CN104718801A - Coverlay film, flexible printed circuit board using same, and production method therefor - Google Patents

Coverlay film, flexible printed circuit board using same, and production method therefor Download PDF

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Publication number
CN104718801A
CN104718801A CN201380054077.0A CN201380054077A CN104718801A CN 104718801 A CN104718801 A CN 104718801A CN 201380054077 A CN201380054077 A CN 201380054077A CN 104718801 A CN104718801 A CN 104718801A
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coverlay
alkyl
halogen atom
phenyl
carbon number
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CN104718801B (en
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桑野広志
寺木慎
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Namics Corp
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Namics Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials

Abstract

The coverlay film of the present invention comprises (A) a specific vinyl compound, (B) a polystyrene-poly(ethylene/butylene) block copolymer, (C) a polystyrene-poly(ethylene-ethylene/propylene) block copolymer, (D) an epoxy resin, and (E) a bismaleimide. The mass ratio of each component satisfies (A+E)/(B+C) = 0.81-1 and (B)/(C) = 1-4. An adhesive layer containing 1-10 mass% of the component (D) with respect to the total mass of the components (A)-(E) is formed on one surface of an organic film having a melting point that is higher than the thermal curing temperature of the adhesive layer, a dielectric constant of 4 or less in an area having a frequency of 1-10 GHz, and a dielectric loss tangent of 0.02 or less.

Description

Coverlay and use its flexible printing wiring board and their manufacture method
Technical field
The present invention relates to coverlay.More specifically, the coverlay of flexible printing wiring board is related to.
In addition, the invention still further relates to the flexible printing wiring board employing this coverlay.
In addition, the invention still further relates to the manufacture method of this coverlay and this flexible printing wiring board.
Background technology
In recent years, the high performance of electronic equipment, multifunction and miniaturization are being in progress rapidly.The requirement of the densification of the electronic unit used in the electronic device, miniaturization and slimming is in raising.Accompany therewith, for the material of electronic unit, be required will improve all physical property such as thermal endurance, mechanical strength and electrical characteristics further.Such as, for the printed wiring board installing semiconductor element, high density, high function and high-performance is more required.
In such a case, for can narrow space carry out three-dimensional wiring, installation the needs of flexible printing wiring board (hereinafter referred to as FPC) in increase.Usual FPC has following structure: on the polyimide film of thermal endurance and flexibility excellence, form circuitous pattern, its surface is fitted with the cap rock of bond layer, the structure of so-called coverlay.
Require that the coverlay of FPC has excellent adhesive strength to the baseplate material becoming the FPC such as the metal forming of wiring of FPC and polyimide film.The coverlay realizing this requirement is such as proposed by patent documentation 1 ~ 3.
In recent years, the high frequency of the signal transmission in FPC is in remarkable development.So require that the material being used for FPC can at high-frequency region, specifically in the loss of the region of the frequency 1 ~ 10GHz reduction signal of telecommunication.For coverlay, require, at high-frequency region, excellent electrical characteristics (low-k (ε) and low dielectric loss angle tangent (tan δ)) are shown.
The applicant of the application proposes following coverlay in patent documentation 4: have excellent adhesive strength to the baseplate material becoming the FPC such as the metal forming of wiring of FPC and polyimide film, and at the high-frequency region of frequency 1 ~ 10GHz, electrical characteristics are shown, specifically, low-k (ε) and low dielectric loss angle tangent (tan δ) are shown in the region of frequency 1 ~ 10GHz.This coverlay contains at least one party's ((B) composition) of the vinyl compound ((A) composition) of ad hoc structure, polystyrene-poly (ethylene/butylene) block copolymer and polystyrene-poly (ethylene-vinyl/propylene) block copolymer, epoxy resin ((C) composition) and curing catalysts ((D) composition).
[prior art document]
Patent documentation 1: Japanese Unexamined Patent Publication 2008-248141 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2006-169446 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-248048 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-68713 publication
Summary of the invention
When making FPC, the coupling part of the wiring of FPC is implemented plating process, but it is clear that, coverlay due to record in patent documentation 4 forms fine hole, the patience of FPC during matting after plating operation, specifically, the thin copper film of FPC can have problems for the patience of the plating cleaning fluid used during matting after plating operation.
After the assigned position that coverlay is placed in FPC, the position that is namely coated to by coverlay, by thermo-compressed.Thermo-compressed is by after being crimped on by coverlay on FPC temporarily, carries out executing stressed being heating and curing simultaneously.By thermo-compressed, coverlay is heating and curing, and is consequently adhered to FPC.
About the coverlay recorded in patent documentation 4, the imbedibility of the circuit when being adhered to FPC is good.On the contrary, when there is fine protuberance when thermo-compressed at coverlay on the surface of electrolysis (pressurized plane), result from the mobility of the imbedibility bringing this circuit, form the fine concave portions corresponding with this protuberance on coverlay surface.About the reason of the fine protuberance on electrolysis (pressurized plane) surface, the fine protuberance mainly existed on the surface of mold release film.This mold release film is clamped between padded coaming and coverlay when the thermo-compressed of coverlay.Fine protuberance is mainly caused by the release agent be coated with on the surface of mold release film.
The size of the coupling part that coverlay can be formed according to the end of the wiring at FPC is made with less size in advance.When the thermo-compressed of coverlay, in the end of coverlay, film deforms and filming.If have fine protuberance to exist in the position corresponding with the part of the filming of coverlay on pressurized plane surface, then can form recess at coverlay, hole can be formed due to concentrating of electric charge when plating operation.In addition, by this hole, have plating cleaning fluid during matting after plating operation and immerse, blackened (oxidation) or the albefaction (stripping) of the thin copper film of FPC occurs.Its result, the reliability decrease of circuit.
In addition, the coverlay recorded in patent documentation 4, by the intensity of contraction during hot curing and stress, can make FPC be called curling warpage.Occur so curling time, the flexibility of the FPC that originally should require is impaired.Therefore, be such as difficult to be used as FPC cable.
The object of the invention is to, in order to solve the problem points of above-mentioned prior art, providing a kind of coverlay as follows.That is, this coverlay has excellent adhesive strength relative to the baseplate material of the FPC such as polyimide film.In addition, the electrical characteristics of the high-frequency region at frequency 1 ~ 10GHz are shown, specifically, low-k (ε) and the low dielectric loss angle tangent (tan δ) in the region at frequency 1 ~ 10GHz are shown, and then this coverlay is endowed resistance to plating.In addition, curling being suppressed during hot curing.
To achieve these goals, the invention provides a kind of coverlay, it is characterized in that,
The adhesive linkage that its one side being included in organic film is formed, above-mentioned adhesive linkage contains:
(A) following general formula (1) represent vinyl compound,
(B) polystyrene-poly (ethylene/butylene) block copolymer,
(C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer,
(D) epoxy resin,
(E) bismaleimides,
[changing 1]
(in formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7can be identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl.-(O-X-O)-as shown in following structural formula (2).
[changing 2]
R 8, R 9, R 10, R 14, and R 15can be identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl.R 11, R 12, and R 13can be identical or different, be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl.-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement.
[changing 3]
R 16and R 17can be identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl.R 18and R 19can be identical or different, be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl.Z is the organic group of carbon number more than 1, can comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom.A and b represents the integer of 0 ~ 300, and at least one party of a and b is not 0.C and d represents the integer of 0 or 1.)
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B)/(C)=more than 1.00 are below 4.00, and relative to the gross mass of mentioned component (A) ~ (E), containing mentioned component (D) 1 ~ 10 quality %;
Above-mentioned organic film has the fusing point of the heat curing temperature higher than above-mentioned adhesive linkage, and has the dielectric constant (ε) of less than 4.0 and the dielectric loss angle tangent (tan δ) of less than 0.02 in the region of frequency 1 ~ 10GHz.
In coverlay of the present invention, preferably above-mentioned (A) composition-(O-X-O)-as shown in following structural formula (4), above-mentioned (A) composition-(Y-O)-have: the structure that the structure that following structural formula (5) or following structural formula (6) represent or the structure represented by following structural formula (5) and following structural formula (6) represent is through the structure of random arrangement.
[changing 4]
[changing 5]
In coverlay of the present invention, mentioned component (A)-structure that represents of (Y-O)-preferably have structure above (6).
In coverlay of the present invention, preferably the lowest melt viscosity of above-mentioned adhesive linkage of temperature field of 150 ~ 200 DEG C is more than 2000Pas below 10000Pas.
Coverlay of the present invention, preferably after above-mentioned adhesive linkage hot curing, has the dielectric constant (ε) of less than 3.5 and the dielectric loss angle tangent (tan δ) of less than 0.02 in the region of frequency 1 ~ 10GHz.
Coverlay of the present invention, the above-mentioned adhesive linkage after preferred hot curing has the dielectric constant (ε) of less than 2.5 and the dielectric loss angle tangent (tan δ) of less than 0.004 in the region of frequency 1 ~ 10GHz.
In coverlay of the present invention, above-mentioned organic film preferably use in liquid crystal polymer, polyimides, PEN and polytetrafluoroethylene any one make.
In addition, the present invention also provides a kind of flexible printing wiring board, it is characterized in that, formed with the resin substrate connected up and coverlay integration by thermo-compressed, the described resin substrate with wiring is formed with wiring pattern at the interarea of the resin substrate being principal component with any one in liquid crystal polymer, polyimides and PEN, and described coverlay is configured in the wiring pattern side of the described resin substrate with wiring according to the mode of the adhesive linkage subtend of this coverlay.
In addition, the present invention also provides a kind of flexible printing wiring board, it is characterized in that, formed with the resin substrate connected up and coverlay integration by thermo-compressed, the described resin substrate with wiring be the vinyl compound represented with above-mentioned general formula (1) and, rubber and/or thermoplastic elastomer (TPE) be that the interarea of the resin substrate of principal component is formed with wiring pattern, described coverlay is configured in the wiring pattern side of the described resin substrate with wiring according to the mode of the adhesive linkage subtend of this coverlay.
In addition, the invention provides a kind of manufacture method of coverlay, it is the manufacture method of the coverlay containing the adhesive linkage formed in the one side of organic film, it is characterized in that, comprise: by making the varnish-drying containing resin combination of the coated on one side at above-mentioned organic film, form above-mentioned adhesive linkage
Above-mentioned resin combination contains: the vinyl compound that (A) above-mentioned general formula (1) represents, (B) polystyrene-poly (ethylene/butylene) block copolymer, (C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer, (D) epoxy resin, (E) bismaleimides
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B)/(C)=more than 1.00 are below 4.00, and relative to the gross mass of mentioned component (A) ~ (E), containing mentioned component (D) 1 ~ 10 quality %
Above-mentioned organic film has the fusing point of the heat curing temperature higher than above-mentioned resin combination, and has the dielectric constant (ε) of less than 4.0 and the dielectric loss angle tangent (tan δ) of less than 0.02 in the region of frequency 1 ~ 10GHz.
In addition, the present invention also provides a kind of manufacture method of coverlay, and it is the manufacture method of the coverlay containing the adhesive linkage formed in the one side of organic film, it is characterized in that, comprises: make adhesion film with resin combination; And, above-mentioned adhesion film and above-mentioned organic film are fitted, is formed above-mentioned adhesive linkage thus;
Above-mentioned resin combination contains: the vinyl compound that (A) above-mentioned general formula (1) represents, (B) polystyrene-poly (ethylene/butylene) block copolymer, (C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer, (D) epoxy resin, (E) bismaleimides
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B)/(C)=more than 1.00 are below 4.00, and relative to the gross mass of mentioned component (A) ~ (E), containing mentioned component (D) 1 ~ 10 quality %
Above-mentioned organic film has the fusing point of the heat curing temperature higher than this resin combination, is less than 4.0 at the dielectric constant (ε) in the region of frequency 1 ~ 10GHz, and dielectric loss angle tangent (tan δ) is less than 0.02.
In addition, the present invention also provides a kind of manufacture method of flexible printing wiring board, it is characterized in that, comprise: wiring pattern is set at the interarea of the resin substrate being principal component with any one in liquid crystal polymer, polyimides and PEN, make the resin substrate with wiring; In the above-mentioned wiring pattern side of the above-mentioned resin substrate with wiring, configure above-mentioned coverlay according to the mode of the adhesive linkage subtend of coverlay of the present invention; With by thermo-compressed by above-mentioned with wiring resin substrate and above-mentioned coverlay integration.
In addition, the present invention also provides a kind of manufacture method of flexible printing wiring board, it is characterized in that, comprise: the vinyl compound (a) represented with above-mentioned general formula (1) and, the interarea of rubber and/or thermoplastic elastomer (TPE) (b) resin substrate that is principal component arranges wiring pattern, makes the resin substrate with wiring; In the above-mentioned wiring pattern side of the above-mentioned resin substrate with wiring, configure above-mentioned coverlay according to the mode of the adhesive linkage subtend of coverlay of the present invention; With by thermo-compressed by above-mentioned with wiring resin substrate and above-mentioned coverlay integration.
Coverlay of the present invention, relative to the baseplate material becoming the FPC such as the metal forming of wiring of FPC and polyimide film, there is excellent adhesive strength, and at high-frequency region, excellent electrical characteristics are shown, specifically, low-k (ε) and low dielectric loss angle tangent (tan δ) are shown) in the region of frequency 1 ~ 10GHz.Therefore, coverlay of the present invention is suitable as the coverlay of FPC.
In addition, coverlay of the present invention, seepage discharge when being adhered on substrate is suitable.Therefore, workability during bonding coverlay is excellent, and the imbedibility of circuit can not be impaired.
In addition, coverlay of the present invention is endowed resistance to plating.Therefore, during matting after the plating operation of the coupling part of the wiring of FPC, blackened (oxidation) and the albefaction (stripping) of the thin copper film of FPC that prevent the immersion of plating cleaning fluid and cause thus.Consequently the reliability of circuit improves.
In addition, coverlay suppression of the present invention occurs curling when hot curing.Therefore, the flexibility of FPC can not be damaged.
Embodiment
Below, coverlay of the present invention is described in detail.
Coverlay of the present invention has the coverlay being formed with the two-layer structure of adhesive linkage in the one side of organic film.
[organic film]
Organic film in coverlay of the present invention, has the function of protective covering coverlay being given to resistance to plating.
As mentioned above, in order to the imbedibility of circuit time bonding with FPC is good, preferred coverlay is having high fluidity with during FPC thermo-compressed.
But, when with FPC thermo-compressed, if the mobility of coverlay is high, there is filming in the end of coverlay.For this reason, when the position corresponding with the part of the filming of coverlay on pressurized plane surface has fine protuberance to exist, recess can be formed on coverlay, hole can be formed by concentrating of electric charge when plating operation.In addition, by this hole, when having plating cleaning fluid to immerse during matting after plating operation, there is blackened (oxidation) or the albefaction (stripping) of the thin copper film of FPC.Its result, the reliability decrease of circuit.
Coverlay of the present invention, by the imbedibility of the circuit when the adhesive linkage high with mobility during FPC thermo-compressed realizes bonding with FPC.On the other hand, the organic film by being formed with this adhesive linkage in one side gives resistance to plating.
For this reason, organic film of the present invention, be required with during FPC thermo-compressed not adhesive linkage formed with the bad relevant recess of plating process.
In order to realize this requirement, as organic film of the present invention, use fusing point higher than the organic film of the heat curing temperature of adhesive linkage.When not having the resin of fusing point, such as, use glass transition temperature higher than the organic film of the curing temperature of adhesive linkage.As long as organic film has the fusing point of the heat curing temperature higher than adhesive linkage, then, when with FPC thermo-compressed, recess can not be formed at adhesive linkage.Prevent from thus forming hole at coverlay.Its result, is endowed resistance to plating during plating process.
It should be noted that, though detailed content as described later, the heat curing temperature of adhesive linkage is 180 ~ 210 DEG C.
As the requirement characteristic for coverlay of the present invention, be that there is in the region of frequency 1 ~ 10GHz low-k (ε) and low dielectric loss angle tangent (tan δ).Specifically, after bonding with FPC, namely after the hot curing of adhesive linkage, require the region at frequency 1 ~ 10GHz, dielectric constant (ε) is less than 3.5 and dielectric loss angle tangent (tan δ) is less than 0.02.
For this reason, for organic film, require that there is in the region of frequency 1 ~ 10GHz low-k (ε) and low dielectric loss angle tangent (tan δ).Specifically, require the region at frequency 1 ~ 10GHz, dielectric constant (ε) is less than 4.0, and dielectric loss angle tangent (tan δ) is less than 0.02.
It should be noted that, about adhesive linkage, be required the region at frequency 1 ~ 10GHz that there is the dielectric constant (ε) of less than 2.5 and the dielectric loss angle tangent (tan δ) of less than 0.004 after this adhesive linkage hot curing.
Organic film of the present invention, is selected from the organic film meeting the condition relating to above-mentioned fusing point and the condition relating to dielectric constant and dielectric loss angle tangent.
As the concrete example of organic film meeting these conditions, the organic film using liquid crystal polymer (LCP) or polytetrafluoroethylene (PTFE) to make can be enumerated.LCP and PTFE has excellent electrical characteristics at the high-frequency region of frequency 1 ~ 10GHz.Thus, the organic film using LCP or PTFE to make, has the dielectric constant (ε) of less than 3.0 and the dielectric loss angle tangent (tan δ) of less than 0.0030 in the region of frequency 1 ~ 10GHz.
In addition, as other concrete examples of organic film meeting these conditions, the organic film that use polyimides (PI) or PEN (PEN) make is had.This organic film has the dielectric constant (ε) of less than 4.0 and the dielectric loss angle tangent (tan δ) of less than 0.02 in the region of frequency 1 ~ 10GHz.
The grade of the organic film made by these PI or PEN of suitable choice for use, in the region of frequency 1 ~ 10GHz, this organic film has the dielectric constant (ε) of less than 4.0 and the dielectric loss angle tangent (tan δ) of less than 0.02.In addition, by the grade of PI and PEN and the thickness of film, can make that the dielectric constant in the region of frequency 1 ~ 10GHz is less than 3.0, dielectric loss angle tangent is less than 0.006.
Therefore, the material corresponding to the organic film used carrys out the thickness of selective membrane.Here, LCP and PTFE has excellent electrical characteristics at high-frequency region as mentioned above.Therefore thickness is not particularly limited.But from the view point of the filming of coverlay, preferred thickness is 1 ~ 100 μm, is more preferably 1 ~ 50 μm, more preferably 1 ~ 30 μm.
When the organic film using PI or PEN to make, different because of its grade, but thickness is preferably 0.5 ~ 100 μm, is more preferably 0.5 ~ 50 μm, more preferably 0.5 ~ 30 μm.
When the film using LCP to make, the LCP masking such as " VECSTAR (registered trade mark) " of Kuraray Co., Ltd. and " BIAC " of Japanese Gore Co., Ltd. can be used.In addition, use after the commercially available LCP material films such as " VECTRA (registered trade mark) " of Polyplastics Co., Ltd., " SIVERAS (registered trade mark) " of Dongli Ltd. and " SUMIKA SUPER (the ス ミ カ ス ー パ ー) LCP " of Sumitomo Chemical Company Ltd can also being changed into desired thickness.
When the film using PI to make, PI masking such as " APICAL (registered trade mark) " of " KAPTON (registered trade mark) " of Dong Li E.I.Du Pont Company, " XENOMAX (registered trade mark) " of Toyo Boseki K.K, " UPILEX (registered trade mark) S " of Ube Industries, Ltd and Co., Ltd. KANEKA can be used.In addition, use after the PI material film of " AURUM (registered trade mark) " of Mitsui Chemicals, Inc and so on can also being changed into desired thickness.
When the film using PEN to make, can use " TEONEX (registered trade mark) " of Di Ren DuPont Film Inc..
When the film using PTFE to make, can use " NITOFLON (registered trade mark) " of Nitto Denko Corp, " NAFLON (registered trade mark) " of NICHIAS Co., Ltd. and Japanese VALQUA Industrial Co., Ltd " VALFLON (registered trade mark) ".
[adhesive linkage]
As mentioned above, about coverlay of the present invention, the imbedibility of circuit during in order to make bonding with FPC is good, when with FPC thermo-compressed, requires that the mobility of adhesive linkage is high.As described later, temperature during the interim crimping of coverlay of the present invention is 100 ~ 150 DEG C.In addition, temperature during being heating and curing of this coverlay is 150 ~ 210 DEG C.In coverlay of the present invention, be preferably more than 2000Pas below 10000Pas in the lowest melt viscosity of the adhesive linkage of the temperature field of 150 ~ 210 DEG C.Here, lowest melt viscosity refers to when heating adhesive linkage, the minimum of viscosity when this adhesive linkage there occurs melting.
As the requirement characteristic for coverlay of the present invention, be that there is in the region of frequency 1 ~ 10GHz low-k (ε) and low dielectric loss angle tangent (tan δ).Specifically, require after bonding with FPC, namely after being heating and curing of adhesive linkage, be less than 3.5 and dielectric loss angle tangent (tan δ) is less than 0.02 at the region dielectric constant (ε) of frequency 1 ~ 10GHz.
For this reason, adhesive linkage of the present invention is required that its solidfied material is less than 2.5 and dielectric loss angle tangent (tan δ) is less than 0.004 at the region dielectric constant (ε) of frequency 1 ~ 10GHz.
In order to meet relate to the condition of above-mentioned lowest melt viscosity and relate to the condition of dielectric constant and dielectric loss angle tangent, adhesive linkage of the present invention using composition (A) ~ (E) shown below as essential component.
(A): the vinyl compound that following general formula (1) represents
[changing 6]
In general formula (1), R 1, R 2, R 3, R 4, R 5, R 6, and R 7can be identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl.Wherein, R 1, R 2, R 3, R 4, R 5, R 6, and R 7be preferably hydrogen atom.
In formula ,-(O-X-O)-as shown in following structural formula (2).
[changing 7]
In structural formula (2), R 8, R 9, R 10, R 14, and R 15can be identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl.Wherein, R 8, R 9, R 10, R 14, and R 15be preferably the alkyl of carbon number less than 6.Wherein, R 11, R 12, and R 13be preferably the alkyl of hydrogen atom, halogen atom or carbon number less than 6.
In general formula (1) ,-(Y-O) has: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement.
[changing 8]
In structural formula (3), R 16and R 17can be identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl.Wherein, R 16and R 17be preferably the alkyl of carbon number less than 6.
R 18and R 19can be identical or different, be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl.Wherein, R 18and R 19the preferably alkyl of hydrogen atom or carbon number less than 3.
In general formula (1), Z is the organic group of carbon number more than 1, can comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom.Wherein, the preferred methylene of Z.
A and b represents the integer of 0 ~ 300.At least one party of a and b is not 0.
C and d represents the integer of 0 or 1.Wherein, c and d is preferably 1.
Wherein, preferred R 8, R 9, R 10, R 14, and R 15the alkyl of carbon number less than 3, R 11, R 12, and R 13the alkyl of hydrogen atom or carbon number less than 3, R 16and R 17the alkyl of carbon number less than 3, R 18and R 19it is hydrogen atom.
In addition, in above-mentioned general formula (1)-(O-X-O)-be preferably as follows state structural formula (4) In and show.
[changing 9]
In addition, in general formula (1)-(Y-O)-preferably have: the structure that the structure that following structural formula (5) or following structural formula (6) represent or the structure represented by following structural formula (5) and following structural formula (6) represent is through the structure of random arrangement.Wherein ,-(Y-O)-there is the structure of structure through arranging defined by following structural formula (6).
[changing 10]
In coverlay of the present invention, the electrical characteristics excellent under contributing to the Thermocurable of adhesive linkage, thermal endurance and high frequency of composition (A), low-k (ε) namely in the region of frequency 1 ~ 10GHz and low dielectric loss angle tangent (tan δ).
In addition, composition (A) plays a role as the phase solvation of composition described later (B), composition (C), composition (D) and composition (E).
The method for making of the vinyl compound that above-mentioned general formula (1) represents is not particularly limited, can any means manufactured be used.Such as, can under the existence of the base catalysts such as NaOH, potash or caustic alcohol, also use the phase transfer catalysts such as benzyl three n-butyl ammonium bromide, 18-crown-6-ether as required, the compound that 1-chloro-4-methyl-benzene and following general formula (7) are represented reacts and obtains.
[changing 11]
About in general formula (7)-(O-X-O) and-(Y-O)-, as described in general formula (1).
Composition (B): polystyrene-poly (ethylene/butylene) block copolymer
Composition (C): polystyrene-poly (ethylene-vinyl/propylene) block copolymer
In coverlay of the present invention, composition (B) and (C) contribute to the excellent electrical characteristic at high frequency (low-k (ε) in the region of frequency 1 ~ 10GHz and low dielectric loss angle tangent (tan δ)) and the thermal endurance of adhesive linkage.
Wherein, about composition (B), because the crystallinity of its poly-(ethylene/butylene) part is high, so have high-fire resistance.Thus, composition (B) gives thermal endurance to adhesive linkage.On the other hand, poly-(ethylene-vinyl/propylene) of composition (C) crystallinity is partly lower than the corresponding part (poly-(ethylene/butylene) part) of composition (B).Therefore, composition (C) is compared with composition (B), and the adhesive strength for base material is higher.
For this reason, in the present invention, use in adhesive linkage with the composition (B) of special ratios as described below cooperation and (C).
In the present invention, the composition (B) in adhesive linkage and mass ratio (B)/(C) of (C) are less than more than 1.00 4.00.
(B)/(C) lower than 1.00 time, although obtain desired by adhesive strength, adhesive linkage becomes high resiliency.Its result, stress during solidification is comparatively strong, so easily occur curling.
On the other hand, when (B)/(C) is more than 4.00, adhesive linkage has low elasticity, so can suppress curling generation.But, desired adhesive strength can not be obtained.
Mass ratio (B)/(C) of composition (B) and (C) is more preferably less than more than 1.5 3.5.
Composition (D): epoxy resin
In coverlay of the present invention, composition (D) contributes to Thermocurable and the cementability of the adhesive linkage of coverlay.
The adhesive linkage of coverlay of the present invention, contains composition (D) 1 ~ 10 quality % relative to the gross mass of composition (A) ~ (E).
When mentioned component (D) is lower than 1 quality %, have the problems such as the cementability of coverlay is insufficient.
When mentioned component (D) is more than 10 quality %, intermiscibility worsens.In addition, desired dielectric loss angle tangent (tan δ) value can not be obtained.In addition, the seepage discharge of coverlay when bonding can become excessive.And then the increasing proportion that composition (D) is shared in whole composition, so the characteristic of the composition (D) of thermal endurance variation can affect the whole adhesive linkage of coverlay.For this reason, the thermal endurance of the adhesive linkage of coverlay, curability likely decline.
Coverlay of the present invention more preferably contains composition (D) 1 ~ 5 quality % relative to the gross mass of composition (A) ~ (E).
The epoxy resin being used as composition (D) is not particularly limited.The various epoxy resin such as phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin and biphenyl type epoxy resin can be used.
As the concrete example of phenol aldehyde type epoxy resin, JER 152 (japan epoxy resin Co., Ltd. system) can be enumerated.
As the concrete example of bisphenol A type epoxy resin, JER 828 (japan epoxy resin Co., Ltd. system) can be enumerated.
As the concrete example of bisphenol f type epoxy resin, JER 806 (japan epoxy resin Co., Ltd. system) can be enumerated.
As the concrete example of biphenyl type epoxy resin, JER FX4000 (japan epoxy resin Co., Ltd. system), NC3000H (Nippon Kayaku K. K's system) can be enumerated.
It should be noted that, can use any a kind in above-mentioned epoxy resin, also two or more kinds may be used.
In addition, in above-mentioned epoxy resin, from the view point of bonding force excellence, preferred bisphenol A type epoxy resin and biphenyl type epoxy resin, more preferably biphenyl type epoxy resin.
As the epoxy resin of composition (D), from the reason of the mechanical property after Thermocurable, cementability and solidification, preferred number average molecular weight (Mn) is 150 ~ 2500.
Composition (E): bismaleimides
In coverlay of the present invention, the bismaleimides of composition (E) and the vinyl compound effect of composition (A), can make being heating and curing of the adhesive linkage of coverlay carry out at lower temperature (such as make usually at the materials of 200 DEG C of solidifications 150 DEG C of solidifications).
In the present invention, the reason of bismaleimides is used to be, from the preferred bismaleimides of viewpoint that imparting and the high Tg (glass transition temperature) of the maintenance of dielectric property, adhesive strength change.
The use level of the bismaleimides of composition (E), is preferably decided by the equivalent proportion of the vinyl of the vinyl compound relative to composition (A).Specifically, relative to vinyl 1 equivalent of the vinyl compound of composition (A), the bismaleimides of composition (E) is 0.1 ~ 3 equivalent, is preferably 0.5 ~ 1.5 equivalent, is more preferably 0.8 ~ 1.3 equivalent.
In coverlay of the present invention, composition (A) and (E) are the resin materials of Thermocurable, and composition (B) and (C) are thermoplastic resin materials.
In coverlay of the present invention, the resin material of these Thermocurables and the mixing ratio of thermoplastic resin material, can affect the physical property of the adhesive linkage contained by coverlay.For this reason, use (composition (A) and (E)) and (composition (B) and (C)) that coordinate with special ratios as described below.
It should be noted that, the epoxy resin of composition (D) is also the resin material of Thermocurable, but as mentioned above, the content of composition (D) is 1 ~ 10 a small amount of quality % relative to the gross mass of composition (A) ~ (E).For this reason, as long as coordinated with (composition (A) and (E)) and (composition (B) and (C)) by composition (D) with special ratios as described below, composition (D) just can be ignored on the impact of the physical property of the adhesive linkage contained by coverlay.
In coverlay of the present invention, the total amount of composition (A) and (E), be less than more than 0.81 1.00 with mass ratio (A+E)/(B+C) of the total amount of composition (B) and (C).
Each composition mass ratio (A+E)/(B+C) lower than 0.81 time, desired adhesive strength can not be obtained.
On the other hand, when (A+E)/(B+C) is more than 1.00, be high resiliency, so stress during solidification strengthens.For this reason, easily generation is become curling.
The adhesive linkage of coverlay of the present invention, except mentioned component (A) ~ (E), can also containing curing catalysts as composition (F).This curing catalysts plays a role as the curing catalysts of the epoxy resin of composition (D).
When containing the curing catalysts as composition (F), preferably contain the composition (F) of 0.001 ~ 5 quality % relative to the gross mass of composition (A) ~ (F).
When the content of composition (F) is lower than 0.001 quality %, the adhesive linkage of coverlay cannot carry out hot curing at short notice, therefore, has cementability and becomes the problem such as insufficient.
On the other hand, when the content of composition (F) is more than 5 quality %, has curing catalysts and the problem such as separate out after formation adhesive linkage.
When containing the curing catalysts as composition (F), more preferably contain the composition (F) of 0.01 ~ 3 quality % relative to the gross mass of composition (A) ~ (F).
As the curing catalysts of composition (F), as long as the curing catalysts of epoxy resin, be just not particularly limited.Known curing catalysts can be used to use.Such as can enumerate imidazoles system curing catalysts, amine system curing catalysts and phosphorus system curing catalysts etc.
As imidazoles system curing catalysts, the imidazolium compoundss such as glyoxal ethyline, 2-undecyl imidazole, 1-cyanoethyl-2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazoles, 2-phenylimidazole and 2-phenyl-4-methylimidazole can be enumerated.Wherein, preferred 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole and 1-cyanoethyl-2-ethyl-4-imidazoles.
As amine system curing catalysts, can enumerate 2, the triaizine compounds such as 4-diaminourea-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine and 1,8-diazabicylo [5,4,0] endecatylene-7 (DBU), triethylene diamine, benzyl dimethyl amine, the tertiary amine compound such as triethanolamine.Wherein, preferably 2,4-diaminourea-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine.
In addition, as phosphorus system curing catalysts, triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphines and three (nonyl phenyl) phosphine etc. can be enumerated.
Wherein, imidazoles system curing catalysts, owing to only promoting low-temperature setting, so particularly preferably with organic principle.
In addition, in the adhesive linkage of coverlay of the present invention, other compositions can also be contained as required.As the concrete example of such composition, fire retardant, modifier and filler can be enumerated.
In addition, in order to improve the cementability to substrate, it can be made to contain silane coupler, this silane coupler is the silicone alkoxyl oligomer with functional groups such as hydroxyl, epoxy, vinyl, methyl, amino, isocyanates.
(fire retardant)
As fire retardant, known fire retardant can be used, such as, use the phosphates such as trimethyl phosphate, triphenyl phosphate and tricresyl phosphate.
When containing fire retardant, preferably contain fire retardant 1 ~ 200 quality % relative to the gross mass of composition (A) ~ (F) and fire retardant, more preferably containing 5 ~ 100 quality %, further preferably containing 10 ~ 50 quality %.
Then, the making step of coverlay of the present invention is shown, namely forms the step of adhesive linkage in the one side of organic film.
Such as, deposit in case there being solvent or do not have solvent to deposit in case, heating, vacuum blender is utilized to mix composition (A) ~ (E) of above-mentioned adhesive linkage (when containing also blending constituent (F) composition (F), and also mix these any compositions when containing other any compositions), obtain the resin combination containing these compositions.
Specifically, according to mentioned component (A) ~ composition (E) for desired contains proportional mode (when containing mentioned component (F), other any compositions, these any compositions are also made to be desired containing proportional mode), composition (A) ~ composition (E) is dissolved into the solvent strength of regulation, these diffluent compositions are rendered to ormal weight in the reactor being heated to 10 ~ 80 DEG C.While make the composition by throwing in rotate with rotating speed 100 ~ 1000rpm, while carry out the normal pressure mixing of 3 hours.
Varnish containing the resin combination so obtained coated the one side of organic film and make it dry, the one side that can be manufactured on organic film is thus formed with the coverlay of adhesive linkage.
As the solvent that can be used as varnish, the ketone such as methyl ethyl ketone and methyl iso-butyl ketone (MIBK) can be enumerated; The aromatic solvent such as toluene and dimethylbenzene; The high boiling solvent such as dioctyl phthalate and dibatyl phithalate etc.The use amount of solvent is not particularly limited.The solvent of the amount all the time used can be used.Preferred amount is 20 ~ 90 quality % relative to solid state component.
The method of coating varnish is not particularly limited.Such as can enumerate seam die head mode, micro-plate gravure coating method and blade coating mode etc., the method for coating varnish suitably can be selected corresponding to the thickness etc. of desired adhesive linkage.From the view point of can must be thinner by the Thickness Design of adhesive linkage, particularly preferably seam die head mode.Be coated with according to make dry after the thickness of adhesive linkage that formed be that the mode of desired thickness is carried out.About such thickness, as long as those skilled in the art just can derive from solvent.
About the condition of drying, kind and amount, the use amount of varnish and the thickness etc. of coating that can correspond to the solvent that varnish uses suitably design, and are in addition not particularly limited.Dry condition is such as 60 ~ 120 DEG C, can under atmospheric pressure carry out.
The thickness of the adhesive linkage formed after dry is generally 1 ~ 100 μm.When requiring filming, preferably 1 ~ 30 μm.In fact, the thickness of adhesive linkage is that the wiring corresponded on the FPC attaching coverlay is highly selected.
In addition, the varnish obtained in above-mentioned step can be coated at least one side of supporting mass.After making the varnish-drying on supporting mass, the adhesion film peeled off from supporting mass and organic film are fitted by being crimped at 100 ~ 150 DEG C temporarily, the one side that can be manufactured on organic film is thus formed with the coverlay of adhesive linkage.
Supporting mass is not particularly limited.Such as can enumerate the carrier film etc. of the resins such as the metal forming such as copper and aluminium, polyester and polyethylene.Supporting mass preferably carries out demoulding process with silicone compounds etc.
Coverlay of the present invention is as follows, has the characteristic of the coverlay being suitable as FPC.
Coverlay of the present invention, after being heating and curing, has excellent electrical characteristics in high frequency.Specifically, the coverlay after being heating and curing preferably has the dielectric constant (ε) of less than 3.5 in the region of frequency 1 ~ 10GHz, more preferably have the dielectric constant (ε) of less than 3.0.
In addition, preferably there is in the region of frequency 1 ~ 10GHz the dielectric loss angle tangent (tan δ) of less than 0.02, more preferably there is the dielectric loss angle tangent (tan δ) of less than 0.01, preferably there is the dielectric loss angle tangent (tan δ) of less than 0.0075 further.
Be above-mentioned scope by the dielectric constant (ε) in the region at frequency 1 ~ 10GHz and dielectric loss angle tangent (tan δ), the signal of telecommunication loss in the region of frequency 1 ~ 10GHz can be reduced in.
In order to realize these, the adhesive linkage of coverlay of the present invention is required that its solidfied material has the dielectric constant (ε) of less than 2.5, the dielectric loss angle tangent (tan δ) of less than 0.004 in the region of frequency 1 ~ 10GHz.
It should be noted that, the dielectric constant (ε) of the adhesion film shown in embodiment described later and dielectric loss angle tangent (tan δ), with the dielectric constant (ε) of the solidfied material of adhesive linkage and dielectric loss angle tangent (tan δ) suitable.
Coverlay of the present invention, from the view point of the stress relaxation that low elasticity causes, preferably has the tensile modulus of elasticity of 250 ~ 400MPa after being heating and curing of adhesive linkage.
From the view point of thermal endurance, long-term reliability, the glass transition temperature of the adhesive linkage contained by preferred coverlay of the present invention is 190 ~ 250 DEG C.
Adhesive linkage contained by coverlay of the present invention curling, when being used in the step measurements recorded in embodiment described later, is preferably below D<15mm.
Then, the use step of coverlay of the present invention is shown.
By coverlay of the present invention, according to the mode of the adhesive linkage subtend of this coverlay, be configured at interarea be formed the resin substrate with wiring of wiring pattern assigned position, be namely formed with the coating position of the coating epiphragma of the side of wiring pattern.Then, thermo-compressed is carried out with set point of temperature and stipulated time.
Temperature in thermo-compressed during interim crimping is preferably 100 ~ 150 DEG C.Preferably 0.5 ~ 10 minute time of interim crimping.
The temperature be heating and curing is preferably 150 ~ 210 DEG C.The time of being heating and curing is preferably 30 ~ 120 minutes.
In flexible printing wiring board of the present invention (FPC), the wiring pattern side of the resin substrate with wiring of wiring pattern is formed at interarea, this coverlay is configured with according to the mode of the adhesive linkage subtend of coverlay of the present invention, then carry out thermo-compressed, thus by with wiring resin substrate and coverlay integration.
The resin substrate that FPC of the present invention uses, also preferably has the electrical characteristics of excellent high-frequency region, namely has low-k (ε) and low dielectric loss angle tangent (tan δ) in the region of frequency 1 ~ 10GHz.As the concrete example of such resin substrate, can enumerate with any one of liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimides (PI) and PEN (PEN) is the resin substrate of principal component.
In addition, as other concrete examples of resin substrate being applicable to FPC of the present invention, the vinyl compound and (b) rubber that represent with (a) following general formula (1) can be enumerated and/or thermoplastic elastomer (TPE) is the resin substrate of principal component.
[changing 12]
About the vinyl compound that the above-mentioned formula (1) of composition (a) represents, as described in the explanation in the adhesive linkage of coverlay of the present invention.
The vinyl compound represented with (a) above-mentioned general formula (1) and (b) rubber and/or thermoplastic elastomer (TPE) are the resin substrate of principal component, there is the formation identical with coverlay of the present invention, also there is low-k and low dielectric loss angle tangent.For this reason, by combining with coverlay of the present invention, the FPC of high frequency characteristics excellence can be obtained.
Composition (b): rubber and/or thermoplastic elastomer (TPE)
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, containing at least one party in rubber and thermoplastic elastomer (TPE) as composition (b).Resin substrate can also contain rubber and thermoplastic elastomer (TPE) both sides.
As the rubber of composition (b), the rubber-like such as styrene butadiene rubbers, butyl rubber, butadiene rubber and acrylic rubber can be enumerated.Can be used alone a kind of these rubber-like, also two or more kinds may be used.
On the other hand, as thermoplastic elastomer (TPE), styrene series thermoplastic elastomer, olefin series thermoplastic elastomer and Polyester thermoplastic elastomer (TPE) etc. can be enumerated.Can be used alone a kind of thermoplastic elastomer (TPE), also two or more kinds may be used.
As composition (b), there is from resin substrate the reasons such as excellent flexibility, preferred thermoplastic elastomer, particularly preferably styrene series thermoplastic elastomer.
As the concrete example of styrene series thermoplastic elastomer, the copolymer that styrene-butadiene block copolymer, SIS or a part of hydrogenation by their double bond obtain can be enumerated.More specifically, SBS (SBS), SIS (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS) and styrene ethylene-propylene-styrene block copolymer (SEEPS) etc. can be enumerated.Wherein, preferred SBS and SEBS.
As composition (b), when using styrene series thermoplastic elastomer, its weight average molecular weight is preferably 20000 ~ 250000.In addition, good with the intermiscibility of composition (a), and resin substrate has the excellent transparency, so styrene-content is preferably 25 ~ 60 quality % in styrene series thermoplastic elastomer, is more preferably 30 ~ 50 quality %.It should be noted that, weight average molecular weight is the value using the calibration curve based on polystyrene standard to obtain by GPC.
As the concrete example of styrene series thermoplastic elastomer, can enumerate JSR Corp. styrene-butadiene block copolymer " JSR TR " series and styrene-isoprene block copolymer " JSR SIS " series etc.
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, except above-mentioned composition (a) and (b), preferably there is the carbamate prepolymer of the NCO of more than 2 or the NCO of end-blocking as composition (c) containing in 1 molecule.Such carbamate prepolymer constituent is the compound in polyalcohol and at least 1 molecule with the NCO of more than 2 or the NCO of end-blocking.
The carbamate prepolymer of composition (c) contributes to the adhesiveness of resin substrate.Composition (c) makes to improve in the adhesiveness of the resin substrate to temperature field during resin substrate transfer printing wiring pattern.
As the concrete example of the polyalcohol of the raw material of the carbamate prepolymer of composition (c), the dimer acid polyester polyhydric alcohols etc. polybutadiene polyol, polyisoprene polyol or the polyolefin polyalcohol hydrogenations such as polyisoprene polyol obtained can be enumerated, obtaining dimeric dibasic acid as carboxylic acid composition.
In addition, as other concrete examples of polyalcohol of raw material of carbamate prepolymer being used as composition (c), can enumerate 1,4-butanediol, 1, the dihydroxylic alcohols such as 6-hexane diol and ethylene glycol and, the trihydroxy alcohol such as trimethylolpropane.
Two or more kinds may be used for these polyalcohols.
As the compound with NCO of the raw material of the carbamate prepolymer of composition (c), as long as the NCO in 1 molecule with NCO or end-blocking amounts to the compound of more than 2, be just not particularly limited.As the concrete example of compound in 1 molecule with more than 2 NCOs, such as can enumerate tolylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, IPDI, hexamethylene diisocyanate and 4,4 '-dicyclohexyl methyl hydride diisocyanate etc.Particularly preferably tolylene diisocyanate and IPDI.In addition, as the compound of NCO with end-blocking, can enumerate and illustrative compound alcohols, the end-capping reagent such as phenols and oximes with NCO is herein carried out the compound that end-blocking obtains.
Preferably as the carbamate prepolymer of composition (c), be containing by polybutadiene polyol and 1, more than carbamate prepolymer 50 mass parts that obtains of 4-butanediol and tolylene diisocyanate, IPDI or hexamethylene diisocyanate carbamate prepolymer.
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, except above-mentioned composition (a) ~ (c), preferably contain silane coupler as composition (d).The silane coupler of composition (d), when when resin substrate transfer printing wiring pattern, contributes to the adhesion of resin substrate and wiring pattern.
As the concrete example of the silane coupler as composition (d), the oligomer of vinyl silanes system silane coupler, (methyl) acryloxy silane system silane coupler, isocynate silane system silane coupler, epoxy silane system silane coupler, amino silicone methane series silane coupler, hydrosulphonyl silane system silane coupler, chloropropyl silane system's silane coupler and these silane couplers can be enumerated.Wherein, preferably (methyl) acryloxy silane system's silane coupler and amino silicone methane series silane coupler.
As vinyl silanes system silane coupler, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane and trichloroethylene base silane etc. can be enumerated.
As (methyl) acryloxy silane system silane coupler, γ-acryloxypropyl trimethoxy silane, 3-(trimethoxysilyl) propyl acrylate and γ-methacryloxypropyl trimethoxy silane etc. can be enumerated.
As isocynate silane system silane coupler, 3-(triethoxysilyl) propylisocyanate etc. can be enumerated.
As epoxy silane system silane coupler, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. can be enumerated.
As amino silicone methane series silane coupler, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330, APTES, 3-TSL 8330 and 3-aminopropyl diethoxymethylsilane etc. can be enumerated.
As chloropropyl silane system silane coupler, 3-chloropropyl trichloro-silane etc. can be enumerated.
As hydrosulphonyl silane system silane coupler, (3-mercaptopropyi) triethoxysilane and (3-mercaptopropyi) trimethoxy silane etc. can be enumerated.
In addition, the oligomer of these silane couplers also can be used as composition (d).
Wherein, the preferably amino silicone methane series silane coupler such as (methyl) acryloxy silane system's silane coupler and N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330, APTES and 3-TSL 8330 such as γ-acryloxypropyl trimethoxy silane, 3-(trimethoxysilyl) propyl acrylate, γ-methacryloxypropyl trimethoxy silane.
In the concrete example of resin substrate being applicable to above-mentioned FPC of the present invention, the mass ratio of composition (a) and composition (b) is preferably 3:7 ~ 7:3, is more preferably 4:6 ~ 6:4.
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, when containing carbamate prepolymer as composition (c), composition (c) is preferably 99:1 ~ 40:60 relative to composition (a) and the mass ratio of the total amount of (b), be more preferably 97.5:2.5 ~ 50:50, more preferably 95:5 ~ 60:40.
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, when containing silane coupler as composition (d), composition (d) is preferably 99.99:0.01 ~ 90:10 relative to the mass ratio of the total amount of composition (a) ~ (c), be more preferably 99.9:0.1 ~ 95:5, more preferably 99.7:0.3 ~ 98:2.
Be applicable to the concrete example of the resin substrate of above-mentioned FPC of the present invention, can containing any composition beyond above-mentioned composition (a) ~ (d).As the concrete example of so any composition, the filler used to make the mechanical strength of resin substrate improve can be enumerated.As the concrete example of such filler, can enumerate the metallic compounds such as the metals such as silver powder, bronze and copper powder, silica, aluminium oxide, titanium oxide, boron nitride, iron oxide or, the organic filler such as carbon.
When containing filler as any composition, filler is preferably 9:1 ~ 1:9 relative to the mass ratio of the total amount of composition (a) ~ (d), is more preferably 8:2 ~ 2:8, more preferably 7:3 ~ 3:7.
In addition, be applicable to the resin substrate of above-mentioned FPC of the present invention, for the object of the mechanical strength of raising resin substrate, can contain the organic fiber of the inorfil or aramid fibre and so on of above-mentioned filler and glass fibre and carbon fiber and so on, or the organic fiber of the inorfil or aramid fibre and so on that contain glass fibre and carbon fiber and so on replaces above-mentioned filler.
[embodiment]
Below, describe the present invention in detail by embodiment, but the present invention is not limited to them.
(embodiment 1 ~ 12, comparative example 1 ~ 9)
< sample is made and assay method (being only adhesion film) >
Replace the adhesive linkage of coverlay of the present invention, make the adhesion film that composition is identical with this adhesive linkage, its physical property is evaluated.
According to the mode coordinating each composition with the ratio (quality %) shown in following table, metering coordinates each composition.Then, they are rendered in the reactor being heated to 70 DEG C.While make each composition of input carry out rotation limit with rotating speed 300rpm mix 3 hours at ambient pressure.When adding curing agent, after cooling, with the addition of curing agent.
Varnish containing the resin combination so obtained is coated the one side of supporting mass (implementing this PET film of demoulding process).Make the varnish-drying on supporting mass at 100 DEG C, resulting in the adhesion film of band supporting mass.
It should be noted that, the shorthand notation in table is as follows respectively.
Composition (A)
OPE2200: oligomeric phenylate (vinyl compound that above-mentioned general formula (1) represents) (Mn=2200), Mitsubishi Gas Chemical Co., Ltd's system
Composition (B)
TUFTEC H1052: polystyrene-poly (ethylene/butylene) block copolymer (styrene amount 20%), Asahi Kasei Corporation's system
TUFTEC H1031: polystyrene-poly (ethylene/butylene) block copolymer (styrene amount 30%), Asahi Kasei Corporation's system
Composition (C)
SEPTON 4044: polystyrene-poly (ethylene-vinyl/propylene) block copolymer (styrene amount 32%), Kuraray Co., Ltd.'s system
Composition (B ')
TR2003: polystyrene-polybutadiene block copolymer (phenylethylene/butadiene=43/57), JSR Corp.'s system
Composition (D)
NC3000H: biphenyl type epoxy resin, Nippon Kayaku K. K's system
Composition (E)
BMI-70: bismaleimides, KI change into Co., Ltd.'s system
Composition (F)
C11ZCN:1-cyanoethyl-2-undecyl imidazole, Shikoku Chem's system
2E4MZ:2-ethyl-4-methylimidazole, Shikoku Chem's system
TPP-MK: tetraphenylphosphoniphenolate four ptolylboronic acid salt, Hokko Chemical Industry Co., Ltd.'s system
Intermiscibility: be diluted to suitable concentration with solvent (toluene), coat strippable base material, after 100 DEG C × 10min drying, becomes 20 μm of thick films.The state of observing the varnish obtained through solvent dilution and both the states on the surface of film formed by this varnish, carry out the evaluation of intermiscibility.Visually judge whether varnish has muddiness.The surface of film is observed by CCD camera (× 100 times).
Varnish is had muddiness and have on the surface of the film formed by this varnish the grivelle of more than 100 μm or cannot the situation of membranization be designated as ×.Though varnish is had muddiness but does not have on the surface of the film formed by this varnish the situation of the grivelle of more than 100 μm to be designated as zero.Varnish is designated as ◎ without muddy and on the surface of the film formed by this varnish without the grivelle of more than 100 μm situation.
Dielectric constant (ε) and dielectric loss angle tangent (tan δ): adhesion film is heating and curing at 200 DEG C.From supporting mass by adhesion film peel off after, cut out test film (40 ± 0.5mm × 100 ± 2mm) from this adhesion film, measure its thickness.Test film is rolled into the tubular of length 100mm, below diameter 2mm.By cavity resonator perturbation method (10GHz), the dielectric constant (ε) of the test film spooled and dielectric loss angle tangent (tan δ) are measured.
Glass transition temperature Tg: measure by Measurement of Dynamic Viscoelasticity (DMA).Adhesion film is heating and curing at 200 DEG C, after supporting mass is peeled off, cuts out test film (10 ± 0.5mm × 40 ± 1mm) from this adhesion film, the width of test film and thickness are measured.Then, carry out measuring (3 DEG C/min 25-300 DEG C) with DMS 6100.Read the peak temperature of tanD, as Tg.
Cross cut cementability: at the one side laminating Copper Foil glassy surface of adhesion film, then utilize forcing press to implement thermo-compressed (200 DEG C of 60min, 10kgf).Then, supporting mass is peeled off.Then, at this cementability face with 1mm interval incision clathrate cut channel, thus form 100 pieces.Band is attached on these 100 blocks.Then, instantaneously band is stripped off with the angle in 90 ° relative to face.Judge now whether film is peeled off from Copper Foil glassy surface.It should be noted that, the following benchmark of result is judged.
In zero: 100 piece 1 piece all unstripped.
×: have 1 piece of stripping in 100 pieces at least.
Tensile modulus of elasticity: adhesion film is heating and curing at 200 DEG C.From supporting mass by after adhesion film stripping, cut out 5 test films (25 ± 0.5mm × 220 ± 2mm) from this adhesion film along MD direction, its thickness is measured.This test film is sandwiched universal testing machine (AUTOGRAPH), clamp jaw width is set as 170mm, then implement to measure under the condition of draw speed 1mm/min, stroke 5mm.Using the mean value of N=5 as measured value.
Curling evaluation: the LCP film (VECSTAR (registered trade mark) CT-Z (Kuraray Co., Ltd.'s system)) of thickness 50 μm is cut out 50 ± 0.5mm square.With forcing press, the adhesion film hot pressing of being cut into same size is connected to the one side (200 DEG C of 60min, 10kgf) of LCP film.Then, after supporting mass is peeled off, will facing up of adhesion film be pasted with, be placed on the horizontal plane of smooth desk, observe curling degree thus.Float the maximum D of upper height according to the horizontal plane test film end from desk, judge according to following benchmark.
Zero: test film does not become tubular and D≤15mm.
△: test film does not become tubular and 15mm<D.
×: test film becomes tubular.
Table 1
Table 2
Table 3
Table 4
In embodiment 1 ~ 11, electrical characteristics (dielectric constant (ε), dielectric loss angle tangent (tan δ)) and the tensile modulus of elasticity of intermiscibility, curling, cross cut cementability, high-frequency region are all very excellent.Particularly in embodiment 1,3 ~ 8,10, intermiscibility is excellent especially.In addition, increasing in the embodiment 5 of B/C compared with embodiment 1, tensile modulus of elasticity can be reduced.
In the embodiment 6 that B/C compared with embodiment 5 is larger, tensile modulus of elasticity can be reduced further.
In addition, in the embodiment 8 that the content of the epoxy resin of (D) composition compared with embodiment 1 is less, dielectric loss angle tangent (tan δ) can be reduced further.
In replacement composition (B) and (C) and use polystyrene-polybutadiene block copolymer as in the comparative example 1 of thermoplastic elastomer (TPE), tensile modulus of elasticity raises, and in addition, curlingly to worsen.
Not containing in the comparative example 2 of composition (B), tensile modulus of elasticity raises, and in addition, curlingly to worsen.
At mass ratio (A+E)/(B+C) of each composition lower than in the comparative example 3 of 0.81, cross cut cementability is deteriorated.
In comparative example 4 more than 1.00 of mass ratio (A+E)/(B+C) of each composition, intermiscibility declines, and in addition, tensile modulus of elasticity raises, and curlingly worsens.
At mass ratio (B)/(C) of composition (B) and (C) lower than in the comparative example 5 and 6 of 1.00, tensile modulus of elasticity raises, and curlingly worsens.
In comparative example 7 more than 4.00 of mass ratio (B)/(C) of composition (B) and (C), intermiscibility and cross cut cementability are deteriorated.
Not containing in the comparative example 8 of composition (C), because intermiscibility declines, so cannot obtain smooth film.For this reason, curling etc. evaluation cannot be implemented.
At the content of the epoxy resin of composition (D) relative to composition (A) more than in the comparative example 9 of 6 mass parts, intermiscibility declines.In addition, the dielectric loss angle tangent (tan δ) of the thing that is heating and curing of adhesion film is more than 0.004.
< sample is made (to be had with assay method and is formed with the coverlay of 2 Rotating fields of adhesive linkage at fusing point higher than the one side of the organic film of the heat curing temperature of adhesive linkage.)>
By the varnish containing the resin combination (embodiment 5) obtained by step same as described above, coat the one side of fusing point higher than the organic film of the heat curing temperature of resin combination.Make varnish on organic film 100 DEG C of dryings, resulting in the coverlay having and be formed with 2 Rotating fields of adhesive linkage in the one side of organic film.
In addition, as additive method, by the adhesion film (embodiment 5) of band supporting mass obtained by step same as described above, be crimped on the one side of fusing point higher than the organic film of the heat curing temperature of this adhesion film at 120 DEG C temporarily, resulting in the coverlay having and be formed with 2 Rotating fields of adhesive linkage in the one side of organic film.
It should be noted that, with regard to organic film, use VECSTAR (registered trade mark) CT-Z (Kuraray Co., Ltd.'s system) of thickness 25 μm as LCP film.The fusing point of this LCP film is 335 DEG C.In addition, 2 kinds of adhesive linkages of the thickness with 15 μm and 25 μm have been made.
About the coverlay with 2 Rotating fields made, implement following evaluation.
Dielectric constant (ε), dielectric loss angle tangent (tan δ): the coverlay with 2 Rotating fields is heating and curing at 200 DEG C.Cut out test film (40 ± 0.5mm × 100 ± 2mm) from this coverlay with 2 Rotating fields, its thickness is measured.Test film is rolled into the tubular of length 100mm, below diameter 2mm.By cavity resonator perturbation method (10GHz), the dielectric constant (ε) of the test film spooled and dielectric loss angle tangent (tan δ) are measured.
Peel strength: after the adhesive linkage laminating Copper Foil glassy surface of the coverlay of 2 Rotating fields, utilize forcing press to implement thermo-compressed (200 DEG C of 60min, 10kgf).Then, this test film is cut into 10mm width.To be torn Copper Foil from the test film after cutting by universal testing machine (AUTOGRAPH), peel strength is measured.About measurement result, the mean value of each N=5 is calculated.
Cross cut cementability: after the adhesive linkage laminating Copper Foil glassy surface of coverlay with 2 Rotating fields, utilize forcing press to implement thermo-compressed (200 DEG C of 60min, 10kgf).In organic film (LCP film) face of this coverlay with 1mm interval incision clathrate cut channel, form 100 pieces.Band is attached on these 100 blocks.Then, instantaneously band is stripped off with the angle in 90 ° relative to organic film (LCP film) face.Judge now whether organic film (LCP film) is peeled off from Copper Foil glassy surface.
The dielectric constant (ε) of the coverlay of the adhesive linkage containing thickness 15 μm is 2.9, and dielectric loss angle tangent (tan δ) is 0.0024.Its peel strength is 6.58N/cm.Peel off in the evaluation of cross cut cementability.
Be in the coverlay of 25 μm at the thickness of adhesive linkage, dielectric constant (ε) is 2.8, and dielectric loss angle tangent (tan δ) is 0.0026.Peel strength is 6.77N/cm.Peel off in the evaluation of cross cut cementability.
Can confirm according to these results, according to the coverlay with 2 Rotating fields that the mode of the thickness changing adhesive linkage makes, all there is the electrical characteristics (DIELECTRIC CONSTANT ε, dielectric loss angle tangent tan δ) of excellent high-frequency region, peel strength and cross cut cementability.
It should be noted that, the dielectric constant (ε) of independent LCP film is 3.2, and dielectric loss angle tangent (tan δ) is 0.0022.In addition, the dielectric constant (ε) of independent adhesive linkage (adhesion film) (thickness 25 μm) is 2.3, and dielectric loss angle tangent (tan δ) is 0.0030.
In addition, utilize step same as described above, use PI film as organic film, make the coverlay with 2 Rotating fields, its dielectric constant (ε) and dielectric loss angle tangent (tan δ) are evaluated.
As PI film, employ following film.
XENOMAX (registered trade mark), Toyo Boseki K.K's system, thickness 12.5 μm
KAPTON (registered trade mark) 100EN, Dong Li Dupont Kabushiki Kaisha system, thickness 25 μm
KAPTON (registered trade mark) 300H, Dong Li Dupont Kabushiki Kaisha system, thickness 77 μm,
Result is as follows respectively.
The independent XENOMAX of < (registered trade mark) >
Dielectric constant (ε): 3.6
Dielectric loss angle tangent (tan δ): 0.0114
The coverlay > of < two-layer structure
Dielectric constant (ε): 2.8
Dielectric loss angle tangent (tan δ): 0.0059
The independent KAPTON of < (registered trade mark) 100EN>
Dielectric constant (ε): 3.3
Dielectric loss angle tangent (tan δ): 0.0086
The coverlay > of < two-layer structure
Dielectric constant (ε): 2.8
Dielectric loss angle tangent (tan δ): 0.0059
The independent KAPTON of < (registered trade mark) 300H>
Dielectric constant (ε): 3.3
Dielectric loss angle tangent (tan δ): 0.0144
The coverlay > of < two-layer structure
Dielectric constant (ε): 3.0
Dielectric loss angle tangent (tan δ): 0.0108
Can confirm according to these results, use different types of PI film as organic film and the coverlay with 2 Rotating fields made according to the mode of the thickness changing adhesive linkage, also there are the electrical characteristics (DIELECTRIC CONSTANT ε, dielectric loss angle tangent tan δ) of excellent high-frequency region.
The FPC that < will be principal component using composition (a) and (b) is as the manufacture method > of the printed wiring version of matrix
In being made of resin substrate of FPC, employ the resin combination containing following compositions.
Composition (a): OPE2st: oligomeric phenylate (vinyl compound that above-mentioned general formula (1) represents) (Mn=1200), Mitsubishi Gas Chemical Co., Ltd's system 54.3 parts
Composition (b): polystyrene-polybutadiene block copolymer (JSR Corp.'s system: " TR2003 ": weight average molecular weight about 100,000, styrene-content 43 quality %) 36.2 parts
Composition (c): carbamate prepolymer 9 parts
To in the four-hole boiling flask of 2000ml possessing reflux condenser, agitator and thermometer, put into toluene 600g, polyalcohol (" EPOL PIP-H ", bright dipping petrochemistry system; Sp=8.20) 633.3g, 1,4-butanediol 33.3g and IPDI 233.3g.After by these compound uniform dissolution, add triethylene diamine 0.06g as catalyst.Heating makes flask interior temperature be 70 DEG C to 80 DEG C, carries out the urethane reaction of 7 hours.Then, the toluene solution of carbamate prepolymer is obtained by cooling.The free isocyanate amount of the unit solid state component of this solution is 3.5 quality %.
Composition (d): silane coupler 0.5 part
γ-acryloxypropyl trimethoxy silane (" KBM-5103 ", Shin-Etsu Chemial Co., Ltd's system)
Use Three-One Motor (Xin Dong science Co., Ltd. system, BLW1200), with peripheral speed 400rpm, dry type mixing is carried out to above-mentioned each composition, prepared resin combination.After being added to by this resin combination in the methyl ethyl ketone of solvent, prepare varnish (solid component concentration about 30 quality %) by adding thermal agitation.With gravure coater, this varnish is coated as in the PET film (thickness 50 μm) of supporting mass.Then, carry out the drying of 10 minutes at 100 DEG C, and place cooling.By being peeled off from PET film by varnish, obtain the resin substrate of FPC.The thickness of resin substrate is 30 μm.
On the two sides of the resin substrate obtained by above-mentioned step, with alligatoring face for inner side has been fitted after Copper Foil, forcing press is utilized to implement thermo-compressed (200 DEG C of 60min, 10kgf).Describe wiring pattern by the etching of the one or both sides of the Copper Foil after thermo-compressed, make the resin substrate with wiring thus.In this wiring pattern side of resin substrate with wiring, configure this coverlay according to the mode with the coverlay subtend of 2 Rotating fields obtained by above-mentioned step.Printed wiring version is made by utilizing the thermo-compressed of forcing press (200 DEG C of 60min, 10kgf).

Claims (13)

1. a coverlay, is characterized in that,
It is formed with adhesive linkage in the one side of organic film,
Described adhesive linkage contains:
(A) following general formula (1) represent vinyl compound,
(B) polystyrene-poly (ethylene/butylene) block copolymer,
(C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer,
(D) epoxy resin,
(E) bismaleimides,
In formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl ,-(O-X-O)-as shown in following structural formula (2),
R 8, R 9, R 10, R 14, and R 15identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 11, R 12, and R 13identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl,-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement
R 16and R 17identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 18and R 19identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl, Z is the organic group of carbon number more than 1, comprise or do not comprise oxygen atom, nitrogen-atoms, sulphur atom or halogen atom, a and b represents the integer of 0 ~ 300, the at least one party of a and b is not the integer that 0, c and d represents 0 or 1
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B) described composition (D) 1 ~ 10 quality % below 4.00, and is contained relative to the gross mass of described composition (A) ~ (E) in/(C)=more than 1.00;
Described organic film has the fusing point of the heat curing temperature higher than described adhesive linkage, and has the DIELECTRIC CONSTANT ε of less than 4.0 and the dielectric loss angle tangent tan δ of less than 0.02 in the region of frequency 1 ~ 10GHz.
2. coverlay as claimed in claim 1, wherein,
Described (A) composition-(O-X-O)-as shown in following structural formula (4),
Described (A) composition-(Y-O)-have: the structure that following structural formula (5) or following structural formula (6) represent or the structure that following structural formula (5) represents and the structure that following structural formula (6) represents are through the structure of random arrangement
3. coverlay as claimed in claim 2, wherein,
Described composition (A)-structure that represents of (Y-O)-have described structural formula (6).
4. as the coverlay in claims 1 to 3 as described in any one, wherein,
The lowest melt viscosity of the described adhesive linkage of the temperature field of 150 ~ 200 DEG C is more than 2000Pas below 10000Pas.
5. as the coverlay in Claims 1 to 4 as described in any one, wherein,
After the hot curing of described adhesive linkage, there is in the region of frequency 1 ~ 10GHz the DIELECTRIC CONSTANT ε of less than 3.5 and the dielectric loss angle tangent tan δ of less than 0.02.
6. as the coverlay in Claims 1 to 5 as described in any one, wherein,
Described adhesive linkage after hot curing illustrates the DIELECTRIC CONSTANT ε of less than 2.5 and the dielectric loss angle tangent tan δ of less than 0.004 in the region of frequency 1 ~ 10GHz.
7. as the coverlay in claim 1 ~ 6 as described in any one, wherein,
Any one in described organic film use liquid crystal polymer, polyimides, PEN and polytetrafluoroethylene is made.
8. a flexible printing wiring board, is characterized in that,
Form through thermo-compressed integration by with the coverlay in the resin substrate connected up and claim 1 ~ 7 described in any one,
The described resin substrate with wiring is formed with wiring pattern at the interarea of any one resin substrate being principal component with liquid crystal polymer, polyimides and PEN,
Described coverlay is configured at the wiring pattern side of the described resin substrate with wiring according to the mode of adhesive linkage subtend.
9. a flexible printing wiring board, is characterized in that,
Form through thermo-compressed integration by with the coverlay in the resin substrate connected up and claim 1 ~ 7 described in any one,
The described resin substrate with wiring be the vinyl compound (a) represented with following general formula (1) and, the interarea of rubber and/or thermoplastic elastomer (TPE) (b) resin substrate that is principal component is formed with wiring pattern,
Described coverlay is configured at the wiring pattern side of the described resin substrate with wiring according to the mode of adhesive linkage subtend,
In formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl ,-(O-X-O)-as shown in following structural formula (2),
R 8, R 9, R 10, R 14, and R 15identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 11, R 12, and R 13identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl,-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement
R 16and R 17identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 18and R 19identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl, Z is the organic group of carbon number more than 1, comprise or do not comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300, the at least one party of a and b is not the integer that 0, c and d represents 0 or 1.
10. a manufacture method for coverlay, is characterized in that,
The manufacture method of the coverlay of the adhesive linkage that its one side being included in organic film is formed, comprises:
By making the varnish-drying containing resin combination of the coated on one side at described organic film, form described adhesive linkage;
Described resin combination contains:
(A) following general formula (1) represent vinyl compound,
(B) polystyrene-poly (ethylene/butylene) block copolymer,
(C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer,
(D) epoxy resin,
(E) bismaleimides,
In formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl ,-(O-X-O)-as shown in following structural formula (2),
R 8, R 9, R 10, R 14, and R 15identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 11, R 12, and R 13identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl,-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement
R 16and R 17identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 18and R 19identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl, Z is the organic group of carbon number more than 1, comprise or do not comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300, the at least one party of a and b is not the integer that 0, c and d represents 0 or 1
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B)/(C)=more than 1.00 are below 4.00, and contain described composition (D) 1 ~ 10 quality % relative to the gross mass of described composition (A) ~ (E)
Described organic film has the fusing point of the heat curing temperature higher than described resin combination, and has the DIELECTRIC CONSTANT ε of less than 4.0 and the dielectric loss angle tangent tan δ of less than 0.02 in the region of frequency 1 ~ 10GHz.
The manufacture method of 11. 1 kinds of coverlays, is characterized in that,
The manufacture method of the coverlay of the adhesive linkage that its one side being included in organic film is formed, comprises:
Adhesion film is made by resin combination, and,
Described adhesive linkage is formed by described adhesion film and described organic film being fitted;
Described resin combination comprises:
(A) following general formula (1) represent vinyl compound,
(B) polystyrene-poly (ethylene/butylene) block copolymer,
(C) polystyrene-poly (ethylene-vinyl/propylene) block copolymer,
(D) epoxy resin,
(E) bismaleimides,
In formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl ,-(O-X-O)-as shown in following structural formula (2),
R 8, R 9, R 10, R 14, and R 15identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 11, R 12, and R 13identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl,-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement
R 16and R 17identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 18and R 19identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl, Z is the organic group of carbon number more than 1, comprise or do not comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300, the at least one party of a and b is not the integer that 0, c and d represents 0 or 1
Here, the mass ratio of each composition is that (A+E)/(B+C)=more than 0.81 is below 1.00, (B)/(C)=more than 1.00 are below 4.00, and contain described composition (D) 1 ~ 10 quality % relative to the gross mass of described composition (A) ~ (E)
Described organic film has the fusing point of the heat curing temperature higher than described adhesion film, and has the DIELECTRIC CONSTANT ε of less than 4.0 and the dielectric loss angle tangent tan δ of less than 0.02 in the region of frequency 1 ~ 10GHz.
The manufacture method of 12. 1 kinds of flexible printing wiring boards, is characterized in that, comprises:
By arranging wiring pattern at the interarea of the resin substrate being principal component with any one in liquid crystal polymer, polyimides and PEN, make the resin substrate with wiring;
In the described wiring pattern side of the described resin substrate with wiring, configure described coverlay according to the mode of the adhesive linkage subtend of the coverlay in claim 1 ~ 7 described in any one; And,
The described resin substrate with wiring and the integration of described coverlay is made by thermo-compressed.
The manufacture method of 13. 1 kinds of flexible printing wiring boards, is characterized in that, comprises:
By the vinyl compound represented with following general formula (1) and, rubber and/or thermoplastic elastomer (TPE) be that the interarea of the resin substrate of principal component arranges wiring pattern, makes the resin substrate with wiring;
In the described wiring pattern side of the described resin substrate with wiring, configure described coverlay according to the mode of the adhesive linkage subtend of the coverlay in claim 1 ~ 7 described in any one; And,
The described resin substrate with wiring and the integration of described coverlay is made by thermo-compressed;
In formula, R 1, R 2, R 3, R 4, R 5, R 6, and R 7identical or different, be hydrogen atom, halogen atom, alkyl, halogenated alkyl or phenyl ,-(O-X-O)-as shown in following structural formula (2),
R 8, R 9, R 10, R 14, and R 15identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 11, R 12, and R 13identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl,-(Y-O)-have: the a kind of structure defined by following structural formula (3) or the structure of more than two kinds defined by following structural formula (3) of random arrangement
R 16and R 17identical or different, be halogen atom, the alkyl of carbon number less than 6 or phenyl, R 18and R 19identical or different, hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl, Z is the organic group of carbon number more than 1, comprise or do not comprise oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300, the at least one party of a and b is not the integer that 0, c and d represents 0 or 1.
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