CN107109182B - Laminated body containing low dielectric adhesive layer - Google Patents

Laminated body containing low dielectric adhesive layer Download PDF

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Publication number
CN107109182B
CN107109182B CN201680004408.3A CN201680004408A CN107109182B CN 107109182 B CN107109182 B CN 107109182B CN 201680004408 A CN201680004408 A CN 201680004408A CN 107109182 B CN107109182 B CN 107109182B
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China
Prior art keywords
laminated body
adhesive phase
resin
base material
laminated
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CN201680004408.3A
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CN107109182A (en
Inventor
三上忠彦
伊藤武
薗田辽
坂田秀行
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Dongyang Textile Mc Co ltd
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Toyobo Co Ltd
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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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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

Abstract

The present invention provides a kind of laminated body below: it is not only with traditional polyimides and polyester film, and also low polar resin substrate and metal base have high adherence with LCP etc., can obtain high scolding tin heat resistance, and low dielectric property is excellent.Laminated body (Z) of the invention is the laminated body (Z) that resin base material and metal base are laminated by adhesive phase and is formed, and described adhesive layer includes: carboxylic polyolefin resin (A)；It is characterized by: relative dielectric constant (the ε under the frequency 1MHz of (1) adhesive phasec) it is 3.0 or less, (2) dielectric loss angle tangent (tan δ) under the frequency 1MHz of adhesive phase is 0.02 or less, (3) peel strength between resin base material and metal base is 0.5N/mm or more, and the wetting scolding tin heat resistance of (4) laminated body (Z) is 240 DEG C or more.

Description

Laminated body containing low dielectric adhesive layer
Technical field
The present invention relates to a kind of stackings containing the adhesive phase for showing low-k and low-dielectric loss angle tangent Body.More particularly it relates to a kind of adhesive phase by showing low-k and low-dielectric loss angle tangent Laminated body made of resin base material and metal base is laminated.In particular, the present invention relates to one kind for flexible printed circuit board (with Be referred to as FPC down) laminated body and covering layer film comprising the laminated body, plywood, resin copper foil and adhesive sheet.
Background technique
In recent years, with the high speed of the transmission signal in printed circuit board, the high frequency of signal is advanced.Along with this Ground, the requirement in FPC to the low dielectric property (low-k, low-dielectric loss angle tangent) in high-frequency region also accordingly mention It is high.For the requirement, as base material film used in FPC, there has been proposed with the liquid crystal polymer with low dielectric property (LCP), the base material films such as syndiotactic polytyrene (SPS) and polyphenylene sulfide (PPS), to replace previous polyimides (PI) and poly- pair The scheme of ethylene terephthalate film.
However, the polarity of the base material film with low dielectric property is low, thus, using traditional epoxy adhesive or third When olefin(e) acid system adhesive, bonding force is weak, it is difficult to make the FPC component such as covering layer film and plywood.In addition, epoxy adhesive Or acrylic adhesive does not have excellent low dielectric property, can damage the dielectric property of FPC.
On the other hand, known polyolefin resin has low dielectric property.Therefore, there has been proposed use polyolefin resin FPC adhesive composite.For example, proposing in patent document 1 and using polyolefin copolymer, aromatic series containing carboxyl The block copolymer and epoxy resin of vinyl compound polymer block and conjugation diene compound polymer blocks Heat reactivity adhesive composition.In addition, proposing in patent document 2 and using carboxylic styrenic elastomer and asphalt mixtures modified by epoxy resin The adhesive composition of rouge.
Existing technical literature
Patent document
Patent document 1: No. 3621351 bulletins of Japanese Patent Laid
Patent document 2:WO2014/147903A1 bulletin
Summary of the invention
Problems to be solved by the invention
Though not described however, describing the adhesiveness and scolding tin heat resistance of polyimide film and SUS in patent document 1 Dielectric property, it is also difficult to obtain the adhesiveness with base material films with low dielectric property such as LCP.In addition, in patent document 2, though The adhesiveness between dielectric property and polyimide film and copper foil is described, but does not describe that there is low dielectric property with LCP etc. Base material film adhesiveness.Though the scolding tin heat resistance after wetting is difficult to call it in addition, describing the scolding tin heat resistance after drying Sufficiently.
The present invention furthers investigate in order to solve the above problem, as a result, it has been found that the adhesive phase with specific physical property can not only make Traditional polyimide film can also make the resin base material with low dielectric property such as unimagined LCP in the prior art, with copper foil There is high adherence, high scolding tin heat resistance and excellent low dielectric property between equal metal bases, thereby completing the present invention.
That is, the purpose of the present invention is to provide a kind of laminated body being laminated by adhesive phase, it should Adhesive phase have with the various resin base materials such as polyimides, LCP and with the good adhesive property of both metal bases, and it is resistance to Hot and low dielectric property is also excellent.
The means solved the problems, such as
A kind of laminated body (Z) is laminated body made of resin base material and metal base are laminated by adhesive phase (Z), described adhesive layer includes: carboxylic polyolefin resin (A)；It is characterized by: under the frequency 1MHz of (1) adhesive phase Relative dielectric constant (εc) it is 3.0 or less；(2) dielectric loss angle tangent (tan δ) under the frequency 1MHz of adhesive phase is 0.02 or less；(3) peel strength between resin base material and metal base is 0.5N/mm or more；(4) wetting of laminated body (Z) Scolding tin heat resistance is 240 DEG C or more.
A kind of laminated body (X) is the laminated body (X) of adhesive phase and resin base material, for passing through described adhesive layer It is laminated in laminated body made of the resin base material and metal base (Z), described adhesive layer includes: carboxylic polyolefin Resin (A)；It is characterized by: relative dielectric constant (the ε under the frequency 1MHz of (1) adhesive phasec) it is 3.0 or less；(2) it bonds Dielectric loss angle tangent (tan δ) under the frequency 1MHz of oxidant layer is 0.02 or less；(3) in the face of the adhesive phase of laminated body (X) When upper stacking metal base, the peel strength between resin base material and metal base in the laminated body is 0.5N/mm or more； (4) when metal base is laminated on the face of the adhesive phase of laminated body (X), the wetting scolding tin heat resistance of the laminated body is 240 DEG C More than.
A kind of laminated body (Y) is the laminated body (Y) of adhesive phase and metal base, for passing through described adhesive layer It is laminated in laminated body (Z) made of resin base material and the metal base, described adhesive layer includes: carboxylic polyolefin Resin (A)；It is characterized by: relative dielectric constant (the ε under the frequency 1MHz of (1) adhesive phasec) it is 3.0 or less；(2) it bonds Dielectric loss angle tangent (tan δ) under the frequency 1MHz of oxidant layer is 0.02 or less；(3) in the face of the adhesive phase of laminated body (Y) When upper stacking resin base material, the peel strength between resin base material and metal base in the laminated body is 0.5N/mm or more； (4) when resin base material is laminated on the face of the adhesive phase of laminated body (Y), the wetting scolding tin heat resistance of the laminated body is 240 DEG C More than.
A kind of adhesive phase, for for laminated body made of resin base material and metal base to be laminated by adhesive phase (Z) the described adhesive layer in, described adhesive layer includes: carboxylic polyolefin resin (A)；It is characterized by: (1) bonds Relative dielectric constant (ε under the frequency 1MHz of oxidant layerc) it is 3.0 or less；(2) dielectric loss under the frequency 1MHz of adhesive phase Angle tangent (tan δ) is 0.02 or less；(3) resin base material and the another side in adhesive phase are laminated in the one side of adhesive phase When upper stacking metal base, the peel strength between resin base material and metal base in the laminated body is 0.5N/mm or more； (4) in stacking resin base material in the one side of adhesive phase and when metal base is laminated on the another side of adhesive phase, the stacking The wetting scolding tin heat resistance of body is 240 DEG C or more.
A kind of adhesive sheet contains above-mentioned laminated body (Z), laminated body (X), laminated body (Y) or adhesive phase.
A kind of printed circuit board, it includes above-mentioned adhesive sheets as constituent element.
Invention effect
Resin base material is laminated due to the adhesive phase of the present invention by the inclusion of carboxylic polyolefin resin (A) Meet the following conditions with laminated body made of metal base: (1) relative dielectric constant (ε under the frequency 1MHz of adhesive phasec) It is 3.0 or less；(2) dielectric loss angle tangent (tan δ) under the frequency 1MHz of adhesive phase is 0.02 or less；(3) resin base material Peel strength between metal base is 0.5N/mm or more；(4) the wetting scolding tin heat resistance of laminated body is 240 DEG C or more；Cause This, not only with traditional polyimide film and polyester film, but also the low polar tree with LCP film unimagined in current art etc. Aliphatic radical material and metal base have high adhesiveness, can obtain high scolding tin heat resistance, and low dielectric property is excellent.
Specific embodiment
Hereinafter, detailed description of embodiments of the present invention.Laminated body (Z) of the invention be by adhesive phase come It is laminated made of resin base material and metal base, described adhesive layer includes: carboxylic polyolefin resin (A).
<carboxylic polyolefin resin base (A)>
Carboxylic polyolefin resin base (A) (hereinafter, can be also simply referred to as (A) ingredient) used in the present invention is not Limit, but preferably by being grafted α on polyolefin resin, at least one of beta-unsaturated carboxylic acid and its acid anhydrides and obtain (A) ingredient.Polyolefin resin refers to the homopolymerization of olefinic monomer exemplified by ethylene, propylene, butylene, butadiene and isoprene etc. Or the polymer with the hydride or halide of the copolymerization of other monomers and resulting polymers etc., based on hydrocarbon skeleton. That is, carboxylic polyolefin is preferably by least one of polyethylene, polypropylene and propylene-alpha-olefin copolymers Upper grafting at least one of alpha, beta-unsaturated carboxylic acid and its acid anhydrides and obtain.
Propylene-alpha-olefin copolymers are by obtaining propylene and alpha-olefin as main body and carrying out combined polymerization.Make For alpha-olefin, for example, can be used in ethylene, 1- butylene, 1- heptene, 1- octene, 4-methyl-1-pentene and vinyl acetate etc. It is one or more.In these alpha-olefins, optimal ethylene and 1- butylene.Propylene ingredient and α-alkene in propylene-alpha-olefin copolymers The ratio of hydrocarbon ingredient does not limit, but propylene ingredient preferably 50 moles of % or more, more preferable 70 moles of % or more.
As α, at least one of beta-unsaturated carboxylic acid and its acid anhydrides, for example, maleic acid, itaconic acid, lemon health can be enumerated Acid and their acid anhydrides.In these, preferred anhydrides, more preferable maleic anhydride.Specifically, maleic anhydride modified poly- third can be enumerated Alkene, maleic anhydride modified propylene-ethylene copolymers, maleic anhydride modified propene-1-butene copolymer and maleic anhydride modified propylene- Ethylene-butene copolymer etc., and by one of these acid modified polyolefins or can be used in combination of two or more.
From heat resistance and with from the viewpoint of the adhesiveness of resin base material or metal base, carboxylic polyolefin resin (A) lower limit of acid value is preferably 100 equivalent/106G or more, more preferable 200 equivalent/106G or more, further preferably 250 work as Amount/106g.Acid value be less than above-mentioned value when, exist it is low with the compatibility of epoxy resin (D), carbodiimides resin (C) and can not The case where embodying adhesive strength.In addition, it is low there is also crosslink density and the case where lack heat resistance.The upper limit of acid value is preferably 1000 equivalent/106G is hereinafter, more preferable 700 equivalent/106G is hereinafter, further preferred 500 equivalent/106G or less.Acid value is more than upper When stating value, the case where there are adhesiveness reductions.In addition, there is also the viscosity of solution or stability decline, working life property to reduce Situation.Further, manufacture efficiency also reduces, thus, not preferably.
The weight average molecular weight (Mw) of carboxylic polyolefin resin (A) is preferably 10000~180000 range.More preferably 20000~160000 range, further preferred 30000~150000 range, particularly preferred 40000~140000 model It encloses, most preferably 50000~130000 range.When Mw is less than above-mentioned value, there are cohesive force die down and the case where poor adhesion.Separately On the one hand, Mw be more than above-mentioned value when, it is low there are mobility and bonding when generate operational problem the case where.
It as the manufacturing method of carboxylic polyolefin resin (A), is not particularly limited, for example, free object can be enumerated Base graft reaction (that is, the polymer as main chain is made to generate free radicals species, and make the free radical kind as polymerization initiation point and Reacted with what unsaturated carboxylic acid and acid anhydrides were graft-polymerized) etc..
It as free-radical generating agent, is not particularly limited, but it is preferable to use organic peroxides.As organic peroxy Object is not particularly limited, but it is different to enumerate phthalic peroxide di tert butyl carbonate, tert-butyl hydroperoxide, peroxidating two Propyl benzene, benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide -2-ethyl hexanoic acid tert-butyl, the tertiary fourth of peroxidating neopentanoic acid The peroxide such as ester, methyl ethyl ketone peroxide, di-tert-butyl peroxide and lauroyl peroxide；And azodiisobutyronitrile With the azos nitrile such as azo diisopropyl nitrile etc..
<adhesive phase>
In the present invention, adhesive phase refers to that the adhesive after adhesive composition is coated on substrate and is made it dry combines The layer of object.The thickness of adhesive phase is not particularly limited, but preferably 5 μm or more, and more preferable 10 μm or more, further preferably 15 μm or more.In addition, thickness be preferably 200 μm hereinafter, more preferable 100 μm hereinafter, further preferred 50 μm or less.Thickness is excessively thin When, exist and is unable to fully the case where obtaining bond properties；And thickness it is blocked up when, can enumerate following problem: it is dry insufficient and Residual solvent is set to be easy to become more, to generate bubble when manufacturing the printing of printed circuit board.
It as the method for the coating adhesive composition on substrate, is not particularly limited, but the painting of comma roll-type can be enumerated Cloth machine and reverse roll coater etc..Alternatively, as needed, in the rolled copper foil as printed circuit board constituent material or can gather Transfer printing setting adhesive phase is directed or through on acid imide film.Drying condition is not particularly limited, but after preferred drying Residual solvent rate be 1 mass % or less.When residual solvent rate is more than 1 mass %, following problems can be enumerated: printed circuit board print When processed, residual solvent foams and generates bubble.
<resin base material>
For the resin base material in the present invention, as long as dry adhesive composition of the invention can be coated with and form bonding If the material of oxidant layer, there is no particular limitation, but the resin base materials such as preferred film shape resin are (hereinafter also referred to as base material film Layer).Specifically, can example to go out polyester resin, polyamide, polyimide resin, polyamide-imide resin, liquid crystal poly- Conjunction object (LCP), polyphenylene sulfide, syndiotactic polytyrene, polyolefin-based resins and fluorine resin etc..As the commercial product of LCP film, For example, the ベ Network ス タ ー (registered trademark) of Kuraray Co., Ltd. (Network ラ レ) system can be enumerated.In addition, as polyimide film Commercial product, for example, can enumerate Kanegafuchi Chemical Ind (カ ネ カ) system ア ピ カ Le (registered trademark).
It for the thickness of resin base material, is not particularly limited, but preferably 1 μm or more, more preferable 3 μm or more, into one Preferably 10 μm or more of step.In addition, the thickness be preferably 50 μm hereinafter, more preferable 30 μm hereinafter, further preferred 20 μm or less.It is thick When spending thin, there is the case where abundant electric property for being difficult to obtain circuit；On the other hand, when thickness is blocked up, there are circuit systems The case where processing efficiency when making etc. declines.In addition, relative dielectric constant (the ε of resin base materialc) it is preferably 5.0 hereinafter, more excellent It selects 4.0 hereinafter, further preferred 3.5 or less.The lower limit value of the relative dielectric constant is not particularly limited, industrially for example If 0.1 or more.
<metal base>
As metal base, any known conductive material that can be used in circuit substrate can be used.As this Material, can example go out the various metals such as SUS, copper, aluminium, iron, steel, zinc and nickel and their own alloy, plated article, with zinc or Other metals such as chromium compound treated metal etc..Preferably metal foil, more preferable copper foil.For the thickness of metal foil, and To being not particularly limited, but preferably 1 μm or more, more preferable 3 μm or more, further preferred 10 μm or more.In addition, the thickness is excellent Be selected as 50 μm hereinafter, more preferable 30 μm hereinafter, further preferred 20 μm or less.When thickness is excessively thin, exists and be difficult to obtain circuit The case where abundant electric property；On the other hand, when thickness is blocked up, the case where decline there are the processing efficiency etc. when circuit production. For metal foil, provided usually in the form of web-like.Used metal foil when manufacture printed circuit board of the invention Form be not particularly limited.Using belt shape metal foil when, length is not particularly limited.In addition, its width Also it is not particularly limited, but preferably 250~500cm or so.
<laminated body>
Laminated body (Z) of the invention is that resin base material and metal base carry out that the stack to be formed is laminated by adhesive phase (resin base material/3 layer laminates of adhesive phase/metal base), laminated body (X) are that stacking resin base material and adhesive phase form Laminated body (resin base material/adhesive phase), laminated body (Y) be laminated body made of laminated metal substrate and adhesive phase (gold Belong to substrate/adhesive phase).In the present invention, exists and laminated body (X), laminated body (Y) and laminated body (Z) are all referred to as laminated The case where body.Laminated body (X) is that adhesive composition is conventionally coated on resin base material and is dried and obtains 's.In addition, laminated body (Y) is that adhesive composition is conventionally coated on metal base and is dried and obtains 's.Laminated body (Z) is by the way that laminated metal substrate or resin base material and obtain respectively on laminated body (X) or laminated body (Y). Release substrate can also be folded on the adhesive level upper layer of laminated body (X) or laminated body (Y).In addition, the resin base material of laminated body (Z) Or it can also further laminate adhesive oxidant layer (adhesive phase/resin base material/adhesive phase/metal base, resin base on metal base Material/adhesive phase/metal base/adhesive phase, adhesive phase/resin base material/adhesive phase/metal base/adhesive phase).
Laminated body of the invention also meets following requirement (1)~(4).
It is required that (1)
To requiring (1) to be illustrated.In laminated body (Z) of the present invention, under the frequency 1MHz for needing adhesive phase Relative dielectric constant (εc) it is 3.0 or less.Specifically, after adhesive composition being coated on release substrate to make it dry With a thickness of 25 μm, and it is about 3 minutes dry at about 130 DEG C.Then, it is heat-treated about 4 hours and is solidified at about 140 DEG C, and Adhesive composition layer (adhesive phase) after removing solidifies from release film.Measure the adhesive composition layer after removing Relative dielectric constant (ε under frequency 1MHzc).Relative dielectric constant (εc) be 3.0 hereinafter, it is preferred that 2.6 hereinafter, more preferable 2.3 with Under.Relative dielectric constant (εc) lower limit be not particularly limited, but it is practical it is upper be 2.0.In addition, frequency 1MHz~10GHz Relative dielectric constant (ε in entire areac) it is preferably 3.0 hereinafter, more preferable 2.6 hereinafter, further preferred 2.3 or less.
Relative dielectric constant (the ε of the adhesive phase in laminated body (Z) can be measured as followsc).That is, can show Example goes out the following method: neatly removing the metal base of laminated body (Z) with etching solution, obtains adhesive phase and resin base material Two-layer laminate body (X).Etching is also not particularly limited, ferric chloride in aqueous solution, copper chloride solution, sulfuric acid mistake can be used Hydrogen oxide water mixes liquid, alkaline etching and nickel etchant etc..Then, the resin base material of (removal) laminated body (X) is neatly removed, By carrying out the methods of the membrane processes such as vapor deposition and sputtering method or applying conductive paste on two surfaces of remaining adhesive layer, It forms metal layer and as capacitor, measures capacitance, and according to thickness and area, calculate relative dielectric constant (εc).In addition, As method for distinguishing, metal layer can be formed on the resin base material face of laminated body (X) according to the method described above, and as capacitor, In the combined capacity amount relative dielectric constant (ε of measurement resin base material and adhesive phasec) after, it is neatly shelled from laminated body (X) From (removal) metal layer and adhesive phase, and equally to the relative dielectric constant (ε of cull substratec) capacitor is carried out, Measure capacitance.Since the dielectric layer of the capacitor obtained based on laminated body (X) can be considered the more of resin base material and adhesive phase Therefore layer dielectric can calculate the relative dielectric constant (ε of adhesive phase according to difference between the twoc)。
It is required that (2)
To requiring (2) to be illustrated.In laminated body (Z) of the present invention, under the frequency 1MHz for needing adhesive phase Dielectric loss angle tangent (tan δ) is 0.02 or less.Specifically, adhesive composition is coated on release substrate so that it is done After dry with a thickness of 25 μm, and dry about 3 minutes at about 130 DEG C.Then, it is heat-treated about 4 hours and is consolidated at about 140 DEG C Change, the adhesive composition layer (adhesive phase) after removing solidifies from release film.The adhesive composition after measurement removing Frequency 1MHz under dielectric loss angle tangent (tan δ).Dielectric loss angle tangent (tan δ) is 0.02 hereinafter, preferably 0.01 Hereinafter, more preferable 0.005 or less.The lower limit of dielectric loss angle tangent (tan δ) is not particularly limited, and practical is above 0.0001. In addition, the dielectric loss angle tangent (tan δ) in the entire area of frequency 1MHz~10GHz is preferably 0.02 hereinafter, more preferable 0.01 Hereinafter, further preferred 0.005 or less.
It, can also be according to normal with above-mentioned dielectric for the dielectric loss angle tangent (tan δ) of the adhesive phase in laminated body (Z) The identical operation of number is measured.
It is required that (3)
(3) will be required to be illustrated.In laminated body (Z) of the present invention, need between resin base material and metal base Peel strength be 0.5N/mm or more.Specifically, adhesive composition is coated on resin base material with the thickness after making it dry Degree is about 25 μm, and about 3 minutes dry at about 130 DEG C.Then, it is pasted on the surface of adhesive composition layer (adhesive phase) Close metal base.Fitting refer in a manner of contacting the glassy surface of metal base with adhesive composition layer, about 160 DEG C, About 40kgf/cm2Pressurization under vacuum suppress and bonded for about 30 seconds.Then, it is heat-treated about 4 hours and is consolidated at about 140 DEG C Change, makes resin base material/3 layer laminates of adhesive phase/metal base (Z).Under room temperature (about 25 DEG C), in tensile speed The resin base material of the laminated body (Z) is removed under 50mm/min with 90 °, measures peel strength.90 ° of peel strengths are needed in 0.5N/ Mm or more, preferably 0.8N/mm or more, more preferable 1.0N/mm or more.In addition, even by the method other than the above method Made laminated body (Z) is also included in the present invention as long as its 90 ° of peel strengths are 0.5N/mm or more.
It, can be by layer by being bonded metal base on the surface of the adhesive composition layer of laminated body (X) (adhesive phase) Stack (X) obtains laminated body (Z) of the invention.Fitting refers to so that the glassy surface of metal base is contacted with adhesive composition layer Mode, in about 160 DEG C, about 40kgf/cm2Pressurization under vacuum suppress and bonded for about 30 seconds.Then, hot at about 140 DEG C Processing is solidified for about 4 hours, makes resin base material/3 layer laminates of adhesive phase/metal base (Z).In room temperature (about 25 DEG C) under, the resin base material of the laminated body (Z) is removed with 90 ° at tensile speed 50mm/min, measures peel strength.90 ° of removings Intensity is needed in 0.5N/mm or more, preferably 0.8N/mm or more, more preferable 1.0N/mm or more.
It, can be by layer by being bonded resin base material on the surface of the adhesive composition layer of laminated body (Y) (adhesive phase) Stack (Y) obtains laminated body (Z) of the invention.It is bonded and refers in a manner of contacting resin base material with adhesive composition layer, In about 160 DEG C, about 40kgf/cm2Pressurization under vacuum suppress and bonded for about 30 seconds.Then, about 4 are heat-treated at about 140 DEG C Hour is solidified, and resin base material/3 layer laminates of adhesive phase/metal base (Z) are made.Under room temperature (about 25 DEG C), The resin base material of the laminated body (Z) is removed under tensile speed 50mm/min with 90 °, measures peel strength.90 ° of peel strengths need In 0.5N/mm or more, preferably 0.8N/mm or more, more preferable 1.0N/mm or more.
By being bonded resin base material on a face of adhesive phase, the gloss of metal base is bonded on its another face Face can be obtained laminated body of the invention (Z) by adhesive phase.Fitting refers in about 100 DEG C, about 3kgf/cm2Pressurization under with about 1m/min roll laminating after being bonded release substrate/adhesive phase and resin base material, removes release substrate, so that the light of metal base The mode that damp face is contacted with adhesive composition layer, in about 160 DEG C, about 40kgf/cm2Pressurization under vacuum suppress about 30 seconds into Row bonding.Then, it is heat-treated about 4 hours and is solidified at about 140 DEG C, make resin base material/adhesive phase/metal base 3 layer laminates (Z).Under room temperature (about 25 DEG C), the resin of the laminated body (Z) is removed with 90 ° at tensile speed 50mm/min Substrate measures peel strength.90 ° of peel strengths are needed in 0.5N/mm or more, preferably 0.8N/mm or more, more preferable 1.0N/ Mm or more.
It is required that (4)
To requiring (4) to be illustrated.It is 240 DEG C or more that laminated body (Z) of the present invention, which needs to soak scolding tin heat resistance,. Specifically, adhesive composition is coated on resin base material with after making it dry with a thickness of 25 μm, it is dry at about 130 DEG C About 3 minutes.Then, metal base is bonded on the surface of adhesive composition layer (adhesive phase).Fitting refers to so that Metal Substrate The mode that the glassy surface of material is contacted with adhesive composition layer, in about 160 DEG C, about 40kgf/cm2Pressurization under vacuum compacting about It is bonded within 30 seconds.Then, it is heat-treated about 4 hours and is solidified at about 140 DEG C, make resin base material/adhesive phase/metal 3 layer laminates (Z) of substrate.The laminated body (Z) is handled under conditions of about 40 DEG C, about 80RH% about 72 hours, and in each temperature It is flowed 1 minute in solder bath after the lower fusing of degree, measurement does not generate the temperature of the cosmetic variations such as blistering (swollen れ).It is resistance to soak scolding tin Hot needs are at 240 DEG C or more, and preferably 250 DEG C or more, more preferable 260 DEG C or more.In addition, even by the above method with Laminated body made by outer method (Z) is also included in the present invention as long as it is 240 DEG C or more that it, which soaks scolding tin heat resistance,.
It, can be by layer by being bonded metal base on the surface of the adhesive composition layer of laminated body (X) (adhesive phase) Stack (X) obtains laminated body (Z) of the invention.Fitting refers to so that the glassy surface of metal base is contacted with adhesive composition layer Mode, in about 160 DEG C, about 40kgf/cm2Pressurization under vacuum suppress and bonded for about 30 seconds.Then, hot at about 140 DEG C Processing is solidified for about 4 hours, makes resin base material/3 layer laminates of adhesive phase/metal base (Z).About 40 DEG C, about The laminated body (Z) is handled under conditions of 80RH% about 72 hours, and flow 1 minute in the solder bath after fusing at each temperature, Measurement does not generate the temperature of the cosmetic variations such as blistering.It soaks scolding tin heat resistance to need at 240 DEG C or more, preferably 250 DEG C or more, More preferable 260 DEG C or more.
It, can be by layer by being bonded resin base material on the surface of the adhesive composition layer of laminated body (Y) (adhesive phase) Stack (Y) obtains laminated body (Z) of the invention.It is bonded and refers in a manner of contacting resin base material with adhesive composition layer, In about 160 DEG C, about 40kgf/cm2Pressurization under vacuum suppress and bonded for about 30 seconds.Then, about 4 are heat-treated at about 140 DEG C Hour is solidified, and resin base material/3 layer laminates of adhesive phase/metal base (Z) are made.In about 40 DEG C, about 80RH% Under the conditions of handle the laminated body (Z) about 72 hours, and at each temperature melt after solder bath in flow 1 minute, measure do not produce The temperature of the cosmetic variations such as raw blistering.It soaks scolding tin heat resistance to need at 240 DEG C or more, preferably 250 DEG C or more, more preferably 260 DEG C or more.
In addition, being bonded resin base material on a face for passing through adhesive phase, metal base is bonded on its another face Glassy surface can be obtained laminated body of the invention (Z) by adhesive phase.It is bonded and refers to after adhesive phase is bonded with resin base material, In a manner of glassy surface to make metal base is contacted with adhesive composition layer, in about 160 DEG C, about 40kgf/cm2Pressurization under Vacuum is suppressed about 30 seconds and is bonded.Then, it is heat-treated about 4 hours and is solidified at about 140 DEG C, production resin base material/viscous 3 layer laminates of mixture layer/metal base (Z).It is small that the laminated body (Z) about 72 is handled under conditions of about 40 DEG C, about 80RH% When, and flowed 1 minute in the solder bath after fusing at each temperature, measurement does not generate the temperature of the cosmetic variations such as blistering.Wetting Scolding tin heat resistance is needed at 240 DEG C or more, and preferably 250 DEG C or more, more preferable 260 DEG C or more.
<adhesive composition>
Adhesive composition used in the present invention includes at least: carboxylic polyolefin-based resins (A).By containing The polyolefin-based resins (A) of carboxyl can embody above-mentioned by the laminated body for the adhesive phase being made of the adhesive composition (1)~(4) excellent performance.
Adhesive composition of the invention preferably other than containing above-mentioned (A) ingredient, also contains: carboxylic styrene Resin (B) (hereinafter, also referred to as (B) ingredient), carbodiimide resin (C) (hereinafter, also referred to as (C) ingredient) and/or epoxy Resin (D) (hereinafter, also referred to as (D) ingredient).By containing this 4 kinds of resins of above-mentioned (A) ingredient~(D) ingredient, it is not only to pass The polyimides and polyester film of system, even the low polar resin substrate of unimagined LCP film etc. in the prior art, can also have With the high adherence of metal base, high scolding tin heat resistance can be obtained, and low dielectric property is excellent.
<carboxylic styrene resin (B)>
There is no restrictions for workable carboxylic styrene resin (B) in the present invention, but preferably use unsaturated carboxylic acid Modified following substance forms: with the homopolymerization of aromatic ethenyl compound or aromatic ethenyl compound and conjugated diene The block of compound and/or the copolymer based on disordered structure and its hydride.As aromatic ethenyl compound, and It is not particularly limited, for example, styrene, t-butyl styrene, α-methylstyrene, p-methylstyrene, divinyl can be enumerated Base benzene, 1,1- diphenyl benzene ethylene, N, N- diethyl-is to amino-ethyl styrene, vinyltoluene and p-tert-butylstyrene Deng.In addition, as conjugated diene compound, for example, butadiene, isoprene, 1,3-pentadiene, 2,3- dimethyl-can be enumerated 1,3- butadiene etc..It, can as the specific example of these aromatic ethenyl compounds and the copolymer of conjugated diene compound Enumerate styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene ethylene-propylene-styrene block copolymer (SEPS) and styrene-ethylene-ethylene propylene-styrene block copolymer (SEEPS) etc..
The modification of carboxylic styrene resin (B), for example, can by the polymerization of styrene resin, make its with not Saturated carboxylic acid is copolymerized and carries out.In addition, can also in the presence of organic peroxides, by heating mixing styrene resin and not Saturated carboxylic acid and carry out.As unsaturated carboxylic acid, be not particularly limited, can enumerate acrylic acid, methacrylic acid, maleic acid, Itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride and fumaric acid anhydride etc..
From heat resistance and with from the viewpoint of the adhesiveness of resin base material or metal base, carboxylic styrene resin (B) lower limit of acid value is preferably 10 equivalent/106G or more, more preferable 100 equivalent/106G or more, further preferred 150 equivalent/ 106g.When acid value is less than above-mentioned value, exists low with the compatibility of epoxy resin (D), carbodiimide resin (C) and can not embody viscous The case where closing intensity.In addition, it is low there is also crosslink density and the case where lack heat resistance.The upper limit of acid value is preferably 1000 to work as Amount/106G is hereinafter, more preferable 700 equivalent/106G is hereinafter, further preferred 500 equivalent/106G or less.Acid value is more than above-mentioned value When, the case where decline there are adhesiveness and low dielectric property.
In adhesive composition used in the present invention, for the content of carboxylic styrene resin (B), relative to containing 5~95 mass parts of polyolefin resin (A) of carboxyl, carboxylic styrene resin (B) is preferably in the range of 95~5 mass parts It is interior, i.e. (A) ingredient/ingredient=5~95/95~5 (B) (mass ratio).More preferably (A) ingredient/ingredient=10~90/90 (B)~ 10 (mass ratioes), most preferably (A) ingredient/(B) ingredient is in the range of 15~85/85~15 (mass ratio).(A) component amount is less than The case where when above-mentioned value, there are crosslink densities to reduce, wetting scolding tin heat resistance decline.(A) when component amount is more than above-mentioned value, exist The case where wetability decline of substrate, adhesive strength are reduced.
<carbodiimide resin (C)>
It is not particularly limited as carbodiimide resin (C) as long as its intramolecular has carbodiimide group.It is preferred that Intramolecular has the poly- carbodiimide of 2 or more carbodiimide groups.It is carboxylic poly- by using carbodiimide resin (C) The carboxyl of olefin resin (A) or carboxylic styrene resin (B) is reacted with carbodiimide, can increase adhesive composition and base Interaction between material, and adhesiveness can be improved.
In adhesive composition used in the present invention, relative to carboxylic polyolefin resin (A) and carboxylic benzene Total 100 mass parts of vinyl (B), the content of carbodiimide resin (C) is preferably in the range of 0.1~30 mass parts. More preferably in the range of 1~25 mass parts, most preferably in the range of 2~20 mass parts.When the content is less than above-mentioned value, deposit The problem of can not embody the interaction with substrate, adhesiveness reduces.When the content is more than above-mentioned value, there are the suitable of adhesive The problem of being reduced with phase reduction, low dielectric property.
<epoxy resin (D)>
As epoxy resin (D), as long as having glycidyl in its molecule, there is no particular limitation, but preferred molecule In with 2 or more glycidyls epoxy resin.Specifically, epoxy resin (D) is not particularly limited, but choosing can be used Free biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolaks type ring Oxygen resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, four glycidyl group diaminodiphenylmethane, three are shunk The double aminomethyl cyclohexanones of glyceryl para-aminophenol, four glycidyl group and N, N, N', N'- four glycidyl group meta-xylene At least one of the group that diamines is constituted.It is preferred that bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin or dicyclopentadiene type Epoxy resin.
In adhesive composition used in the present invention, relative to carboxylic polyolefin resin (A) and carboxylic benzene Total 100 mass parts of vinyl (B), the content of epoxy resin (D) is preferably in the range of 1~30 mass parts, more preferably In the range of 2~15 mass parts, most preferably in the range of 3~10 mass parts.When the content is less than above range, there are nothings Method obtains the case where sufficient solidification effect, adhesiveness and heat resistance reduce.In addition, being deposited when the content is more than above range The problem of the working life of adhesive reduces, low dielectric property reduces.
Organic solvent can also be contained in adhesive composition used in the present invention.For organic molten used in the present invention Agent, as long as it is to dissolve carboxylic polyolefin resin (A), carboxylic styrene resin (B), carbodiimide resin (C) With the organic solvent of epoxy resin (D), just it is not particularly limited.Specifically, for example, can be used: benzene, toluene and dimethylbenzene etc. Aromatic hydrocarbon, the fatty families hydrocarbon such as hexane, heptane, octane and decane, hexamethylene, cyclohexene, hexahydrotoluene and cyclohexyl The clicyclic hydrocarbons such as alkane, the halogenated hydrocarbons such as trichloro ethylene, dichloroethylene, chlorobenzene and chloroform, methanol, ethyl alcohol, isopropanol, butanol, amylalcohol, The alcohol series solvents such as hexanol, propylene glycol and phenol, it is acetone, methyl iso-butyl ketone (MIBK), methyl ethyl ketone, pentanone, hexanone, cyclohexanone, different The ketone series solvents such as phorone and acetophenone, the dioxanes such as methyl cellosolve and ethyl cellosolve, methyl acetate, ethyl acetate, The ester series solvents such as butyl acetate, methyl propionate and butyl formate, ethylene glycol list n-butyl ether, ethylene glycol list isobutyl ether, second two Alcohol list tertbutyl ether, diethylene glycol list n-butyl ether, diethylene glycol list isobutyl ether, triethylene glycol list n-butyl ether and tetrem two Glycol ether series solvents such as alcohol list n-butyl ether etc.；And one of these can be used or be used in combination two or more.
Relative to total 100 mass parts of carboxylic polyolefin resin (A) and carboxylic styrene resin (B), have Solvent preferably in the range of 100~1000 mass parts, more preferably in the range of 200~900 mass parts, most preferably exists In the range of 300~800 mass parts.When the content of organic solvent is less than above range, decline there are liquid and working life property Situation.In addition, in terms of manufacturing cost and transportation cost, there are unfavorable when the content of organic solvent is more than above range The problem of.
In addition, as needed, other ingredients can be also contained in adhesive composition used in the present invention.As such The specific example of ingredient can enumerate fire retardant, tackifier, filler and silane coupling agent.
<fire retardant>
As needed, fire retardant can be also mixed into adhesive composition used in the present invention.As fire retardant, can enumerate Bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, hydroxide metallic compound etc..Wherein, preferred phosphorus flame retardant, can make With phosphate (for example, trimethyl phosphate, triphenyl phosphate, tricresyl phosphate etc.), phosphate (for example, phosphinic acids aluminium etc.), Phosphorus flame retardant well known to phosphonitrile etc..These can be used alone or are used in any combination two or more.When containing fire retardant, phase For total 100 mass parts of (A)~(D) ingredient, the content of fire retardant is preferably in the range of 1~200 mass parts, more preferably In the range of 5~150 mass parts, most preferably in the range of 10~100 mass parts.When the content is less than range, there is resistance The low situation of combustion property.When the content is more than above range, there are problems that the variation such as adhesiveness, heat resistance and electrical characteristic.
<tackifier>
As needed, tackifier can be also mixed into adhesive composition used in the present invention.As tackifier, can enumerate Polyterpene resin, rosin series resin, fatty family Petropols, alicyclic ring family Petropols, copolymerization through-stone oleoresin, styrene Resin and hydrogenated petroleum resin etc. are used to improve adhesive strength.These can be used alone or will be two or more It is used in any combination.
<filler>
As needed, the fillers such as silica can be also mixed into adhesive composition used in the present invention.By being mixed into The characteristic of heat resistance can be improved in silica, thus, very preferably.It is generally known to have hydrophobicity titanium dioxide as silica Silicon and hydrophilic silicon oxides, but herein, in terms of assigning resistance to hygroscopicity, preferably use two silicon of dimethyldichlorosilane or hexamethyl Azane, octyl silane etc. carry out treated hydrophobic silica.Add up to 100 mass parts relative to (A)~(D) ingredient, The combined amount of silica is preferably the combined amount of 0.05~30 mass parts.When the combined amount is less than 0.05 mass parts, there are nothings Method plays the case where heat resistance improvement effect.On the other hand, when which is more than 30 mass parts, there are following situations: generating The bad dispersion of silica, solution viscosity excessively get higher and generate the bad state of operability or adhesiveness decline.
<silane coupling agent>
As needed, silane coupling agent can be also mixed into adhesive composition used in the present invention.By being mixed into silane The characteristic of the adhesiveness or heat resistance to metal can be improved in coupling agent, thus, very preferably.As silane coupling agent, not It is particularly limited to, the silane coupling agent with unsaturated group, the silane coupling agent with glycidyl can be enumerated and there is ammonia The silane coupling agent etc. of base.In these, from the viewpoint of heat resistance, more preferable γ-glycidoxypropyl trimethoxy Silane or β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane or β-(3,4- epoxycyclohexyl) ethyl triethoxysilane Deng the silane coupling agent with glycidyl.Relative to total 100 mass parts of (A)~(D) ingredient, silane coupling agent is mixed Resultant is preferably the combined amount of 0.5~20 mass parts.When the combined amount is less than 0.5 mass parts, the case where there are heat resistance variation. On the other hand, when which is more than 20 mass parts, the case where decline there are poor heat resistance or adhesiveness.
<adhesive sheet>
In the present invention, adhesive sheet refers to be stated laminated body (Z) and forms with release substrate by the way that adhesive composition layer is stacked on Adhesive sheet, or release substrate is laminated on the face of laminated body (X) or the adhesive phase of laminated body (Y) and the bonding that is formed Sheet material, or release substrate is laminated at least one face of adhesive phase and the adhesive sheet that is formed.It is constituted as specific Form, can enumerate release substrate/adhesive phase, release substrate/adhesive phase/release substrate, resin base material/adhesive phase/from Type substrate, metal base/adhesive phase/release substrate, laminated body/adhesive phase/release substrate or release substrate/adhesive Layer/laminated body/adhesive phase/release substrate.By the way that release substrate is laminated, function it as the protective layer of substrate.Separately Outside, by using release substrate, release substrate can be removed from adhesive sheet, and adhesive phase is further transferred to other base On material.
Conventionally, by the way that adhesive composition used in the present invention is coated on various laminated bodies and is carried out It is dry, adhesive sheet of the invention can be obtained.In addition, after the drying, when adhesive phase is fitted in release substrate, making not generate Substrate batches be possibly realized set-off occurs, and operability is excellent, meanwhile, adhesive phase can be protected, thus, keeping quality is excellent, makes With being also easy.In addition, after dry to the coating of release substrate, it as needed, also can be by adhesive when being bonded other release substrate Layer is transferred to other substrates in itself.
<release substrate>
It as release substrate, is not particularly limited, for example, material below can be enumerated: in good quality paper (pure Paper), the coating of filler (clay, polyethylene and polypropylene etc.) is set on the two sides of the paper such as brown paper, roll web and glassine paper Layer, and be coated on its each coating layer silicone-based, fluorine system, alkyd system release agent and the material that is formed.In addition, can also enumerate Various individual alkene films such as polyethylene, polypropylene, ethene-alpha-olefin copolymer, propylene-alpha-olefin copolymers and poly- to benzene The material for being coated with above-mentioned release agent on the films such as naphthalate and being formed.Based on the stripping between release substrate and adhesive phase The reasons such as electrical characteristic adverse effect can be given from power and silicone, reclaimed polypropylene is carried out preferably on the two sides of good quality paper and fills place Reason and the material formed above it using alkyd system release agent use alkyd system on polyethylene terephthalate Release agent and the material formed.
<printed circuit board>
" printed circuit board " in the present invention includes the stacking formed by the metal foil and resin base material of formation conductor circuit Body is as constituent element.For printed circuit board, for example, can be by using metal-clad stack and previous public according to subtractive process etc. The method known is manufactured.Circuit board below can be referred to as: as needed, with the part such as cover film or screen printing ink or entirely Portion's covering so-called flexible circuit board (FPC), flat cable, automatic carrier band welding formed by the conductor circuit that metal foil is formed (TAB) circuit board etc..
Printed circuit board of the invention, which has, is used as the adoptable any stepped construction of printed circuit board.For example, can serve as reasons The printed circuit board of this 4 layers composition of substrate film layer, metal foil layer, adhesive phase and cover layer.In addition, for example, can be for by base The printed circuit board of this 5 layers composition of material film layer, adhesive phase, metal foil layer, adhesive phase and cover layer.
Further, as needed, above-mentioned printed circuit board can also form 2 layers or 3 layers or more the structures being laminated.
Adhesive composition used in the present invention can be suitably used for each adhesive phase of printed circuit board.In particular, this hair It is bright used in adhesive composition as adhesive in use, not only with traditionally composition printed circuit board polyimides, Polyester film and copper foil, also low polar resin substrate has high adherence with LCP's etc., and can obtain resistance to scolding tin reflux, bonds The low dielectric property of oxidant layer itself is excellent.Therefore, it is suitable as institute in the copper foil and adhesive sheet of cover film, plywood, resin The adhesive composition used.
In printed circuit board of the invention, as base material film, it can be used and used as the substrate of previous printed circuit board Any resin film.As the resin of base material film, can example go out polyester resin, polyamide, polyimide resin, polyamide Imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polytyrene, polyolefin-based resins and fluorine resin etc..In particular, Even for the low polar substrates such as liquid crystal polymer, polyphenylene sulfide, syndiotactic polytyrene and polyolefin-based resins, it may have excellent Adhesiveness.
<cover film>
As cover film, known any insulating film as printed circuit board insulating film can be used.For example, can Using by polyimides, polyester, polyphenylene sulfide, polyether sulfone, polyether-ether-ketone, aromatic polyamides, polycarbonate, polyarylate, polyamides The various polymer such as imines, polyamidoimide, liquid crystal polymer, polyphenylene sulfide, syndiotactic polytyrene and polyolefin-based resins Manufactured film.More preferably polyimide film or liquid crystalline polymer film.
For printed circuit board of the invention, other than the material of above layers can be used, also can be used previous known Any means manufacture.
In one preferred embodiment, the semi-finished product that adhesive phase has been laminated on cover layer and has been formed are manufactured (hereinafter referred to as " cover film side semi-finished product ").On the other hand, manufacture is folded desired by metal foil layer and formation on substrate film layer upper layer Circuit pattern semi-finished product (hereinafter referred to as " two layers of base material film side semi-finished product ") or substrate film layer upper layer fold adhesive phase simultaneously Above it laminated metal layers of foil and formed desired circuit pattern semi-finished product (hereinafter referred to as " and base material film side three and half at Product ") (hereinafter, two layers of base material film side semi-finished product and three layers of base material film side semi-finished product are referred to as " base material film side semi-finished product ").It is logical It crosses thus obtained cover film side semi-finished product and the fitting of base material film side semi-finished product, can get four layers or five layers of printed circuit Plate.
For base material film side semi-finished product, for example, can obtain by the inclusion of the autofrettage of following process: (A) is in above-mentioned gold The process for belonging to the solution that the resin as base material film is coated on foil and initial dry coating；(B) to metal foil obtained in (A) The dry process of heat treatment (hereinafter referred to as " heat treatment and desolventizing process ") is carried out with the sandwich of initial dry coating.
Circuit in metal foil layer is formed, known method can be used.Activation method or subtractive process can be used.It is excellent Select subtractive process.
For resulting base material film side semi-finished product, it can be directly bonded with cover film side semi-finished product to use, Huo Zhe After fitting release film is taken care of, it is bonded with cover film side semi-finished product to use.
For cover film side semi-finished product, for example, can by cover film coating adhesive manufacture.As needed, may be used Cross-linking reaction is carried out in adhesive after coating.In a preferred embodiment, make adhesive phase semi-solid preparation.
For resulting cover film side semi-finished product, it can be directly bonded with base material film side semi-finished product to use, Huo Zhe After fitting release film is taken care of, it is bonded with base material film side semi-finished product to use.
For base material film side semi-finished product and cover film side semi-finished product, for example, can be pasted after keeping in the form of volume respectively It closes and manufactures printed circuit board.As the method for fitting, any means can be used, for example, being pasted using pressuring machine or roller etc. It closes.In addition, can also be by using the methods of hot press or heating roller arrangement, the two is bonded by the side Bian Jiare.
For armature side semi-finished product, for example, being suitable for when using the armature that soft can be batched as polyimide film By on armature coating adhesive manufacture.In addition, for example, making glass using metal plates such as SUS and aluminium, with epoxy resin It is viscous on release substrate advantageously by that will be coated in advance when the stiffening plate that can not be batched firmly as plate after fiber solidifying etc. Mixture carries out print-on coating to manufacture.In addition, as needed, cross-linking reaction can be carried out in adhesive after coating.Preferred Embodiment in, make adhesive phase semi-solid preparation.
For resulting armature film side semi-finished product, it can be directly bonded to use with printed circuit back, or After fitting release film is taken care of, it is bonded with base material film side semi-finished product to use.
Base material film side semi-finished product, cover film side semi-finished product and reinforcing agent side semi-finished product are the printed circuit board in the present invention Use laminated body.
<embodiment>
Hereinafter, the present invention will be described in more detail by enumerating embodiment.However, the invention is not limited to this A little embodiments.Part of abbreviation indicates mass parts in embodiment and comparative example.
(evaluation of physical property method)
Acid value (A) ingredient: carboxylic polyolefin resin
About acid value (equivalent/10 in the present invention6G), using FT-IR, (society, Shimadzu Seisakusho Ltd. is manufactured, FT- IR8200PC), using the flexible peak (1780cm of the carbonyl of maleic anhydride (C=O) key-1) absorbance (I), isotactic spy Levy peak (840cm-1) absorbance (II) and the standard curve institute that is made by the chloroformic solution of maleic anhydride (Tokyo chemical conversion system) The value calculated according to following formula, is expressed as equivalent (equivalent/10 in resin 1ton by the factor (f) obtained6g)。
Acid value=[absorbance (I)/absorbance (II) × (f)/maleic anhydride molecular weight × 2 × 104]
The molecular weight of maleic anhydride: 98.06
Acid value (B) ingredient: carboxylic styrene resin
Acid value (equivalent/10 in the present invention6G) it is measured in the following manner: by carboxylic styrene resin It is dissolved in toluene, uses the methanol solution of sodium methoxide and is titrated using phenolphthalein as indicator.The acid value is in resin 1ton Equivalent (equivalent/106G) it indicates.
Weight average molecular weight (Mw)
Weight average molecular weight in the present invention is by gel permeation chromatography (hereinafter referred to as GPC, standard substance: polystyrene Resin, mobile phase: tetrahydrofuran) value that is measured.
(1) peel strength (adhesiveness)
Aftermentioned adhesive composition is coated on thick 12.5 μm of polyimide film, and (Co., Ltd.'s clock is made at (カ ネ カ) Make, ア ピ カ Le) or thick 25 μm of LCP film (Kuraray Co., Ltd. (Network ラ レ) manufacture, ベ Network ス タ ー) on make it dry Afterwards with a thickness of 25 μm, dry 3 minutes at 130 DEG C.By thus obtained adhesiveness film (B-stage product) and 18 μm of calendering copper Foil fitting.Fitting is in a manner of making the glassy surface of rolled copper foil contact with adhesive, in 160 DEG C, 40kgf/cm2Pressurization under Compacting is bonded for 30 seconds.Then, it is heat-treated 4 hours and is solidified at 140 DEG C, obtain peel strength sample for evaluation. About peel strength, at 25 DEG C, film stretching is carried out, and 90 ° of disbonded tests are carried out at tensile speed 50mm/min, measurement stripping From intensity.The test is to show the test of adhesive strength under room temperature.
<evaluation criterion>
◎: 1.0N/mm or more
Zero: 0.8N/mm or more, and it is less than 1.0N/mm
Δ: 0.5N/mm or more, and it is less than 0.8N/mm
×: less than 0.5N/mm
(2) dry scolding tin heat resistance
Sample is made by method same as described above, and 2.0cm × 2.0cm sample strip is dried at 120 DEG C It 30 minutes, flows 1 minute in melting solder bath at each temperature, measurement does not generate the temperature of the cosmetic variations such as blistering.
<evaluation criterion>
◎: 310 DEG C or more
Zero: 300 DEG C or more, and less than 310 DEG C
Δ: 290 DEG C or more, and less than 300 DEG C
×: less than 290 DEG C
(3) scolding tin heat resistance is soaked
Sample is made by method same as described above, and by 2.0cm × 2.0cm sample strip at 40 DEG C × 80RH% It manages 72 hours, is flowed 1 minute in melting solder bath at each temperature, measurement does not generate the temperature of the cosmetic variations such as blistering.
<evaluation criterion>
◎: 260 DEG C or more
Zero: 250 DEG C or more, and less than 260 DEG C
Δ: 240 DEG C or more, and less than 250 DEG C
×: less than 240 DEG C
(4) relative dielectric constant (εc) and dielectric loss angle tangent (tan δ)
Aftermentioned adhesive composition is coated on to the glassy surface of 35 μm of thickness of electrolytic copper foil, makes it dry the thickness after solidifying Degree is 25 μm, and 3 minutes dry at 130 DEG C.Then, it is heat-treated 4 hours and is solidified at 140 DEG C, obtain test Copper-clad laminated board.It is steamed on adhesive composition face after the solidification of the copper-clad laminated board of gained test using silk-screen printing coating The conductive silver paste of dry curable type makes the circle of its diameter 50mm, dry solidification 30 minutes at 120 DEG C, and passes through conduction Property adhesive the lead of long 30mm is bonded in the center of the circle being made of conductive silver paste, obtain parallel plate capacitor.Make With PRECISION LCR meter HP-4284A, under conditions of 22 DEG C, frequency 1MHz, measurement gained parallel plate capacitor Capacitance CapRelative dielectric constant (ε is calculated and by following formula with loss factor D (dielectric loss angle tangent)c)。
εc=(Cap×d)/(S×ε0)
Herein, Cap: capacitance [F]
D: dielectric layer thickness=25 × 10-6[m]
S: it is measured dielectric area=π × (25 × 10-3)2
ε0: the dielectric constant 8.854 × 10 of vacuum-12。
For resulting relative dielectric constant and dielectric loss angle tangent, evaluated as described below.
<evaluation criterion of relative dielectric constant>
◎: 2.3 or less
Zero: more than 2.3, and below 2.6
Δ: more than 2.6, and below 3.0
×: more than 3.0
<evaluation criterion of dielectric loss tangent>
◎: 0.005 or less
Zero: more than 0.005, and below 0.01
Δ: more than 0.01, and below 0.02
×: more than 0.02
(carboxylic polyolefin resin)
Production Example 1
In 1L autoclave, propene-1-butene copolymer is added, and (Mitsui Chemicals, Inc.'s system makes " タ フ マ ー (registered trademark) XM7080 ") 6 mass parts of 100 mass parts, 150 mass parts of toluene and 19 mass parts of maleic anhydride and di-tert-butyl peroxide, After being heated to 140 DEG C, it is stirred for 3 hours.Then, by after the cooling of resulting reaction solution, injection is equipped with a large amount of methyl ethyl ketones In container, resin is precipitated.Then, by being centrifugated the solution containing the resin, the acid after graft polymerization maleic anhydride is changed Property propene-1-butene copolymer is separated with (poly-) maleic anhydride and low molecular weight substance, is purified.Then, by decompression, 70 It is 5 hours dry at DEG C, obtain maleic anhydride modified propene-1-butene copolymer (CO-1,410 equivalent/10 of acid value6When g, divide equally again 80 DEG C of 60000, Tm of son amount, Δ H 35J/g).
Production Example 2
It is other such as Production Example 1 other than maleic anhydride additional amount is changed to 11 mass parts, it obtains maleic anhydride and changes Property propene-1-butene copolymer (CO-2,220 equivalent/10 of acid value6When g, weight average molecular weight 65000,78 DEG C of Tm, Δ H25J/g).
Embodiment 1
In the 500mL four-hole boiling flask equipped with watercooled reflux condenser and blender, the Malaysia that Production Example 1 obtains is added 80 mass parts of anhydride-modified propylene-butylene copolymer (CO-1), carboxylic styrene resin (タ Off テ ッ Network (registrar Mark) M1943) 500 mass parts of 20 mass parts and toluene, it is heated to 80 DEG C while stirring, and molten by persistently stirring progress in 1 hour Solution.In the solution obtained through cooling, it is mixed into the carbodiimide resin V-05 of 5 mass parts and the epoxy resin of 10 mass parts HP-7200 obtains adhesive composition.Combined amount, adhesive strength, scolding tin heat resistance and electrical characteristic are as shown in table 1.
Embodiment 2~10
By carboxylic polyolefin resin (A), carboxylic styrene resin (B), carbodiimide resin (C) and asphalt mixtures modified by epoxy resin Rouge (D) is changed to substance shown in table 1, and according to the method such as embodiment 1, each combined amount is made to be changed to value shown in table 1, Implement embodiment 2~14.Adhesive strength, scolding tin heat resistance and electrical characteristic are as shown in table 1.
Comparative example 1~7
By carboxylic polyolefin resin (A), carboxylic styrene resin (B), carbodiimide resin (C) and asphalt mixtures modified by epoxy resin Rouge (D) is changed to substance shown in table 2, and according to the method such as embodiment 1, each combined amount is made to be changed to value shown in table 2, Implement comparative example 1~7.Combined amount, adhesive strength, scolding tin heat resistance and electrical characteristic are as shown in table 2.
[table 2]
Polyolefin resin used in table 1,2, carboxylic styrene resin (B), carbodiimide resin (C) and epoxy Resin (D) is substance below.
Carboxylic styrene resin: タ Off テ ッ Network (registered trademark) M1911 (manufacture of ケ ミ カ Le ズ company, Asahi Chemical Industry)
Carboxylic styrene resin: タ Off テ ッ Network (registered trademark) M1913 (manufacture of ケ ミ カ Le ズ company, Asahi Chemical Industry)
Carboxylic styrene resin: タ Off テ ッ Network (registered trademark) M1943 (manufacture of ケ ミ カ Le ズ company, Asahi Chemical Industry)
Polyolefin resin: タ フ マ ー (registered trademark) XM7080 (Mitsui Chemicals, Inc.'s system is made)
Styrene resin: タ Off テ ッ Network (registered trademark) H1052 (manufacture of ケ ミ カ Le ズ company, Asahi Chemical Industry)
Carboxylic acrylonitrile butadiene rubber NBR (J Co., Ltd. SR manufacture)
Carbodiimide resin: V-05 (manufacture of Nisshinbo ケ ミ カ Le company)
Carbodiimide resin: V-03 (manufacture of Nisshinbo ケ ミ カ Le company)
O-cresol phenolic epoxy varnish: YDCN-700-10 (manufacture of aurification company is lived by Nippon Steel)
Dicyclopentadiene-type epoxy resin: HP-7200 (manufacture of DIC company)
By table 1 it will be apparent that, in embodiment 1~14, between polyimides (PI) and copper foil with excellent adhesiveness and Scolding tin heat resistance, meanwhile, also there is excellent adhesiveness and scolding tin heat resistance between liquid crystal polymer (LCP) and copper foil.In addition, For the electrical characteristic of adhesive composition, the value of dielectric constant and dielectric loss angle tangent is lower, and electrical characteristic is good.With This relatively, by table 2 it will be apparent that, in comparative example 1, is not mixed into carboxylic styrene resin, thus, wetting scolding tin is heat-resisting Property and adhesive strength are poor.In comparative example 2, it is not mixed into carboxylic polyolefin resin, thus, crosslink density is low, soaks scolding tin Poor heat resistance.In comparative example 3, polyolefin resin does not contain carboxyl, thus, crosslink density is low, soaks scolding tin poor heat resistance.Compare In example 4, styrene resin does not contain carboxyl, thus, crosslink density is low, soaks scolding tin poor heat resistance.In comparative example 5, it is not mixed into Carbodiimide resin, thus, smaller with the interaction at the interface LCP, adhesive strength is low.In comparative example 6, it is not mixed into asphalt mixtures modified by epoxy resin Rouge, thus, crosslink density is low, scolding tin poor heat resistance.In comparative example 7, it is not mixed into polyolefin resin and styrene resin, thus, The low dielectric property of adhesive composition is poor.
Utilization possibility in industry
According to the present invention, it is possible to provide a kind of laminated body below: it not only makes traditional polyimides and poly- terephthaldehyde There is high bonding between sour glycol ester film, the resin base material with low dielectric property for also making LCP etc. and the metal base of copper foil etc. Property, high scolding tin heat resistance can be obtained, and low dielectric property is excellent.Due to above-mentioned characteristic, can be used for flexible printed circuit board purposes, Especially require the FPC of the low dielectric property (low-k, low-dielectric loss angle tangent) in high-frequency region on the way.

Claims (6)

1. a kind of laminated body Z, described for laminated body Z made of resin base material and metal base is laminated by adhesive phase Adhesive phase includes: carboxylic polyolefin resin A and carbodiimide resin C；It is characterized in that,
(1) the relative dielectric constant ε under the frequency 1MHz of adhesive phasecIt is 3.0 or less；
(2) the dielectric loss angle tangent tan δ under the frequency 1MHz of adhesive phase is 0.02 or less；
(3) peel strength between resin base material and metal base is 0.5N/mm or more；
(4) the wetting scolding tin heat resistance of laminated body Z is 240 DEG C or more.
2. a kind of laminated body X is the laminated body X of adhesive phase and resin base material, for being laminated by described adhesive layer In laminated body Z made of the resin base material and metal base, described adhesive layer includes: carboxylic polyolefin resin A and Carbodiimide resin C；It is characterized in that,
(1) the relative dielectric constant ε under the frequency 1MHz of adhesive phasecIt is 3.0 or less；
(2) the dielectric loss angle tangent tan δ under the frequency 1MHz of adhesive phase is 0.02 or less；
(3) resin base material and Metal Substrate when metal base is laminated on the face of the adhesive phase of laminated body X, in gained laminated body Peel strength between material is 0.5N/mm or more；
(4) when metal base is laminated on the face of the adhesive phase of laminated body X, the wetting scolding tin heat resistance of gained laminated body is 240 DEG C or more.
3. a kind of laminated body Y is the laminated body Y of adhesive phase and metal base, for being laminated by described adhesive layer In laminated body Z made of resin base material and the metal base, described adhesive layer includes: carboxylic polyolefin resin A and Carbodiimide resin C；It is characterized in that,
(1) the relative dielectric constant ε under the frequency 1MHz of adhesive phasecIt is 3.0 or less；
(2) the dielectric loss angle tangent tan δ under the frequency 1MHz of adhesive phase is 0.02 or less；
(3) resin base material and Metal Substrate when resin base material is laminated on the face of the adhesive phase of laminated body Y, in gained laminated body Peel strength between material is 0.5N/mm or more；
(4) when resin base material is laminated on the face of the adhesive phase of laminated body Y, the wetting scolding tin heat resistance of gained laminated body is 240 DEG C or more.
4. a kind of adhesive phase, for for laminated body Z made of resin base material and metal base to be laminated by adhesive phase In described adhesive layer, described adhesive layer includes: carboxylic polyolefin resin A and carbodiimide resin C；Its feature exists In,
(1) the relative dielectric constant ε under the frequency 1MHz of adhesive phasecIt is 3.0 or less；
(2) the dielectric loss angle tangent tan δ under the frequency 1MHz of adhesive phase is 0.02 or less；
(3) resin base material is laminated on a face of adhesive phase and metal base is laminated on another face of adhesive phase When, the peel strength between resin base material and metal base in gained laminated body is 0.5N/mm or more；
(4) resin base material is laminated on a face of adhesive phase and metal base is laminated on another face of adhesive phase When, the wetting scolding tin heat resistance of gained laminated body is 240 DEG C or more.
5. a kind of adhesive sheet, the laminated body Z recorded containing claim 1, the laminated body X of claim 2 record, right are wanted Ask the laminated body Y of 3 records or the adhesive phase of claim 4 record.
6. a kind of printed circuit board, it includes the adhesive sheets of claim 5 record as constituent element.
CN201680004408.3A 2015-05-15 2016-05-11 Laminated body containing low dielectric adhesive layer Active CN107109182B (en)

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KR102324559B1 (en) * 2020-02-28 2021-11-10 (주)이녹스첨단소재 Bonding film, bonding film laminate comprising the same and metal clad laminate comprising the same
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