS、銅、鋁、鐵、鋼、鋅、鎳等各種金屬及各自的合金、鍍敷物、以鋅或鉻化合物等其他金屬進行處理的金屬等。金屬箔為較佳，銅箔更佳。金屬箔的厚度並無特別限定，宜為1μm以上較佳，3μm以上更佳，10μm以上尤佳。又，宜為50μm以下較佳，30μm以下更佳，20μm以下尤佳。厚度過薄時，會有電路難以獲得充分的電氣性能的情況，另一方面，厚度過厚時，會有電路製作時的加工能率等降低的情況。金屬箔通常係以捲軸狀的形態提供。製造本發明之印刷電路板時所使用之金屬箔的形態並無特別限定。使用帶狀形態的金屬箔時，其長度並無特別限定。又，其寬度亦無特別限定，宜為250~500cm左右較佳。<Metal substrate> As 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 alloys, plating materials, and metals treated with other metals such as zinc or chromium compounds. A metal foil is preferred, and a copper foil is preferred. The thickness of the metal foil is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more. Further, it is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. When the thickness is too small, it may be difficult to obtain sufficient electrical performance in the circuit. On the other hand, when the thickness is too thick, the processing energy rate at the time of circuit production may be lowered. The metal foil is usually provided in the form of a reel. The form of the metal foil used in the production of the printed wiring board of the present invention is not particularly limited. When a metal foil in a strip form is used, the length is not particularly limited. Further, the width thereof is not particularly limited, and is preferably about 250 to 500 cm.

＜疊層體＞ 本發明之疊層體(Z)係樹脂基材與金屬基材介由接著劑層疊層而成者(樹脂基材/接著劑層/金屬基材之3層疊層體)，疊層體(X)係樹脂基材與接著劑層疊層而成者(樹脂基材/接著劑層)，疊層體(Y)係金屬基材與接著劑層疊層而成者(金屬基材/接著劑層)。本發明中，有時將疊層體(X)、疊層體(Y)及疊層體(Z)合稱為疊層體。疊層體(X)可藉由將接著劑組成物依常規方法塗布於樹脂基材並乾燥而獲得。又，疊層體(Y)可藉由將接著劑組成物依常規方法塗布於金屬基材並乾燥而獲得。疊層體(Z)可藉由於疊層體(X)或疊層體(Y)，分別疊層金屬基材或樹脂基材而獲得。亦可於疊層體(X)或疊層體(Y)之接著劑層的面上疊層脫模基材。又，在疊層體(Z)之樹脂基材或金屬基材上進一步疊層接著劑層(接著劑層/樹脂基材/接著劑層/金屬基材、樹脂基材/接著劑層/金屬基材/接著劑層、接著劑層/樹脂基材/接著劑層/金屬基材/接著劑層)亦無妨。<Laminate> The laminate (Z)-based resin substrate of the present invention and the metal substrate are laminated with an adhesive layer (a resin laminate/adhesive layer/three-layer laminate of a metal substrate). Laminate (X)-based resin substrate and adhesive layer laminated layer (resin base material/adhesive layer), laminate (Y)-based metal substrate and adhesive layer laminated layer (metal substrate) / adhesive layer). In the present invention, the laminate (X), the laminate (Y), and the laminate (Z) may be collectively referred to as a laminate. The laminate (X) can be obtained by applying an adhesive composition to a resin substrate by a conventional method and drying. Further, the laminate (Y) can be obtained by applying the adhesive composition to a metal substrate by a conventional method and drying. The laminate (Z) can be obtained by laminating a metal substrate or a resin substrate by a laminate (X) or a laminate (Y), respectively. A release substrate may be laminated on the surface of the laminate layer of the laminate (X) or the laminate (Y). Further, an adhesive layer (adhesive layer/resin substrate/adhesive layer/metal substrate, resin substrate/adhesive layer/metal) is further laminated on the resin substrate or the metal substrate of the laminate (Z). The substrate/adhesive layer, the adhesive layer/resin substrate/adhesive layer/metal substrate/adhesive layer may also be used.

本發明之疊層體更滿足下列要件(1)～(4)。The laminate of the present invention more satisfies the following requirements (1) to (4).

＜要件(1)＞ 針對要件(1)進行說明。關於本案發明之疊層體(Z)，接著劑層之於頻率1MHz的相對介電常數(εc )3.0以下係必要。具體而言，以使乾燥後之厚度成為25μm的方式，將接著劑組成物塗布於脫模基材，並在約130℃乾燥約3分鐘。然後在約140℃熱處理約4小時而使其硬化，將硬化後之接著劑組成物層(接著劑層)從脫模膜剝離。測定剝離後之該接著劑組成物層之於頻率1MHz的相對介電常數(εc )。相對介電常數(εc )為3.0以下，2.6以下較佳，2.3以下更佳。下限並無特別限定，實用上為2.0。又，於頻率1MHz～10GHz之全區域的相對介電常數(εc )宜為3.0以下較佳，2.6以下更佳，2.3以下尤佳。<Requirements (1)> Explain the requirements (1). In the laminate (Z) of the invention of the present invention, it is necessary that the adhesive layer has a relative dielectric constant (? c ) of 3.0 or less at a frequency of 1 MHz. Specifically, the adhesive composition was applied to a release substrate so that the thickness after drying became 25 μm, and dried at about 130 ° C for about 3 minutes. Then, it is heat-treated at about 140 ° C for about 4 hours to be hardened, and the hardened adhesive composition layer (adhesive layer) is peeled off from the release film. The relative dielectric constant (? c ) of the adhesive composition layer after peeling at a frequency of 1 MHz was measured. The relative dielectric constant (? c ) is 3.0 or less, preferably 2.6 or less, and more preferably 2.3 or less. The lower limit is not particularly limited, and is practically 2.0. Further, the relative dielectric constant (? c ) of the entire region at a frequency of 1 MHz to 10 GHz is preferably 3.0 or less, more preferably 2.6 or less, and particularly preferably 2.3 or less.

疊層體(Z)中之接著劑層的相對介電常數(εc )可如下述般進行測定。亦即，可例示一種方法，係將疊層體(Z)之金屬基材用蝕刻液去除乾淨，得到接著劑層與樹脂基材之2層疊層體(X)。蝕刻液並無特別限定，可使用氯化鐵(III)水溶液、氯化銅(II)水溶液、硫酸過氧化氫水混合液、鹼蝕刻液、鎳蝕刻液等。然後，將疊層體(X)之樹脂基材剝離(去除)乾淨，於殘留的接著劑層之兩面，利用蒸鍍、濺射法等薄膜法、或塗布導電性糊劑等手法形成金屬層以作為電容器，測定靜電電容，並由厚度與面積算出相對介電常數(εc )。又，就另外的方法而言，可利用前述方法於疊層體(X)之樹脂基材面上形成金屬層以作為電容器，測定樹脂基材與接著劑層的組合靜電電容相對介電常數(εc )後，將金屬層與接著劑層從疊層體(X)剝離(去除)乾淨，同樣地電容器化並測定靜電電容，測定殘留的樹脂基材的相對介電常數(εc )。由疊層體(X)所獲得之電容器的介電層視為樹脂基材與接著劑層之多層介電體，故由兩者的差可算出接著劑層的相對介電常數(εc )。The relative dielectric constant (? c ) of the adhesive layer in the laminate (Z) can be measured as follows. In other words, a method in which the metal substrate of the laminate (Z) is removed by an etching solution to obtain a two-layer laminate (X) of the adhesive layer and the resin substrate can be exemplified. The etching liquid is not particularly limited, and an iron chloride (III) aqueous solution, a copper chloride (II) aqueous solution, a sulfuric acid hydrogen peroxide aqueous mixed solution, an alkali etching solution, a nickel etching solution, or the like can be used. Then, the resin substrate of the laminate (X) is peeled off (removed), and a metal layer is formed on both surfaces of the remaining adhesive layer by a thin film method such as vapor deposition or sputtering or a method of applying a conductive paste. The capacitance was measured as a capacitor, and the relative dielectric constant (ε c ) was calculated from the thickness and the area. Further, in another method, a metal layer can be formed on the surface of the resin substrate of the laminate (X) by the above method as a capacitor, and the combined capacitance relative dielectric constant of the resin substrate and the adhesive layer can be measured ( After ε c ), the metal layer and the adhesive layer were peeled off (removed) from the laminate (X), and the capacitance was measured in the same manner, and the capacitance was measured, and the relative dielectric constant (ε c ) of the remaining resin substrate was measured. The dielectric layer of the capacitor obtained from the laminate (X) is regarded as a multilayer dielectric of a resin substrate and an adhesive layer, so that the relative dielectric constant (ε c ) of the adhesive layer can be calculated from the difference between the two. .

＜要件(2)＞ 針對要件(2)進行說明。關於本案發明之疊層體(Z)，接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下係必要。具體而言，以使乾燥後之厚度成為25μm的方式，將接著劑組成物塗布於脫模基材，並在約130℃乾燥約3分鐘。然後在約140℃熱處理約4小時而使其硬化，將硬化後之接著劑組成物層(接著劑層)從脫模膜剝離。測定剝離後之該接著劑組成物之於頻率1MHz的介電正切(tanδ)。介電正切(tanδ)為0.02以下，0.01以下較佳，0.005以下更佳。下限並無特別限定，實用上為0.0001。又，於頻率1MHz～10GHz之全區域的介電正切(tanδ)宜為0.02以下較佳，0.01以下更佳，0.005以下尤佳。<Requirement (2)> Explain the requirements (2). In the laminate (Z) of the present invention, it is necessary that the dielectric layer has a dielectric tangent (tan δ) of 0.02 or less at a frequency of 1 MHz. Specifically, the adhesive composition was applied to a release substrate so that the thickness after drying became 25 μm, and dried at about 130 ° C for about 3 minutes. Then, it is heat-treated at about 140 ° C for about 4 hours to be hardened, and the hardened adhesive composition layer (adhesive layer) is peeled off from the release film. The dielectric tangent (tan δ) of the adhesive composition at a frequency of 1 MHz was measured after peeling. The dielectric tangent (tan δ) 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. Further, the dielectric tangent (tan δ) 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 particularly preferably 0.005 or less.

針對疊層體(Z)中之接著劑層的介電正切(tanδ)，亦可利用與上述介電常數同樣的操作進行測定。The dielectric tangent (tan δ) of the adhesive layer in the laminate (Z) can also be measured by the same operation as the above dielectric constant.

＜要件(3)＞ 針對要件(3)進行說明。關於本案發明之疊層體(Z)，樹脂基材與金屬基材間的剝離強度為0.5N/mm以上係必要。具體而言，以使乾燥後之厚度成為25μm的方式，將接著劑組成物塗布於樹脂基材，並在約130℃乾燥約3分鐘。然後於接著劑組成物層(接著劑層)的面上貼合金屬基材。貼合係以使金屬基材之光澤面與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。於常溫(約25℃)，將該疊層體(Z)之樹脂基材以拉伸速度50mm/min進行90°剝離，並測定剝離強度。90°剝離強度為0.5N/mm以上係必要，0.8N/mm以上較佳，1.0N/mm以上更佳。此外，即使是利用上述方法以外之方法製得的疊層體(Z)，只要90°剝離強度為0.5N/mm以上，即包括於本發明中。<Requirements (3)> Explain the requirements (3). In the laminate (Z) of the present invention, it is necessary that the peel strength between the resin substrate and the metal substrate is 0.5 N/mm or more. Specifically, the adhesive composition was applied to a resin substrate so that the thickness after drying became 25 μm, and dried at about 130° C. for about 3 minutes. Then, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is carried out in such a manner that the shiny side of the metal substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The resin substrate of the laminate (Z) was peeled at 90° at a tensile speed of 50 mm/min at room temperature (about 25° C.), and the peel strength was measured. It is necessary that the 90° peel strength is 0.5 N/mm or more, preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more. Further, even the laminate (Z) obtained by a method other than the above method is included in the present invention as long as the 90° peel strength is 0.5 N/mm or more.

從疊層體(X)，可藉由於疊層體(X)之接著劑組成物層(接著劑層)的面上貼合金屬基材，而獲得本發明之疊層體(Z)。貼合係以使金屬基材之光澤面與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。於常溫(約25℃)，將該疊層體(Z)之樹脂基材以拉伸速度50mm/min進行90°剝離，並測定剝離強度。90°剝離強度為0.5N/mm以上係必要，0.8N/mm以上較佳，1.0N/mm以上更佳。The laminate (Z) of the present invention can be obtained by laminating a metal substrate from the surface of the adhesive composition layer (adhesive layer) of the laminate (X) from the laminate (X). The bonding is carried out in such a manner that the shiny side of the metal substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The resin substrate of the laminate (Z) was peeled at 90° at a tensile speed of 50 mm/min at room temperature (about 25° C.), and the peel strength was measured. It is necessary that the 90° peel strength is 0.5 N/mm or more, preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more.

從疊層體(Y)，可藉由於疊層體(Y)之接著劑組成物層(接著劑層)的面上貼合樹脂基材，而獲得本發明之疊層體(Z)。貼合係以使樹脂基材與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。於常溫(約25℃)，將該疊層體(Z)之樹脂基材以拉伸速度50mm/min進行90°剝離，並測定剝離強度。90°剝離強度為0.5N/mm以上係必要，0.8N/mm以上較佳，1.0N/mm以上更佳。The laminate (Z) of the present invention can be obtained by laminating a resin substrate from the surface of the adhesive composition layer (adhesive layer) of the laminate (Y) from the laminate (Y). The bonding is carried out in such a manner that the resin substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The resin substrate of the laminate (Z) was peeled at 90° at a tensile speed of 50 mm/min at room temperature (about 25° C.), and the peel strength was measured. It is necessary that the 90° peel strength is 0.5 N/mm or more, preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more.

從接著劑層，可藉由於接著劑層之其中一面貼合樹脂基材，於另一面貼合金屬基材之光澤面，而獲得本發明之疊層體(Z)。貼合係將脫模基材/接著劑層與樹脂基材，在約100℃於約3kgf/cm2 之加壓下進行約1m/min輥層壓而貼合後，將脫模基材剝離，以使金屬基材之光澤面與接著劑層接觸的方式，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。於常溫(約25℃)，將該疊層體(Z)之樹脂基材以拉伸速度50mm/min進行90°剝離，並測定剝離強度。90°剝離強度為0.5N/mm以上係必要，0.8N/mm以上較佳，1.0N/mm以上更佳。From the adhesive layer, the laminate (Z) of the present invention can be obtained by bonding a resin substrate to one surface of the adhesive layer and bonding the shiny surface of the metal substrate to the other surface. In the bonding, the release substrate/adhesive layer and the resin substrate are subjected to roll lamination at a pressure of about 3 kgf/cm 2 at about 100 ° C for about 1 m/min, and after lamination, the release substrate is peeled off. The vacuum surface of the metal substrate is brought into contact with the adhesive layer in a vacuum at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The resin substrate of the laminate (Z) was peeled at 90° at a tensile speed of 50 mm/min at room temperature (about 25° C.), and the peel strength was measured. It is necessary that the 90° peel strength is 0.5 N/mm or more, preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more.

＜要件(4)＞ 針對要件(4)進行說明。關於本案發明之疊層體(Z)，加濕焊料耐熱性為240℃以上係必要。具體而言，以使乾燥後之厚度成為25μm的方式，將接著劑組成物塗布於樹脂基材，並約130℃乾燥約3分鐘。然後於接著劑組成物層(接著劑層)的面上貼合金屬基材。貼合係以使金屬基材之光澤面與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。將該疊層體(Z)在約40℃、約80RH%之條件下處理約72小時，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。加濕焊料耐熱性為240℃以上係必要，250℃以上較佳，260℃以上更佳。此外，即使是利用上述方法以外之方法製得的疊層體(Z)，只要加濕焊料耐熱性為240℃以上，即包括於本發明中。<Requirement (4)> Explain the requirement (4). In the laminate (Z) of the invention of the present invention, it is necessary that the heat resistance of the humidifying solder is 240 ° C or higher. Specifically, the adhesive composition was applied to a resin substrate so that the thickness after drying became 25 μm, and dried at about 130° C. for about 3 minutes. Then, a metal substrate is bonded to the surface of the adhesive composition layer (adhesive layer). The bonding is carried out in such a manner that the shiny side of the metal substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The laminate (Z) was treated under conditions of about 40 ° C and about 80 RH% for about 72 hours, and was allowed to flow in a molten solder bath at each temperature for 1 minute, and the temperature at which no change in appearance such as swelling was caused was measured. The heat resistance of the moisturizing solder is required to be 240 ° C or higher, preferably 250 ° C or higher, and more preferably 260 ° C or higher. Further, even the laminate (Z) obtained by a method other than the above method is included in the present invention as long as the heat resistance of the solder is 240 ° C or higher.

從疊層體(X)，可藉由於疊層體(X)之接著劑組成物層(接著劑層)的面上貼合金屬基材，而獲得本發明之疊層體(Z)。貼合係以使金屬基材之光澤面與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。將該疊層體(Z)在約40℃、約80RH%之條件下處理約72小時，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。加濕焊料耐熱性為240℃以上係必要，250℃以上較佳，260℃以上更佳。The laminate (Z) of the present invention can be obtained by laminating a metal substrate from the surface of the adhesive composition layer (adhesive layer) of the laminate (X) from the laminate (X). The bonding is carried out in such a manner that the shiny side of the metal substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The laminate (Z) was treated under conditions of about 40 ° C and about 80 RH% for about 72 hours, and was allowed to flow in a molten solder bath at each temperature for 1 minute, and the temperature at which no change in appearance such as swelling was caused was measured. The heat resistance of the moisturizing solder is required to be 240 ° C or higher, preferably 250 ° C or higher, and more preferably 260 ° C or higher.

從疊層體(Y)，可藉由於疊層體(Y)之接著劑組成物層(接著劑層)的面上貼合樹脂基材，而獲得本發明之疊層體(Z)。貼合係以使樹脂基材與接著劑組成物層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。將該疊層體(Z)在約40℃、約80RH%之條件下處理約72小時，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。加濕焊料耐熱性為240℃以上係必要，250℃以上較佳，260℃以上更佳。The laminate (Z) of the present invention can be obtained by laminating a resin substrate from the surface of the adhesive composition layer (adhesive layer) of the laminate (Y) from the laminate (Y). The bonding is carried out in such a manner that the resin substrate is brought into contact with the adhesive composition layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 for about 30 seconds. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The laminate (Z) was treated under conditions of about 40 ° C and about 80 RH% for about 72 hours, and was allowed to flow in a molten solder bath at each temperature for 1 minute, and the temperature at which no change in appearance such as swelling was caused was measured. The heat resistance of the moisturizing solder is required to be 240 ° C or higher, preferably 250 ° C or higher, and more preferably 260 ° C or higher.

又，從接著劑層，可藉由於接著劑層之其中一面貼合樹脂基材，於另一面貼合金屬基材之光澤面，而獲得本發明之疊層體(Z)。貼合係將接著劑層與樹脂基材貼合後，以使金屬基材之光澤面與接著劑層接觸的方式進行，在約160℃於約40kgf/cm2 之加壓下真空壓製約30秒而接著。然後在約140℃熱處理約4小時而使其硬化，製作樹脂基材/接著劑層/金屬基材之3層疊層體(Z)。將該疊層體(Z)在約40℃、約80RH%之條件下處理約72小時，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。加濕焊料耐熱性為240℃以上係必要，250℃以上較佳，260℃以上更佳。Further, from the adhesive layer, the laminate (Z) of the present invention can be obtained by bonding the resin substrate to one surface of the adhesive layer and bonding the shiny surface of the metal substrate to the other surface. After bonding, the adhesive layer is bonded to the resin substrate, and the shiny surface of the metal substrate is brought into contact with the adhesive layer, and vacuum-pressed at about 160 ° C under a pressure of about 40 kgf / cm 2 . Seconds and then. Then, it was heat-treated at about 140 ° C for about 4 hours to be hardened to prepare a three-layer laminate (Z) of a resin substrate / an adhesive layer / a metal substrate. The laminate (Z) was treated under conditions of about 40 ° C and about 80 RH% for about 72 hours, and was allowed to flow in a molten solder bath at each temperature for 1 minute, and the temperature at which no change in appearance such as swelling was caused was measured. The heat resistance of the moisturizing solder is required to be 240 ° C or higher, preferably 250 ° C or higher, and more preferably 260 ° C or higher.

＜接著劑組成物＞ 本發明所使用之接著劑組成物，係至少包括含有羧基之聚烯烴樹脂(A)者。藉由包括含有羧基之聚烯烴樹脂(A)，介由由該接著劑組成物所構成之接著劑層而成的疊層體可顯現上述(1)～(4)之優異性能。<Adhesive Composition> The adhesive composition used in the present invention is a polyolefin resin (A) containing at least a carboxyl group. The laminates comprising the carboxyl group-containing polyolefin resin (A) and the adhesive layer composed of the adhesive composition can exhibit the excellent properties of the above (1) to (4).

本發明之接著劑組成物，除上述(A)成分以外，宜包括含有羧基之苯乙烯樹脂(B)(以下亦簡稱為(B)成分。)、碳二亞胺樹脂(C)(以下亦簡稱為(C)成分。)及/或環氧樹脂(D)(以下亦簡稱為(D)成分。)較佳。藉由包括上述(A)成分～(D)成分之4種樹脂，不僅是與以往的聚醯亞胺、聚酯膜，與習知技術所未預想之LCP膜等低極性樹脂基材、金屬基材亦具有高接著性，可獲得高焊料耐熱性，且低介電特性優異。In addition to the above component (A), the adhesive composition of the present invention preferably includes a styrene resin (B) having a carboxyl group (hereinafter also referred to simply as a component (B)), and a carbodiimide resin (C) (hereinafter also It is preferably referred to as (C) component.) and/or epoxy resin (D) (hereinafter also referred to simply as component (D).). The four kinds of resins including the components (A) to (D) described above are not only low-polar resin substrates and metals such as LCP films which are not expected from conventional polyimides and polyester films, and which are not contemplated by the prior art. The substrate also has high adhesion, high solder heat resistance, and excellent low dielectric properties.

＜含有羧基之苯乙烯樹脂(B)＞ 本發明可使用之含有羧基之苯乙烯樹脂(B)並無限定，宜為將芳香族乙烯基化合物單獨、或芳香族乙烯基化合物與共軛二烯化合物之以嵌段及/或無規結構為主體的共聚物、及其氫化物以不飽和羧酸進行改性而得者較佳。芳香族乙烯基化合物並無特別限定，例如可列舉苯乙烯、第三丁基苯乙烯、α－甲基苯乙烯、對甲基苯乙烯、二乙烯基苯、1,1－二苯基苯乙烯、N,N－二乙基－對胺基乙基苯乙烯、乙烯基甲苯、對第三丁基苯乙烯等。又，作為共軛二烯化合物，例如，可列舉丁二烯、異戊二烯、1,3－戊二烯、2,3－二甲基－1,3－丁二烯等。該等芳香族乙烯基化合物與共軛二烯化合物之共聚物的具體例，可列舉苯乙烯－乙烯－丁烯－苯乙烯嵌段共聚物(SEBS)、苯乙烯－乙烯－丙烯－苯乙烯嵌段共聚物(SEPS)、苯乙烯－乙烯－乙烯・丙烯－苯乙烯嵌段共聚物(SEEPS)等。<Carboxyl group-containing styrene resin (B)> The carboxy group-containing styrene resin (B) which can be used in the invention is not limited, and it is preferred to use an aromatic vinyl compound alone or an aromatic vinyl compound and a conjugated diene. It is preferred that the compound is a copolymer mainly composed of a block and/or a random structure, and a hydride thereof is modified with an unsaturated carboxylic acid. The aromatic vinyl compound is not particularly limited, and examples thereof include styrene, t-butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, and 1,1-diphenyl styrene. , N,N-diethyl-p-aminoethylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. Further, examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. Specific examples of the copolymer of the aromatic vinyl compound and the conjugated diene compound include styrene-ethylene-butylene-styrene block copolymer (SEBS) and styrene-ethylene-propylene-styrene embedded. Segment copolymer (SEPS), styrene-ethylene-ethylene, propylene-styrene block copolymer (SEEPS), and the like.

含有羧基之苯乙烯樹脂(B)的改性，例如，可藉由於苯乙烯樹脂的聚合時，使不飽和羧酸共聚而進行。又，亦可藉由將苯乙烯樹脂與不飽和羧酸在有機過氧化物的存在下加熱、混練而進行。不飽和羧酸並無特別限定，可列舉丙烯酸、甲基丙烯酸、馬來酸、衣康酸、富馬酸、馬來酸酐、衣康酸酐、富馬酸酐等。The modification of the carboxyl group-containing styrene resin (B) can be carried out, for example, by copolymerizing an unsaturated carboxylic acid during polymerization of a styrene resin. Further, it can be carried out by heating and kneading a styrene resin and an unsaturated carboxylic acid in the presence of an organic peroxide. 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.

含有羧基之苯乙烯樹脂(B)的酸值，以耐熱性及與樹脂基材或金屬基材的接著性的觀點觀之，下限宜為10當量/106 g以上較佳，100當量/106 g以上更佳，150當量/106 g尤佳。未達上述值的話，與環氧樹脂(D)、碳二亞胺樹脂(C)的相容性低，會有無法顯現接著強度的情況。又，會有交聯密度低、欠缺耐熱性的情況。上限宜為1000當量/106 g以下較佳，700當量/106 g以下更佳，500當量/106 g以下尤佳。超過上述值的話，會有接著性、低介電特性降低的情況。The acid value of the carboxyl group-containing styrene resin (B) is preferably 10 equivalents/10 6 g or more, and 100 equivalents or less, in view of heat resistance and adhesion to a resin substrate or a metal substrate. More preferably 6 g or more, and 150 equivalents/10 6 g is particularly preferred. When the above value is not reached, the compatibility with the epoxy resin (D) or the carbodiimide resin (C) is low, and the bonding strength may not be exhibited. Further, there is a case where the crosslinking density is low and heat resistance is lacking. The upper limit is preferably 1000 equivalents/10 6 g or less, more preferably 700 equivalents/10 6 g or less, and particularly preferably 500 equivalents/10 6 g or less. When the value exceeds the above value, there is a case where the adhesion and the low dielectric property are lowered.

本發明所使用之接著劑組成物中，就含有羧基之苯乙烯樹脂(B)的含量而言，相對於含有羧基之聚烯烴樹脂(A)5～95質量份，宜為含有羧基之苯乙烯樹脂(B)95～5質量份之範圍，亦即(A)成分/(B)成分＝5～95/95～5(質量比)較佳。(A)成分/(B)成分10～90/90～10(質量比)更佳，(A)成分/(B)成分＝15～85/85～15(質量比)之範圍最佳。(A)成分量未達上述值的話，交聯密度降低，會有加濕焊料耐熱性降低的情況。(A)成分量超過上述值的話，對於基材的潤濕性降低，會有接著強度降低的情況。In the adhesive composition used in the present invention, the content of the carboxyl group-containing styrene resin (B) is preferably carboxy group-containing styrene in an amount of 5 to 95 parts by mass based on the carboxyl group-containing polyolefin resin (A). The range of 95 to 5 parts by mass of the resin (B), that is, the component (A)/component (B) = 5 to 95/95 to 5 (mass ratio) is preferred. The component (A)/component (B) is preferably 10 to 90/90 to 10 (mass ratio), and the range of (A) component/(B) component = 15 to 85/85 to 15 (mass ratio) is optimal. When the amount of the component (A) is less than the above value, the crosslinking density is lowered, and the heat resistance of the moisturizing solder may be lowered. When the amount of the component (A) exceeds the above value, the wettability of the substrate may be lowered, and the subsequent strength may be lowered.

＜碳二亞胺樹脂(C)＞ 碳二亞胺樹脂(C)只要是於分子內具有碳二亞胺基者即可，並無特別限定。於分子內具有2個以上之碳二亞胺基的聚碳二亞胺較佳。藉由使用碳二亞胺樹脂(C)，含有羧基之聚烯烴樹脂(A)或含有羧基之苯乙烯樹脂(B)的羧基與碳二亞胺反應，可提高接著劑組成物與基材的相互作用，並可改善接著性。<Carbodiimide Resin (C)> The carbodiimide resin (C) is not particularly limited as long as it has a carbodiimide group in the molecule. A polycarbodiimide having two or more carbodiimide groups in the molecule is preferred. By using a carbodiimide resin (C), a carboxyl group-containing polyolefin resin (A) or a carboxyl group-containing styrene resin (B) carboxyl group is reacted with a carbodiimide to improve the composition of the adhesive and the substrate. Interaction and improved adhesion.

本發明所使用之接著劑組成物中，碳二亞胺樹脂(C)的含量，相對於含有羧基之聚烯烴樹脂(A)與含有羧基之苯乙烯樹脂(B)之合計100質量份，宜為0.1～30質量份之範圍較佳。1～25質量份之範圍更佳，2～20質量份之範圍最佳。未達上述值的話，不能顯現與基材的相互作用，會有接著性降低的問題。超過上述值的話，會有接著劑的適用期縮短、低介電特性降低的問題。In the adhesive composition used in the present invention, the content of the carbodiimide resin (C) is preferably 100 parts by mass based on the total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B). It is preferably in the range of 0.1 to 30 parts by mass. The range of 1 to 25 parts by mass is more preferably, and the range of 2 to 20 parts by mass is the best. If the above value is not reached, the interaction with the substrate cannot be exhibited, and there is a problem that the adhesion is lowered. When the value exceeds the above value, there is a problem that the pot life of the adhesive is shortened and the low dielectric property is lowered.

＜環氧樹脂(D)＞ 環氧樹脂(D)只要是於分子中具有環氧丙基者即可，並無特別限定，宜為於分子中具有2個以上之環氧丙基者較佳。具體而言雖無特別限定，但可使用選自於由聯苯基型環氧樹脂、萘型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛型環氧樹脂、脂環族環氧樹脂、二環戊二烯型環氧樹脂、四環氧丙基二胺基二苯基甲烷、三環氧丙基對胺基苯酚、四環氧丙基雙胺基甲基環己酮、N,N,N’,N’－四環氧丙基－間二甲苯二胺構成之群組中之至少1種。宜為雙酚A型環氧樹脂、酚醛型環氧樹脂或二環戊二烯型環氧樹脂較佳。<Epoxy Resin (D)> The epoxy resin (D) is not particularly limited as long as it has an epoxy propyl group in the molecule, and it is preferred to have two or more epoxy propyl groups in the molecule. . Specifically, it is not particularly limited, but may be selected from biphenyl type epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and novolac type epoxy resins. , alicyclic epoxy resin, dicyclopentadiene type epoxy resin, tetraepoxypropyl diaminodiphenylmethane, triepoxypropyl p-aminophenol, tetraepoxypropyl diamine At least one of the group consisting of cyclohexanone, N, N, N', N'-tetraepoxypropyl-m-xylylenediamine. It is preferably a bisphenol A type epoxy resin, a novolac type epoxy resin or a dicyclopentadiene type epoxy resin.

本發明所使用之接著劑組成物中，環氧樹脂(D)的含量，相對於含有羧基之聚烯烴樹脂(A)與含有羧基之苯乙烯樹脂(B)之合計100質量份，宜為1～30質量份之範圍較佳，2～15質量份之範圍更佳，3～10質量份之範圍最佳。未達上述範圍的話，會有不能獲得充分的硬化效果、接著性及耐熱性降低的情況。又，為上述範圍以上的話，會有接著劑的適用期縮短、低介電特性降低的問題。In the adhesive composition used in the present invention, the content of the epoxy resin (D) is preferably 1 part by mass based on 100 parts by mass of the total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B). The range of ～30 parts by mass is more preferably in the range of 2 to 15 parts by mass, and the range of 3 to 10 parts by mass is most preferable. If it is less than the above range, sufficient hardening effect, adhesiveness, and heat resistance may not be obtained. Moreover, when it is more than the above range, there is a problem that the pot life of the adhesive is shortened and the low dielectric property is lowered.

本發明所使用之接著劑組成物，進一步可含有有機溶劑。就本發明所使用之有機溶劑而言，只要是可使含有羧基之聚烯烴樹脂(A)、含有羧基之苯乙烯樹脂(B)、碳二亞胺樹脂(C)、及環氧樹脂(D)溶解者即可，並無特別限定。具體而言，例如，可使用苯、甲苯、二甲苯等芳香族烴；己烷、庚烷、辛烷、癸烷等脂肪族系烴；環己烷、環己烯、甲基環己烷、乙基環己烷等脂環族烴；三氯乙烯、二氯乙烯、氯苯、氯仿等鹵化烴；甲醇、乙醇、異丙醇、丁醇、戊醇、己醇、丙二醇、苯酚等醇系溶劑；丙酮、甲基異丁酮、甲乙酮、戊酮、己酮、環己酮、異佛酮、苯乙酮等酮系溶劑；甲基賽珞蘇、乙基賽珞蘇等賽珞蘇類；乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、甲酸丁酯等酯系溶劑；乙二醇單正丁醚、乙二醇單異丁醚、乙二醇單第三丁醚、二乙二醇單正丁醚、二乙二醇單異丁醚、三乙二醇單正丁醚、四乙二醇單正丁醚等二醇醚系溶劑等，可使用該等中之1種或2種以上倂用。The adhesive composition used in the present invention may further contain an organic solvent. The organic solvent used in the present invention is a polyolefin resin (A) containing a carboxyl group, a styrene resin (B) containing a carboxyl group, a carbodiimide resin (C), and an epoxy resin (D). The solvent is not particularly limited. Specifically, for example, an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as hexane, heptane, octane or decane; cyclohexane, cyclohexene or methylcyclohexane; Alicyclic hydrocarbons such as ethylcyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, chloroform; alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenol Solvent; ketone solvent such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, ketone, cyclohexanone, isophorone, acetophenone; methyl acesulfame, ethyl cyanidin, etc. Ethyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate and other ester solvents; ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-tert-butyl ether And glycol ether solvent such as diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, etc., etc. One type or two or more types are used.

就有機溶劑而言，相對於含有羧基之聚烯烴樹脂(A)與含有羧基之苯乙烯樹脂(B)之合計100質量份，宜為100～1000質量份之範圍較佳，200～900質量份之範圍更佳，300～800質量份之範圍最佳。未達上述範圍的話，會有液體性及適用期特性降低的情況。又，超過上述範圍的話，會有在製造成本、輸送成本的方面變得不利的問題。The organic solvent is preferably in the range of 100 to 1000 parts by mass, and preferably 200 to 900 parts by mass, based on 100 parts by mass of the total of the carboxyl group-containing polyolefin resin (A) and the carboxyl group-containing styrene resin (B). The range is better, and the range of 300 to 800 parts by mass is the best. If the above range is not reached, there will be a case where the liquidity and the pot life characteristics are lowered. Moreover, if it exceeds the above range, there is a problem that it is disadvantageous in terms of manufacturing cost and transportation cost.

又，於本發明所使用之接著劑組成物中，必要時亦可進一步含有其他成分。該等成分的具體例，可列舉阻燃劑、黏接性賦予劑、填料、矽烷偶聯劑。Further, the adhesive composition used in the present invention may further contain other components as necessary. Specific examples of the components include a flame retardant, an adhesion-imparting agent, a filler, and a decane coupling agent.

＜阻燃劑＞ 於本發明所使用之接著劑組成物中，必要時亦可摻合阻燃劑。作為阻燃劑，可列舉溴系、磷系、氮系、氫氧化金屬化合物等。其中，磷系阻燃劑較佳，例如可使用磷酸三甲酯、磷酸三苯酯、磷酸三甲苯酯等磷酸酯；次磷酸鋁等磷酸鹽、磷腈等公知的磷系阻燃劑。該等可單獨使用，亦可將2種以上任意組合使用。含有阻燃劑時，相對於(A)～(D)成分之合計100質量份，以1～200質量份之範圍含有阻燃劑較佳，5～150質量份之範圍更佳，10～100質量份之範圍最佳。未達上述範圍的話，會有阻燃性低的情況。超過上述範圍的話，會有接著性、耐熱性、電氣特性等惡化的問題。<Flame Retardant> In the adhesive composition used in the present invention, a flame retardant may be blended as necessary. Examples of the flame retardant include a bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compound. Among them, a phosphorus-based flame retardant is preferable, and for example, a phosphate ester such as trimethyl phosphate, triphenyl phosphate or tricresyl phosphate; a phosphate such as aluminum hypophosphite or a known phosphorus-based flame retardant such as phosphazene can be used. These may be used alone or in combination of two or more. When the flame retardant is contained, the flame retardant is preferably contained in an amount of from 1 to 200 parts by mass, more preferably from 5 to 150 parts by mass, based on 100 parts by mass of the total of the components (A) to (D), and more preferably from 10 to 100 parts by weight. The range of quality parts is the best. If the above range is not reached, there is a case where the flame retardancy is low. When it exceeds the above range, there is a problem that the adhesion, heat resistance, electrical characteristics, and the like are deteriorated.

＜黏接性賦予劑＞ 於本發明所使用之接著劑組成物中，必要時亦可摻合黏接性賦予劑。黏接性賦予劑，可列舉聚萜烯樹脂、松香系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、共聚系石油樹脂、苯乙烯樹脂及氫化石油樹脂等，係為了提高接著強度而使用。該等可單獨使用，亦可將2種以上任意組合使用。<Adhesiveness-imparting agent> In the adhesive composition used in the present invention, an adhesion-imparting agent may be blended as necessary. Examples of the adhesiveness-imparting agent include a polyterpene resin, a rosin-based resin, an aliphatic petroleum resin, an alicyclic petroleum resin, a copolymerized petroleum resin, a styrene resin, and a hydrogenated petroleum resin, etc., in order to improve the bonding strength. use. These may be used alone or in combination of two or more.

＜填料＞ 於本發明所使用之接著劑組成物中，必要時亦可摻合二氧化矽等填料。藉由摻合二氧化矽，耐熱性之特性得到改善，故非常理想。就二氧化矽而言，一般已知有疏水性二氧化矽與親水性二氧化矽，此處為了賦予耐吸濕性，宜為以二甲基二氯矽烷、或六甲基二矽氮烷、辛基矽烷等進行處理之疏水性二氧化矽。二氧化矽的摻合量，相對於(A)～(D)成分之合計100質量份宜為0.05~30質量份之摻合量較佳。未達0.05質量份的話，會有無法發揮使耐熱性提高的效果的情況。另一方面，超過30質量份的話，會有發生二氧化矽的分散不良、溶液黏度變得過高而作業性產生不便、或接著性降低的情況。<Filler> In the adhesive composition used in the present invention, a filler such as cerium oxide may be blended as necessary. It is highly desirable to improve the heat resistance by blending cerium oxide. As the cerium oxide, hydrophobic cerium oxide and hydrophilic cerium oxide are generally known, and in order to impart moisture absorption resistance, it is preferred to use dimethyldichloromethane or hexamethyldioxane. Hydrophobic cerium oxide treated with octyl decane or the like. The blending amount of the cerium oxide is preferably 0.05 to 30 parts by mass based on 100 parts by mass of the total of the components (A) to (D). When it is less than 0.05 part by mass, the effect of improving heat resistance may not be exhibited. On the other hand, when the amount is more than 30 parts by mass, the dispersion of cerium oxide may occur, the viscosity of the solution may become too high, workability may be inconvenient, or the adhesion may be lowered.

＜矽烷偶聯劑＞ 於本發明所使用之接著劑組成物中，必要時亦可摻合矽烷偶聯劑。藉由摻合矽烷偶聯劑，對於金屬的接著性或耐熱性之特性得到改善，故非常理想。矽烷偶聯劑並無特別限定，可列舉具有不飽和基者、具有環氧丙基者、具有胺基者等。該等中以耐熱性的觀點觀之，γ－環氧丙氧基丙基三甲氧基矽烷、β－(3,4－環氧環己基)乙基三甲氧基矽烷、β－(3,4－環氧環己基)乙基三乙氧基矽烷等具有環氧丙基的矽烷偶聯劑更佳。矽烷偶聯劑的摻合量，相對於(A)～(D)成分之合計100質量份宜為0.5～20質量份之摻合量較佳。未達0.5質量份的話，會有耐熱性變得不良的情況。另一方面，超過20質量份的話，會有耐熱性不良或接著性降低的情況。<Hydrane coupling agent> In the adhesive composition used in the present invention, a decane coupling agent may be blended as necessary. It is highly desirable to improve the properties of the adhesion or heat resistance of the metal by blending the decane coupling agent. The decane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having an epoxy group, and those having an amine group. Among these, from the viewpoint of heat resistance, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β-(3,4) A decane coupling agent having a glycidyl group such as epoxycyclohexyl)ethyltriethoxydecane is more preferable. The blending amount of the decane coupling agent is preferably from 0.5 to 20 parts by mass based on 100 parts by mass of the total of the components (A) to (D). When it is less than 0.5 part by mass, heat resistance may become unfavorable. On the other hand, when it exceeds 20 parts by mass, the heat resistance may be poor or the adhesion may be lowered.

＜接著片＞ 本發明中，接著片係將上述疊層體(Z)與脫模基材介由接著劑組成物疊層而成者、或於疊層體(X)或疊層體(Y)之接著劑層面疊層脫模基材而成者、或於接著劑層之至少其中一面疊層脫模基材而成者。具體的構成態樣，可列舉脫模基材/接著劑層、脫模基材/接著劑層/脫模基材、樹脂基材/接著劑層/脫模基材、金屬基材/接著劑層/脫模基材、疊層體/接著劑層/脫模基材、或脫模基材/接著劑層/疊層體/接著劑層/脫模基材。藉由疊層脫模基材，可發揮作為基材之保護層的功能。又，藉由使用脫模基材，可將脫模基材從接著片脫模，而將接著劑層轉印至另外的基材。<Continuous sheet> In the present invention, the laminate (Z) and the release substrate are laminated via the adhesive composition, or in the laminate (X) or laminate (Y). The laminate layer is formed by laminating a release substrate or laminating a release substrate on at least one of the adhesive layers. Specific examples of the composition include a release substrate/adhesive layer, a release substrate/adhesive layer/release substrate, a resin substrate/adhesive layer/release substrate, and a metal substrate/adhesive agent. Layer/release substrate, laminate/adhesive layer/release substrate, or release substrate/adhesive layer/laminate/adhesive layer/release substrate. By laminating the release substrate, the function as a protective layer of the substrate can be exhibited. Further, by using a release substrate, the release substrate can be released from the release sheet, and the adhesive layer can be transferred to another substrate.

藉由將本發明所使用之接著劑組成物，依常規方法塗布於各種疊層體並乾燥，可獲得本發明之接著片。又，乾燥後將脫模基材貼附於接著劑層的話，可不造成朝基材背面的轉移而進行捲繞，作業性優異，同時接著劑層受到保護，故保存性優異，使用亦容易。又，塗布於脫模基材並乾燥後，視需要貼附另外的脫模基材的話，亦可將接著劑層其本身轉印至其他基材。The adhesive sheet of the present invention can be obtained by applying the adhesive composition used in the present invention to various laminates by a conventional method and drying. In addition, when the release substrate is attached to the adhesive layer after drying, the film can be wound without causing migration to the back surface of the substrate, and the workability is excellent, and the adhesive layer is protected, so that the storage property is excellent and the use is easy. Further, after application to the release substrate and drying, if another release substrate is attached as needed, the adhesive layer itself may be transferred to another substrate.

＜脫模基材＞ 脫模基材並無特別限定，例如，可列舉於優質紙、牛皮紙、捲紙、玻璃紙等紙的兩面，設置黏土、聚乙烯、聚丙烯等填平劑的塗布層，進一步在其各塗布層之上塗布矽酮系、氟系、醇酸系脫模劑而成者。又，亦可列舉於聚乙烯、聚丙烯、乙烯－α－烯烴共聚物、丙烯－α－烯烴共聚物等各種烯烴膜單獨、及聚對苯二甲酸乙二酯等膜上塗布上述脫模劑而成者。由於脫模基材與接著劑層間的脫模力、矽酮會對電氣特性造成不良影響等理由，宜為於優質紙之兩面進行聚丙烯填平處理並於其上使用醇酸系脫模劑者、或於聚對苯二甲酸乙二酯上使用醇酸系脫模劑者較佳。<Release base material> The mold release base material is not particularly limited, and examples thereof include a coating layer of a filler such as clay, polyethylene, or polypropylene on both sides of paper such as high-quality paper, kraft paper, roll paper, and cellophane. Further, an anthrone-based, fluorine-based or alkyd-based release agent is coated on each of the coating layers. Further, the above-mentioned release agent may be applied to various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and the like, and a film such as polyethylene terephthalate. Founder. Due to the release force between the release substrate and the adhesive layer, and the adverse effects of the fluorenone on the electrical properties, it is preferable to carry out the polypropylene filling treatment on both sides of the high-quality paper and use the alkyd-based release agent thereon. It is preferred to use an alkyd-based release agent on polyethylene terephthalate.

＜印刷電路板＞ 本發明中之「印刷電路板」，係包含由形成導體電路之金屬箔與樹脂基材所形成的疊層體作為構成要素者。印刷電路板，例如，可使用覆金屬疊層體並利用減去(subtractive)法等以往公知的方法製造。係必要時將由金屬箔形成的導體電路部分性或全面性地使用表覆膜、網版印刷印墨等被覆之所謂撓性電路板(FPC)、扁平電纜、捲帶式自動接合(TAB)用電路板等的總稱。<Printed Circuit Board> The "printed circuit board" in the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin substrate as a constituent element. The printed circuit board can be produced, for example, by a conventionally known method such as a subtractive method using a metal-clad laminate. A so-called flexible circuit board (FPC), a flat cable, and a tape-type automatic bonding (TAB) which are partially or comprehensively coated with a surface film or a screen printing ink, if necessary, partially or comprehensively. A general term for boards and the like.

本發明之印刷電路板，可為能被採用作為印刷電路板之任意的疊層構成。例如，可為由基材膜層、金屬箔層、接著劑層及表覆膜層之4層所構成的印刷電路板。又，例如可為由基材膜層、接著劑層、金屬箔層、接著劑層及表覆膜層之5層所構成的印刷電路板。The printed circuit board of the present invention can be constructed as any laminate that can be used as a printed circuit board. For example, it may be a printed circuit board composed of four layers of a base film layer, a metal foil layer, an adhesive layer, and a surface coating layer. Further, for example, it may be a printed circuit board comprising five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a surface coating layer.

進一步，必要時亦可為將2個或3個以上之上述印刷電路板疊層而得的構成。Further, if necessary, a configuration may be adopted in which two or more of the above printed circuit boards are laminated.

本發明所使用之接著劑組成物適合使用於印刷電路板之各接著劑層。特別是將本發明所使用之接著劑組成物作為接著劑使用的話，不僅是與構成印刷電路板之以往的聚醯亞胺、聚酯膜、銅箔，與LCP等低極性的樹脂基材亦具有高接著性，可獲得耐焊料回焊性，且接著劑層自身低介電特性優異。因此，適合作為表覆層膜、疊層板、附樹脂之銅箔及黏合片所使用之接著劑組成物。The adhesive composition used in the present invention is suitable for use in each of the adhesive layers of a printed circuit board. In particular, when the adhesive composition used in the present invention is used as an adhesive, it is not only a conventional resin substrate such as a polyimine, a polyester film, a copper foil or an LCP which constitutes a printed circuit board. With high adhesion, solder reflow resistance can be obtained, and the adhesive layer itself is excellent in low dielectric properties. Therefore, it is suitable as a binder composition used for a cover film, a laminated board, a copper foil with a resin, and an adhesive sheet.

本發明之印刷電路板中，就基材膜而言，可使用自以往既已作為印刷電路板之基材而使用之任意的樹脂膜。作為基材膜之樹脂，可例示聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂、及氟系樹脂等。特別是即使對於液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂等的低極性基材，亦具有優異的接著性。In the printed circuit board of the present invention, any resin film which has been conventionally used as a substrate of a printed circuit board can be used as the base film. The resin of the base film may, for example, be a polyester resin, a polyamide resin, a polyimide resin, a polyamide amide resin, a liquid crystal polymer, a polyphenylene sulfide, a para-polystyrene, or a polyolefin. Resin, fluorine resin, etc. In particular, it has excellent adhesion to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, para-polystyrene, and polyolefin-based resins.

＜表覆膜＞ 就表覆膜而言，可使用以往公知的任意絕緣膜作為印刷電路板用之絕緣膜。例如，可使用由聚醯亞胺、聚酯、聚苯硫醚、聚醚碸、聚醚醚酮、芳香族聚醯胺、聚碳酸酯、聚芳酯、聚醯亞胺、聚醯胺醯亞胺、液晶聚合物、對排聚苯乙烯、聚烯烴系樹脂等各種聚合物所製成的膜。聚醯亞胺膜或液晶聚合物膜為更佳。<Table Film> As the surface film, any conventionally known insulating film can be used as the insulating film for a printed circuit board. For example, polyimine, polyester, polyphenylene sulfide, polyether oxime, polyetheretherketone, aromatic polyamine, polycarbonate, polyarylate, polyimine, polyamidoxime can be used. A film made of various polymers such as an imine, a liquid crystal polymer, a pair of polystyrene, and a polyolefin resin. A polyimide film or a liquid crystal polymer film is more preferable.

本發明之印刷電路板，除使用上述各層之材料以外，可使用以往公知的任意製程進行製造。The printed circuit board of the present invention can be produced by any conventionally known process except for using the materials of the above layers.

較佳之實施態様係製造於表覆膜層疊層接著劑層而成的半成品(以下稱為「表覆膜側半成品」)。另一方面，係製造於基材膜層疊層金屬箔層並形成所期望之電路圖案的半成品(以下稱為「基材膜側2層半成品」)、或於基材膜層疊層接著劑層且於其上疊層金屬箔層並形成所期望之電路圖案的半成品(以下稱為「基材膜側3層半成品」)(以下將基材膜側2層半成品與基材膜側3層半成品合稱為「基材膜側半成品」)。藉由將以此種方式所獲得之表覆膜側半成品與基材膜側半成品貼合，可獲得4層或5層之印刷電路板。In a preferred embodiment, the product is a semi-finished product (hereinafter referred to as "surface film side semi-finished product") which is produced by laminating a laminate layer. On the other hand, it is a semi-finished product (hereinafter referred to as "substrate film side two-layer semi-finished product") which is formed on a base film laminated metal foil layer to form a desired circuit pattern, or a base film laminated layer of an adhesive layer. A semi-finished product in which a metal foil layer is laminated thereon to form a desired circuit pattern (hereinafter referred to as "substrate film side three-layer semi-finished product") (hereinafter, the base film side two-layer semi-finished product and the base film side three-layer semi-finished product are combined It is called "substrate film side semi-finished product"). By bonding the surface-coated semi-finished product obtained in this manner to the base film-side semi-finished product, a 4-layer or 5-layer printed circuit board can be obtained.

基材膜側半成品，例如，可藉由包括以下步驟之製造方法而獲得：(A)於上述金屬箔塗布成為基材膜之樹脂的溶液，並將塗膜進行初步乾燥的步驟；(B)將(A)中所獲得之金屬箔與初步乾燥塗膜的疊層物進行熱處理・乾燥的步驟(以下稱為「熱處理・脫溶劑步驟」)。The base film side semi-finished product can be obtained, for example, by a production method including the following steps: (A) a step of applying a solution of the metal foil to the resin of the base film and preliminary drying the coating film; (B) The step of heat-treating and drying the laminate of the metal foil obtained in (A) and the preliminary dried coating film (hereinafter referred to as "heat treatment and solvent removal step").

金屬箔層中之電路的形成，可使用以往公知的方法。可使用加成法(additive)，亦可使用減去法。減去法為較佳。A conventionally known method can be used for forming the circuit in the metal foil layer. Additives can be used, and subtractive methods can also be used. The subtraction method is preferred.

所獲得之基材膜側半成品，可直接使用在與表覆膜側半成品之貼合，又，亦可貼合脫模膜進行保存後，使用在與表覆膜側半成品之貼合。The obtained base film side semi-finished product can be directly used for bonding to the semi-finished product on the surface of the cover film, or can be attached to the semi-finished product on the side of the cover film after being adhered to the release film.

表覆膜側半成品，例如，可於表覆膜塗布接著劑而製造。必要時，可進行所塗布之接著劑中的交聯反應。較佳實施態様中，係使接著劑層半硬化。The film-side semi-finished product can be produced, for example, by applying an adhesive to a surface film. If necessary, a crosslinking reaction in the applied adhesive can be carried out. In a preferred embodiment, the adhesive layer is semi-hardened.

所獲得之表覆膜側半成品，可直接使用在與基材膜側半成品之貼合，又，亦可貼合脫模膜進行保存後，使用在與基材膜側半成品之貼合。The obtained film-side semi-finished product can be directly used for bonding to the base film side semi-finished product, or can be bonded to the release film and stored, and then bonded to the base film side semi-finished product.

基材膜側半成品與表覆膜側半成品，係分別例如以捲軸的形態保存後，進行貼合而製成印刷電路板。就貼合方法而言，可使用任意的方法，例如可使用壓製或滾軸等進行貼合。又，亦可藉由加熱壓製或使用加熱滾軸裝置等方法，邊加熱邊將兩者貼合。The base film side semi-finished product and the surface film side semi-finished product are respectively stored in the form of a reel, and then bonded to form a printed circuit board. As the bonding method, any method can be used, for example, pressing or rolling can be used for lamination. Further, it is also possible to bond the two while heating by heating or pressing or using a heating roller device.

補強材料側半成品，例如，如聚醯亞胺膜般柔軟且可捲繞之補強材料的情況下，於補強材料塗布接著劑而製造較理想。又，例如如以環氧樹脂使SUS、鋁等金屬板、玻璃纖維硬化而得之板等堅硬且無法捲繞之補強板的情況下，藉由將預先塗布於脫模基材之接著劑進行轉印塗布而製造較理想。又，必要時可進行所塗布之接著劑中的交聯反應。較佳實施態様中，係使接著劑層半硬化。In the case of a reinforcing material side semi-finished product, for example, a reinforcing material which is soft and can be wound, such as a polyimide film, it is preferable to apply an adhesive to the reinforcing material. Further, for example, when a reinforcing plate which is hard and cannot be wound, such as a metal plate such as SUS or aluminum, or a glass fiber obtained by curing an epoxy resin, is used, the adhesive agent previously applied to the release substrate is used. It is preferable to manufacture by transfer coating. Further, a crosslinking reaction in the applied adhesive can be carried out as necessary. In a preferred embodiment, the adhesive layer is semi-hardened.

所獲得之補強材料側半成品，可直接使用在與印刷電路板背面之貼合，又，亦可貼合脫模膜進行保存後，使用在與基材膜側半成品之貼合。The obtained semi-finished material of the reinforcing material side can be directly used for bonding to the back surface of the printed circuit board, or can be adhered to the release film and then used for bonding with the semi-finished product on the substrate film side.

基材膜側半成品、表覆膜側半成品、補強材料側半成品皆為本發明中之印刷電路板用疊層體。The substrate film side semi-finished product, the surface film side semi-finished product, and the reinforcing material side semi-finished product are all laminates for printed circuit boards in the present invention.

＜實施例＞ 以下，列舉實施例對本發明進行更詳細地說明。但，本發明並不限定於實施例。實施例中及比較例中之簡稱份表示質量份。<Examples> Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the embodiments. The abbreviated parts in the examples and the comparative examples represent parts by mass.

(物性評價方法)(Physical evaluation method)

(酸值(A)成分：含有羧基之聚烯烴樹脂) 本發明中之酸值(當量/106 g)，係使用FT－IR(島津製作所公司製、FT－IR8200PC)，並利用馬來酸酐之羰基(C=O)鍵之伸縮峰部(1780cm-1 )的吸光度(I)、同排聚合物所特有之峰部(840cm-1 )的吸光度(II)、及由馬來酸酐(東京化成製)之氯仿溶液所作成之檢量線獲得的係數(f)根據下式算出，該算出的值以樹脂1ton中之當量(當量/106 g)表示。 酸值=[吸光度(I)/吸光度(II)×(f)/馬來酸酐的分子量×2×104 ] 馬來酸酐的分子量：98.06(Acid value (A) component: a polyolefin resin containing a carboxyl group) The acid value (equivalent to 10 6 g) in the present invention is FT-IR (FT-IR8200PC, manufactured by Shimadzu Corporation), and maleic anhydride is used. The absorbance (I) of the stretching peak (1780 cm -1 ) of the carbonyl (C=O) bond, the absorbance (II) of the peak (840 cm -1 ) specific to the same-row polymer, and the maleic anhydride (Tokyo) The coefficient (f) obtained by the calibration curve prepared by the chloroform solution of the chemical conversion system was calculated according to the following formula, and the calculated value was expressed by the equivalent (equivalent/10 6 g) in the resin 1ton. Acid value = [absorbance (I) / absorbance (II) × (f) / molecular weight of maleic anhydride × 2 × 10 4 ] Molecular weight of maleic anhydride: 98.06

(酸值(B)成分：含有羧基之苯乙烯樹脂) 本發明中之酸值(當量/106 g)，係將含有羧基之苯乙烯樹脂溶解於甲苯，並在甲醇鈉之甲醇溶液中以酚酞作為指示劑進行滴定。以樹脂1ton中之當量(當量/106 g)表示。(Acid value (B) component: styrene resin containing a carboxyl group) The acid value (equivalent/10 6 g) in the present invention is obtained by dissolving a styrene resin containing a carboxyl group in toluene and in a methanol solution of sodium methoxide. Phenolphthalein was titrated as an indicator. It is represented by the equivalent (equivalent/10 6 g) in the resin 1ton.

(重量平均分子量(Mw)) 本發明中之重量平均分子量係利用凝膠滲透層析法(以下稱GPC，標準物質：聚苯乙烯樹脂，移動相：四氫呋喃)測得的值。(Weight average molecular weight (Mw)) The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran).

(1)剝離強度(接著性) 以使乾燥後之厚度成為25μm的方式，將後述接著劑組成物塗布於厚度12.5μm之聚醯亞胺膜(Kaneka股份有限公司製、Apical)、或厚度25μm之LCP膜(KURARAY股份有限公司製、Vecstar)，並在130℃乾燥3分鐘。將如此獲得之接著性膜(B階段品)與18μm之壓延銅箔貼合。貼合係以使壓延銅箔之光澤面與接著劑接觸的方式進行，在160℃於40kgf/cm2 之加壓下壓製30秒而接著。然後在140℃熱處理4小時而使其硬化，得到剝離強度評價用樣品。剝離強度係於25℃拉伸膜，以拉伸速度50mm/min進行90°剝離試驗並測定剝離強度。該試驗係表示於常溫的接著強度。 ＜評價基準＞ ◎：1.0N/mm以上 ○：0.8N/mm以上未達1.0N/mm △：0.5N/mm以上未達0.8N/mm ×：未達0.5N/mm(1) Peeling strength (adhesiveness) The adhesive composition described later was applied to a polyimide film (available from Kaneka Co., Ltd., Apical) having a thickness of 12.5 μm or a thickness of 25 μm so that the thickness after drying was 25 μm. The LCP film (manufactured by KURARAY Co., Ltd., Vecstar) was dried at 130 ° C for 3 minutes. The adhesive film (B-stage product) thus obtained was bonded to a rolled copper foil of 18 μm. The bonding was carried out so that the shiny side of the rolled copper foil was brought into contact with the adhesive, and pressed at 160 ° C under a pressure of 40 kgf / cm 2 for 30 seconds. Then, it was heat-treated at 140 ° C for 4 hours to be hardened, and a sample for peel strength evaluation was obtained. The peel strength was stretched at 25 ° C, and a 90° peel test was performed at a tensile speed of 50 mm/min to measure the peel strength. This test is expressed as the strength at room temperature. <Evaluation Criteria> ◎: 1.0 N/mm or more ○: 0.8 N/mm or more and less than 1.0 N/mm △: 0.5 N/mm or more and less than 0.8 N/mm ×: less than 0.5 N/mm

(2)乾燥焊料耐熱性 利用與上述相同的方法製作樣品，將2.0cm×2.0cm之樣品片於120℃進行30分鐘乾燥處理，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。 ＜評價基準＞ ◎：310℃以上 ○：300℃以上未達310℃ △：290℃以上未達300℃ ×：未達290℃(2) Dry solder heat resistance A sample was prepared by the same method as described above, and a 2.0 cm × 2.0 cm sample piece was dried at 120 ° C for 30 minutes, and flowed in a molten solder bath at each temperature for 1 minute, and the measurement was not performed. A temperature that causes an appearance change such as swelling. <Evaluation criteria> ◎: 310°C or more ○: 300°C or more and less than 310°C △: 290°C or more and less than 300°C ×: Not up to 290°C

(3)加濕焊料耐熱性 利用與上述相同的方法製作樣品，將2.0cm×2.0cm之樣品片進行40℃×80RH%×72小時處理，並於各溫度在熔融的焊料浴中流動1分鐘，測定不會引起膨起等外觀變化的溫度。 ＜評價基準＞ ◎：260℃以上 ○：250℃以上未達260℃ △：240℃以上未達250℃ ×：未達240℃(3) Humidification solder heat resistance A sample was prepared by the same method as described above, and a 2.0 cm × 2.0 cm sample piece was subjected to treatment at 40 ° C × 80 RH % × 72 hours, and flowed in a molten solder bath at each temperature for 1 minute. The temperature at which the appearance change such as swelling does not occur is measured. <Evaluation criteria> ◎: 260°C or higher ○: 260°C or less at 250°C or more △: 250°C or less at 240°C or less ×: 240°C or less

(4)相對介電常數(εc )及介電正切(tanδ) 以使乾燥硬化後之厚度成為25μm的方式，將後述接著劑組成物塗布於厚度35μm之電解銅箔之光澤面，並在130℃乾燥3分鐘。然後在140℃熱處理4小時使其硬化，而得到試驗用之覆銅疊層板。於所獲得之試驗用覆銅疊層板之已硬化的接著劑組成物面，利用網版印刷塗布蒸發乾固型的導電性銀糊劑成為直徑50mm的圓形，並在120℃乾燥30分鐘使其硬化，進一步於導電性銀糊劑所形成之圓的中央，利用導電性接著劑接著長度30mm的引線，得到平行平板電容器。使用PRECISION LCR meter HP－4284A，在22℃下以頻率1MHz之條件測定所獲得之平行平板電容器的靜電電容Cap與損耗係數D(介電正切)，並根據下式算出相對介電常數(εc )。 εc ＝(Cap×d)/(S×ε0 ) 此處，Cap：靜電電容[F] d：介電體層厚度＝25×10-6 [m] S：被測定介電體面積＝π×(25×10-3 )2 ε0 ：真空的介電常數　8.854×10-12 針對所獲得之相對介電常數、介電正切，如下述般進行評價。 ＜相對介電常數的評價基準＞ ◎：2.3以下 ○：超過2.3至2.6以下 △：超過2.6至3.0以下 ×：超過3.0 ＜介電正切的評價基準＞ ◎：0.005以下 ○：超過0.005至0.01以下 △：超過0.01至0.02以下 ×：超過0.02(4) Relative dielectric constant (ε c ) and dielectric tangent (tan δ) The adhesive composition described later was applied to a glossy surface of an electrolytic copper foil having a thickness of 35 μm so that the thickness after drying and hardening became 25 μm. Dry at 130 ° C for 3 minutes. Then, it was heat-treated at 140 ° C for 4 hours to be hardened to obtain a copper-clad laminate for testing. On the hardened adhesive composition surface of the obtained copper-clad laminate for testing, a conductive dry silver-type conductive silver paste was applied by screen printing to a circular shape of 50 mm in diameter, and dried at 120 ° C for 30 minutes. This was hardened, and further, a parallel plate capacitor was obtained by using a conductive adhesive followed by a lead having a length of 30 mm in the center of a circle formed by the conductive silver paste. Using the PRECISION LCR meter HP-4284A, the electrostatic capacitance Cap and the loss factor D (dielectric tangent) of the obtained parallel plate capacitor were measured at a frequency of 1 MHz at 22 ° C, and the relative dielectric constant (ε c was calculated according to the following formula). ). ε c = (Cap × d) / (S × ε 0 ) Here, Cap: electrostatic capacitance [F] d: dielectric layer thickness = 25 × 10 -6 [m] S: measured dielectric area = π ×(25 × 10 -3 ) 2 ε 0 : The dielectric constant of vacuum 8.854 × 10 -12 was evaluated for the relative dielectric constant and dielectric tangent obtained as follows. <Evaluation Criteria for Relative Dielectric Constant> ◎: 2.3 or less ○: more than 2.3 to 2.6 or less Δ: more than 2.6 to 3.0 or less ×: more than 3.0 <Evaluation criteria of dielectric tangent> ◎: 0.005 or less ○: more than 0.005 to 0.01 or less △: more than 0.01 to 0.02 or less ×: more than 0.02

(含有羧基之聚烯烴樹脂) ［製造例1］ 於1L高壓釜(autoclave)中，加入丙烯－丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7080」)100質量份、甲苯150質量份及馬來酸酐19質量份、二－第三丁基過氧化物6質量份，升溫至140℃後，進一步攪拌3小時。之後，將所獲得之反應液冷卻後，注入裝有大量甲乙酮的容器中並使樹脂析出。然後，藉由離心分離該含有樹脂之溶液，將馬來酸酐接枝聚合而得的酸改性丙烯－丁烯共聚物，與(聚)馬來酸酐及低分子量物進行分離、純化。其後，藉由於減壓下、70℃使其乾燥5小時，得到馬來酸酐改性丙烯－丁烯共聚物(CO－1、酸值410當量/106 g、重量平均分子量60,000、Tm80℃、△H35J/g)。(Polyolefin resin containing a carboxyl group) [Production Example 1] 100 parts by mass of a propylene-butene copolymer ("TAFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals Co., Ltd.) and a toluene 150 mass were added to a 1 L autoclave. 19 parts by mass of maleic anhydride and 6 parts by mass of di-tert-butyl peroxide were heated to 140 ° C, and further stirred for 3 hours. Thereafter, the obtained reaction liquid was cooled, poured into a vessel containing a large amount of methyl ethyl ketone, and the resin was precipitated. Then, the acid-modified propylene-butene copolymer obtained by graft-polymerizing the resin-containing solution by grafting the maleic anhydride with (poly)maleic anhydride and a low molecular weight substance is separated and purified. Thereafter, the maleic anhydride-modified propylene-butene copolymer (CO-1, acid value: 410 equivalent/10 6 g, weight average molecular weight of 60,000, Tm 80 ° C) was obtained by drying at 70 ° C for 5 hours under reduced pressure. , △H35J/g).

［製造例2］ 將馬來酸酐的添加量變更為11質量份，除此以外，利用與製造例1同樣的方法，得到馬來酸酐改性丙烯－丁烯共聚物(CO－2、酸值220當量/106 g、重量平均分子量65,000、Tm78℃、△H25J/g)。[Production Example 2] A maleic anhydride-modified propylene-butene copolymer (CO-2, acid value) was obtained by the same method as in Production Example 1 except that the amount of the maleic anhydride was changed to 11 parts by mass. 220 equivalents/10 6 g, weight average molecular weight 65,000, Tm 78 ° C, ΔH 25 J/g).

［實施例1］ 在配備有水冷回流冷凝器與攪拌器的500mL四口燒瓶中，加入製造例1所獲得之馬來酸酐改性丙烯－丁烯共聚物(CO－1)80質量份、含有羧基之苯乙烯樹脂(Tuftec(註冊商標)M1943)20質量份、甲苯500質量份，邊攪拌邊升溫至80℃，藉由持續攪拌1小時而溶解。於冷卻獲得之溶液中，摻合5質量份碳二亞胺樹脂V－05、10質量份環氧樹脂HP－7200，得到接著劑組成物。摻合量、接著強度、焊料耐熱性、電氣特性顯示於表1中。[Example 1] 80 parts by mass of a maleic anhydride-modified propylene-butene copolymer (CO-1) obtained in Production Example 1 was added to a 500 mL four-necked flask equipped with a water-cooled reflux condenser and a stirrer. 20 parts by mass of a carboxyl group-containing styrene resin (Tuftec (registered trademark) M1943) and 500 parts by mass of toluene were heated to 80 ° C with stirring, and dissolved by continuously stirring for 1 hour. In the solution obtained by cooling, 5 parts by mass of carbodiimide resin V-05 and 10 parts by mass of epoxy resin HP-7200 were blended to obtain an adhesive composition. The blending amount, the bonding strength, the solder heat resistance, and the electrical characteristics are shown in Table 1.

［實施例2～10］ 將含有羧基之聚烯烴樹脂(A)、含有羧基之苯乙烯樹脂(B)、碳二亞胺樹脂(C)、環氧樹脂(D)如表1所示進行變更，利用與實施例1同樣的方法實施實施例2～14，使其變更成為表1所示之各摻合量。接著強度、焊料耐熱性、電氣特性顯示於表1中。[Examples 2 to 10] The carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C), and the epoxy resin (D) were changed as shown in Table 1. Examples 2 to 14 were carried out in the same manner as in Example 1 and changed to the respective blending amounts shown in Table 1. Next, the strength, solder heat resistance, and electrical characteristics are shown in Table 1.

[表1] [Table 1]

［比較例1～7］ 將含有羧基之聚烯烴樹脂(A)、含有羧基之苯乙烯樹脂(B)、碳二亞胺樹脂(C)、環氧樹脂(D)如表2所示進行變更，利用與實施例1同樣的方法實施比較例1～7，使其變更成為表2所示之各摻合量。摻合量、接著強度、焊料耐熱性、電氣特性顯示於表2中。[Comparative Examples 1 to 7] The carboxyl group-containing polyolefin resin (A), the carboxyl group-containing styrene resin (B), the carbodiimide resin (C), and the epoxy resin (D) were changed as shown in Table 2. Comparative Examples 1 to 7 were carried out in the same manner as in Example 1 and changed to the respective blending amounts shown in Table 2. The blending amount, the bonding strength, the solder heat resistance, and the electrical characteristics are shown in Table 2.

[表2] [Table 2]

表1、2中所使用之聚烯烴樹脂、含有羧基之苯乙烯樹脂(B)、碳二亞胺樹脂(C)、環氧樹脂(D)係如以下者。 含有羧基之苯乙烯樹脂：Tuftec(註冊商標)M1911(旭化成化學公司製) 含有羧基之苯乙烯樹脂：Tuftec(註冊商標)M1913(旭化成化學公司製) 含有羧基之苯乙烯樹脂：Tuftec(註冊商標)M1943(旭化成化學公司製) 聚烯烴樹脂：TAFMER(註冊商標)XM7080(三井化學公司製) 苯乙烯樹脂：Tuftec(註冊商標)H1052(旭化成化學公司製) 含有羧基之丙烯腈－丁二烯橡膠NBR(JSR股份有限公司製) 碳二亞胺樹脂：V－05(日清紡化學公司製) 碳二亞胺樹脂：V－03(日清紡化學公司製) 鄰甲酚酚醛型環氧樹脂：YDCN－700－10(新日鐵住金化學公司製) 二環戊二烯型環氧樹脂：HP－7200(DIC公司製)The polyolefin resin used in Tables 1 and 2, the styrene resin (B) containing a carboxyl group, the carbodiimide resin (C), and the epoxy resin (D) are as follows. Styrene resin containing carboxyl group: Tuftec (registered trademark) M1911 (manufactured by Asahi Kasei Chemicals Co., Ltd.) Styrene resin containing carboxyl group: Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Chemicals Co., Ltd.) Styrene resin containing carboxyl group: Tuftec (registered trademark) M1943 (made by Asahi Kasei Chemicals Co., Ltd.) Polyolefin resin: TAFMER (registered trademark) XM7080 (manufactured by Mitsui Chemicals, Inc.) Styrene resin: Tuftec (registered trademark) H1052 (manufactured by Asahi Kasei Chemicals Co., Ltd.) Acrylonitrile-butadiene rubber NBR containing carboxyl group (manufactured by JSR Co., Ltd.) carbodiimide resin: V-05 (manufactured by Nisshinbo Chemical Co., Ltd.) carbodiimide resin: V-03 (manufactured by Nisshinbo Chemical Co., Ltd.) o-cresol novolac type epoxy resin: YDCN-700- 10 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Dicyclopentadiene type epoxy resin: HP-7200 (manufactured by DIC Corporation)

由表1可知：實施例1～14中，和聚醯亞胺(PI)與銅箔具有優異的接著性、焊料耐熱性，同時和液晶聚合物(LCP)與銅箔亦具有優異的接著性、焊料耐熱性。又，關於接著劑組成物的電氣特性，介電常數、介電正切皆低，係良好。反觀由表2可知：比較例1中未摻合含有羧基之苯乙烯樹脂，故加濕焊料耐熱性、接著強度差。比較例2中未摻合含有羧基之聚烯烴樹脂，故交聯密度低，加濕焊料耐熱性差。比較例3中聚烯烴樹脂不含羧基，故交聯密度低，加濕焊料耐熱性差。比較例4中苯乙烯樹脂不含羧基，故交聯密度低，加濕焊料耐熱性差。比較例5中未摻合碳二亞胺樹脂，故與LCP界面的相互作用小，接著強度低。比較例6中未摻合環氧樹脂，故交聯密度低，焊料耐熱性差。比較例7中未摻合聚烯烴樹脂、苯乙烯樹脂，故接著劑組成物的低介電特性差。 [產業上利用性]As is clear from Table 1, in Examples 1 to 14, the polyimine (PI) and the copper foil have excellent adhesion and solder heat resistance, and also have excellent adhesion to liquid crystal polymer (LCP) and copper foil. , solder heat resistance. Further, regarding the electrical characteristics of the adhesive composition, the dielectric constant and the dielectric tangent were both low and good. In contrast, as is clear from Table 2, in Comparative Example 1, the styrene resin containing a carboxyl group was not blended, so that the moisturizing solder had poor heat resistance and subsequent strength. In Comparative Example 2, the polyolefin resin containing a carboxyl group was not blended, so that the crosslinking density was low, and the heat resistance of the humidifying solder was poor. In Comparative Example 3, the polyolefin resin contained no carboxyl group, so the crosslinking density was low, and the moisturizing solder had poor heat resistance. In the comparative example 4, since the styrene resin does not contain a carboxyl group, the crosslinking density is low, and the humidifying solder has poor heat resistance. In Comparative Example 5, the carbodiimide resin was not blended, so the interaction with the LCP interface was small, and the strength was low. In Comparative Example 6, the epoxy resin was not blended, so that the crosslinking density was low and the solder heat resistance was poor. In Comparative Example 7, the polyolefin resin and the styrene resin were not blended, so that the adhesive composition had poor low dielectric properties. [Industrial use]

根據本發明，可提供一種疊層體，不僅是與以往的聚醯亞胺、聚對苯二甲酸乙二酯膜，與LCP等具有低介電特性之樹脂基材、銅箔等金屬基材亦具有高接著性，可獲得高焊料耐熱性，且低介電特性優異。基於上述特性，在可撓性印刷電路板用途，特別是要求於高頻區域之低介電特性(低介電常數、低介電正切)的FPC用途係有用。According to the present invention, it is possible to provide a laminate which is not only a conventional polyimide substrate, a polyethylene terephthalate film, a resin substrate having a low dielectric property such as LCP, or a metal substrate such as a copper foil. It also has high adhesion, high solder heat resistance, and excellent low dielectric properties. Based on the above characteristics, it is useful for flexible printed circuit board applications, particularly FPC applications requiring low dielectric properties (low dielectric constant, low dielectric tangent) in a high frequency region.

無no

Claims (6)

一種疊層體(Z)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成； 其特徵為： (1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下， (2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下， (3)樹脂基材與金屬基材間的剝離強度為0.5N/mm以上， (4)疊層體(Z)之加濕焊料耐熱性為240℃以上。A laminate (Z) comprising a resin substrate and a metal substrate laminated via an adhesive comprising a carboxyl group-containing polyolefin resin (A); characterized by: (1) an adhesive layer at a frequency of 1 MHz The relative dielectric constant (ε c ) is 3.0 or less, (2) the dielectric tangent (tan δ) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, and (3) the peel strength between the resin substrate and the metal substrate is 0.5. N/mm or more, (4) The heat resistance of the solder of the laminate (Z) is 240 ° C or higher. 一種疊層體(X)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層與該樹脂基材的疊層體； 其特徵為： (1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下， (2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下， (3)於疊層體(X)之接著劑層面疊層金屬基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上， (4)於疊層體(X)之接著劑層面疊層金屬基材時，該疊層體之加濕焊料耐熱性為240℃以上。A laminate (X), which is a laminate of a resin substrate and a metal substrate, which is formed by laminating a layer of an adhesive including a carboxyl group-containing polyolefin resin (A). a laminate of the resin substrate; characterized in that: (1) the dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) dielectric tangent of the adhesive layer at a frequency of 1 MHz (tan δ) is 0.02 or less, and (3) when a metal substrate is laminated on the adhesive layer of the laminate (X), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm. As described above, (4) When the metal substrate is laminated on the adhesive layer of the laminate (X), the heat resistance of the solder of the laminate is 240 ° C or higher. 一種疊層體(Y)，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層與該金屬基材的疊層體； 其特徵為： (1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下， (2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下， (3)於疊層體(Y)之接著劑層面疊層樹脂基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上， (4)於疊層體(Y)之接著劑層面疊層樹脂基材時，該疊層體之加濕焊料耐熱性為240℃以上。A laminate (Y) which is a laminate of a resin substrate and a metal substrate which is formed by laminating a layer of an adhesive including a carboxyl group-containing polyolefin resin (A). a laminate of the metal substrate; characterized in that: (1) the dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) dielectric tangent of the adhesive layer at a frequency of 1 MHz (tan δ) is 0.02 or less, and (3) when a resin substrate is laminated on the adhesive layer of the laminate (Y), the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm. As described above, (4) when the resin substrate is laminated on the adhesive layer of the laminate (Y), the heat resistance of the solder of the laminate is 240 ° C or higher. 一種接著劑層，係樹脂基材及金屬基材介由包括含有羧基之聚烯烴樹脂(A)之接著劑層疊層而成的疊層體(Z)所使用之該接著劑層； 其特徵為： (1)接著劑層之於頻率1MHz的相對介電常數(εc )為3.0以下， (2)接著劑層之於頻率1MHz的介電正切(tanδ)為0.02以下， (3)於接著劑層之其中一面疊層樹脂基材，於另一面疊層金屬基材時，該疊層體中之樹脂基材與金屬基材間的剝離強度為0.5N/mm以上， (4)於接著劑層之其中一面疊層樹脂基材，於另一面疊層金屬基材時，該疊層體之加濕焊料耐熱性為240℃以上。An adhesive layer used for a laminate (Z) comprising a resin substrate and a metal substrate via a laminate layer comprising an adhesive containing a carboxyl group-containing polyolefin resin (A); (1) The relative dielectric constant (ε c ) of the adhesive layer at a frequency of 1 MHz is 3.0 or less, and (2) the dielectric tangent (tan δ) of the adhesive layer at a frequency of 1 MHz is 0.02 or less, and (3) When the resin substrate is laminated on one surface of the layer, and the metal substrate is laminated on the other surface, the peel strength between the resin substrate and the metal substrate in the laminate is 0.5 N/mm or more, and (4) When the resin substrate is laminated on one surface of the agent layer and the metal substrate is laminated on the other surface, the heat resistance of the solder of the laminate is 240 ° C or higher. 一種接著片，含有如申請專利範圍第1項之疊層體(Z)、如申請專利範圍第2項之疊層體(X)、如申請專利範圍第3項之疊層體(Y)或如申請專利範圍第4項之接著劑層。An adhesive sheet comprising the laminate (Z) of claim 1 of the patent application, the laminate (X) of claim 2, the laminate (Y) of claim 3, or For example, the adhesive layer of claim 4 is applied. 一種印刷電路板，包含如申請專利範圍第5項之接著片作為構成要素。A printed circuit board comprising a back sheet as in the fifth aspect of the patent application as a constituent element.
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