WO2005025857A1 - 樹脂複合フィルム - Google Patents
樹脂複合フィルム Download PDFInfo
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- WO2005025857A1 WO2005025857A1 PCT/JP2004/013271 JP2004013271W WO2005025857A1 WO 2005025857 A1 WO2005025857 A1 WO 2005025857A1 JP 2004013271 W JP2004013271 W JP 2004013271W WO 2005025857 A1 WO2005025857 A1 WO 2005025857A1
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- Prior art keywords
- resin
- layer
- composite film
- metal
- film
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
- H05K2201/10621—Components characterised by their electrical contacts
- H05K2201/10681—Tape Carrier Package [TCP]; Flexible sheet connector
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a wiring film for a semiconductor package, a film for a flexible printed wiring board, and a wiring film for mounting a semiconductor chip.
- the present invention relates to a resin composite film which is suitable.
- a flexible wiring board in which a roughened copper foil is adhered to a polyimide film via an epoxy-based adhesive or a polyimide-based adhesive has excellent flexibility. Taking advantage of this advantage, such a flexible wiring board can be used as a flexible circuit board that connects circuit boards in fields such as mobile phones, digital cameras, and LCD displays that need to be stored in a small space. It has been used as a flex part of doflex boards and tapes for automated bonding (TAB).
- TAB automated bonding
- an alloy of Ni and Cr is sputtered on the smooth surface of the polyimide film to form a seed layer, and then copper is sputtered on the shield layer.
- a metal-resin composite film obtained by forming a thin film layer and growing copper on this copper foil thin film layer by electrolytic plating has been proposed and has been put to practical use in some electronic devices.
- the insulation resistance tends to deteriorate, which is an important problem especially in recent electronic components that require higher density and higher voltage. ing.
- Japanese Patent Application Laid-Open No. 2003-179357 discloses a method of providing a water vapor blocking layer made of an inorganic insulating film between a polyimide film and a metal layer.
- Japanese Patent Application Laid-Open No. 11-129939 describes a method for solving the deterioration of insulation resistance when a metal layer is directly provided on a polyimide film which is a condensation-polymerized polymer.
- Resin consisting of a film consisting of a ring-opening or addition polymer of a monomer having a ring structure or a modified product thereof hereinafter referred to as a ring structure-containing polymer finolem
- a film consisting of a polycondensation polymer It is disclosed that a composite film is used instead of a polyimide film. It is disclosed that a metal-resin composite film can be obtained by forming a metal layer on the ring-structure-containing polymer film side of the resin composite film. Disclosure of the invention
- the present inventors have conducted intensive studies to obtain a resin composite finolem having excellent adhesion to a metal layer even under high temperature and pressure conditions, and as a result, a resin composite film having a resin A layer and a resin B layer, By controlling the thickness of the layer B within a predetermined range and using an insulating material having a specific water absorption, a resin composite film having excellent adhesion to the metal layer can be obtained even under high temperature and pressure conditions. And completed the present invention.
- an uncured or semi-cured resin layer is obtained by applying an insulating material containing an insulating polymer and a curing agent on the resin A layer, and the resin layer is contacted with a compound having a metal coordinable structure. Then, the resin layer is heated, and a resin composite film obtained by providing a metal layer by a plating method on the resin B layer formed on the resin A layer has a smooth interface with the metal layer of the resin B layer. Nevertheless, the metal layer has excellent adhesion, and the interface is smooth, so that high-density wiring can be formed.
- a resin composite film having a resin A layer formed on at least one surface of a resin A layer, wherein the resin B layer has a thickness of 0.1 to 4 / zm, and The insulating material constituting the resin layer has a water absorption of 0.03 to 0.25% when the thickness is 10 ⁇ .
- a resin composite film is provided.
- the water absorption means the water absorption of a finolem having a thickness of 10 m.
- the resin composite film is characterized in that an insulating material containing an insulating polymer and a curing agent is applied on the resin A layer and then heated to form the resin B layer.
- a method of manufacturing is provided.
- a metal-resin composite film in which a metal layer is provided on the surface of the resin B layer of the resin composite film.
- This composite film is particularly useful as a wiring film for a semiconductor package, a film for a flexible printed wiring board, a wiring finolem for mounting a semiconductor chip, and the like.
- the metal layer may be formed in a pattern.
- the resin composite film of the present invention has a resin B layer formed on at least one surface of the resin A layer.
- the resin A layer used in the present invention may be made of a thermoplastic resin or a thermosetting resin, but has sufficient strength characteristics as a flexible circuit board and reliability of component mounting. From the viewpoint of obtaining the property, a glass transition temperature (Tg) force S of 70 ° C. or more, preferably 100 ° C. or more, more preferably 120 ° C. or more, and a melting point of 190 ° C. As described above, it is preferably at least 220 ° C, more preferably at least 250 ° C.
- the layer A may be a single type of film alone, or may be a film laminated by combining same or different types of films.
- the resin A layer formed by laminating the same or different films in combination may be a layer in which a layer made of an organic or inorganic nonwoven fabric or the like is formed on the surface where the resin B layer is not formed or on the inside.
- the resin A layer include polyphenylene oxide and polycarbonate.
- Polyether resins such as polyether ketone; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate and liquid crystal polyester; Polyamide resin; Polysulfone resin; Polyphenylene sulfide resin; Imide resin; polyimide resin; and the like.
- liquid crystal polyester resin ⁇ polyimide resin is preferred from the viewpoint of mechanical strength and heat resistance.
- the thickness of the resin A layer should be selected in consideration of workability and mechanical characteristics required for the application. ⁇ 200 / im.
- the thickness of the resin A layer is preferably from 10 / zm to 100 ⁇ .
- the surface of the resin layer is contacted with the resin B layer in advance by corona discharge treatment, low temperature or normal pressure plasma treatment, or the like.
- Blast treatment / rubbing Pre-treatment such as physical roughening treatment;
- the thickness of the resin B layer formed on at least one side of the resin A layer is from 0.3 to 4 ⁇ , preferably from 0.3 to 4 ⁇ , and more preferably from 0.5 to 3.5. ⁇ ⁇ . If the resin layer is too thick, there will be a problem that the metal layer will peel off during high-temperature press-mounting.On the other hand, if it is too thin, the insulation resistance may deteriorate or the operability of forming the resin layer may decrease. You.
- the resin layer according to the present invention has a water absorption of 0.3 to 0.25%, preferably 0.05 to 5% when formed into a film having a thickness of 10 ⁇ m. It is made of 0.2% insulating material.
- the resin B layer is formed using an insulating material having an excessively high water absorption in this film state, the insulating performance is significantly reduced.
- the resin A layer and the B3B layer under high temperature and humidification conditions are used. Adhesion tends to decrease.
- This water absorption can be controlled by using a specific insulating polymer as an insulating material or by further mixing a curing agent or the like.
- the water absorption of a 10 / m-thick film is a value calculated in the following manner. That is, the material used for forming the resin B layer is formed into a film having a thickness of 10 ⁇ and a length and a width of 3 cm. After drying at C Open for 2 hours, the weight when cooled to room temperature in a desiccator is W0, then this sample is immersed in distilled water at 25 ° C, and after 24 hours, pulled out of the water and dried. W1 is the weight when weighed immediately after wiping, and is the value calculated from the following equation 1.
- the resin B layer preferably has a tensile elongation at break measured by the following method of 1.5% or more.
- the tensile elongation at break is the material used to form the resin B layer.
- an insulating material containing an insulating polymer and a curing agent is used as a method for forming the resin B layer.
- the insulating polymer examples include an epoxy resin, a maleimide resin, a (meth) acryl resin, a diaryl phthalate resin, a triazine resin, an alicyclic olefin polymer, an aromatic polyether polymer, Benzosi And butene polymers and cyanate ester polymers.
- an alicyclic olefin polymer, an aromatic polyether polymer, a benzocyclobutene polymer, and a cyanoester polymer are preferred from the viewpoint of low water absorption, and an alicyclic olefin polymer or an aromatic polyether polymer is preferred.
- a coalescence is particularly preferred, and an alicyclic olefin polymer is particularly preferred.
- the weight average molecular weight M w of the insulating polymer is usually 10 0 0 0 0 0 0 0 0 0 0 0 and preferably 3 0 0 0 0 0 0 0 3 0 0 0 and 0 0 0. It is desirable that This is because, when plating is performed later, the roughening of the luster B layer due to the pretreatment is suppressed and the mechanical properties of the resin composite film are excellent.
- the weight-average molecular weight Mw is the weight-average molecular weight in terms of polystyrene or polystyrene measured by gel permeation chromatography (GPC).
- the alicyclic polymer which is a particularly preferable insulating polymer, is a polymer of an unsaturated hydrocarbon having an alicyclic structure.
- Specific examples of the alicyclic olefin polymer include a ring-opened polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norpol- ene-based monomer, and a norbornene-based monomer and vinyl. Addition polymer with compound, monocyclic cycloalkene polymer, lunar cyclic conjugated diene polymer, vinyl-based alicyclic hydrocarbon polymer and hydrogenated product thereof, aromatic hydrogenation of aromatic olefin polymer Things are raised.
- a ring-opening polymer of a norpolene-based monomer and its hydrogenated product an addition polymer of a norbornene-based monomer, an addition polymer of a norpol- ene-based monomer and a vinyl compound, and an aromatic olefin polymer
- the hydrogenated aromatic ring is particularly preferable, and a hydrogenated product of a ring-opened polymer of a norpolene-based monomer is particularly preferable.
- alicyclic olefin polymer those having a polar group are preferable. Yes.
- the polar group include a hydroxyl group, a carboxyl group, an alkoxy group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carboyl group, an amino group, an ester group, and a carboxylic anhydride group.
- a carboxyl group or a carboxylic acid anhydride (carboxyloxynoreponyl) group is preferred.
- Alicyclic Orefui down polymer is usually 8 Echiru Ichite Torashikuro [4 4 0 1 2, 5, 1 7-1 0...] Dodeka 3 -. Enyato Li consequent opening [4 3. 0.1 2 '5] Deka 3,7 Jen a norbornene monomer having a norbornene nen ring such as, if necessary by addition polymerization or ring-opening polymerization with other monomers, and optionally It can be obtained by hydrogenating an unsaturated bond portion or by addition-polymerizing an aromatic olefin and hydrogenating an aromatic ring portion of the polymer. Further, an alicyclic olefin polymer having a polar group is, for example,
- a polar group is introduced into the alicyclic polymer by a modification reaction, and (2) a monomer containing a polar group is copolymerized as a copolymer component.
- the alicyclic olefin polymer having a polar group (3) is obtained by copolymerizing a monomer containing a polar group such as an ester group as a copolymerization component, and then hydrolyzing the ester group. And can convert the polar group.
- the alicyclic olefin polymer is obtained by copolymerizing an alicyclic olefin and / or an aromatic olefin with a monomer copolymerizable therewith (for example, 11-hexene). You can also get.
- the glass transition temperature of the alicyclic polymer can be appropriately selected according to the purpose of use, but is usually at least 50 ° C, preferably at least 70 ° C, more preferably at least 100 ° C. Most preferably, it is at least 125 ° C.
- the curing agent is not particularly limited as long as it forms a crosslinked structure by heating and cures.
- ionic curing agent radical
- radical A known heat curing agent such as a curing agent or a curing agent having both a cationic property and a radical property can be used.
- the mixing ratio of the curing agent is usually in the range of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the insulating polymer. It is.
- a curing accelerator together with a curing agent is preferable because it is easy to obtain a resin B layer having a high heat resistance and a low water absorption of a 10 m thick film.
- a polyhydric epoxy compound is used as a curing agent
- a tertiary amine compound such as a triazole compound or a dimidazole compound or a curing accelerator such as a boron trifluoride complex compound is used. You can.
- Insulation materials include flame retardants, fillers, flexible polymers, heat stabilizers, weather stabilizers, anti-aging agents, leveling agents, antistatic agents, slip agents, anti-blocking agents, and anti-blocking agents.
- Fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, eggs, emulsions, magnetic materials, dielectric property modifiers, toughening agents, etc. may be used in combination. These mixing ratios are appropriately selected within a range that does not impair the purpose of the present invention.
- a resin component filler that can be dissolved in an oxidizing treatment solution used for a treatment before plating is contained in an insulator material. Can be included.
- the resin B layer having the above-mentioned water absorption and tensile elongation at break it is particularly necessary to use a sodium hydroxide, which is measured in accordance with JISK7114. It is preferable to use an insulating material having a mass change rate of 0.01 to 0.5%, preferably 0.05 to 0.3% after being immersed in an aqueous solution.
- the details of the evaluation of the rate of change in mass are as follows.
- the condition is adjusted according to the class 2 of JISK 7100: 2001 23 350, and the weight m 1 of the test piece is measured.
- Rate of change of mass (%) [(m 2-ml) / ml] X 100
- the state of the varnish is determined by adding a solvent to the insulating material.
- the method of forming the resin B layer in this manner is preferable because the moldability is good.
- the solvent include aromatic hydrocarbon organic solvents such as toluene, xylene, ethylbenzene, and trimethylbenzene; and aliphatic hydrocarbon organic solvents such as n-pentane, n-hexane, and n-heptane.
- Solvents Alicyclic hydrocarbon organic solvents such as cyclopentane and cyclohexane; Halogenated hydrocarbon organic solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; methyl ethyl ketone, methylino ketoketone And ketone-based organic solvents such as cyclopentanone and cyclohexanone.
- the varnish can be obtained by mixing the above-mentioned insulating polymer, each component used as required, and an organic solvent.
- the mixing method of each component may be in accordance with a conventional method, for example, stirring using a stirrer and a magnetic stirrer; a high-speed homogenizer, a disposable ion, a planetary stirrer, a twin-screw stirrer, a ball mill, and a three-roll mill. And the like;
- the temperature at which these are mixed is within a range in which the reaction by the curing agent does not affect workability, and from the viewpoint of safety, the boiling point of the organic solvent used during mixing is preferably lower than the boiling point.
- the amount of the solvent used is appropriately selected according to the purpose of controlling the thickness and improving the flatness.
- the amount of the solvent is adjusted so that the solid content concentration of the varnish is usually 5 to 70% by weight, preferably 10 to 65% by weight, more preferably 20 to 60% by weight.
- the thickness of the resin B layer is set to the above-mentioned range.
- the method of forming the resin B layer on at least one side of the resin A layer using the above-described insulating material there is no particular limitation on the method of forming the resin B layer on at least one side of the resin A layer using the above-described insulating material, and any method can be adopted in consideration of the thickness of the resin B layer to be formed.
- any method can be adopted in consideration of the thickness of the resin B layer to be formed.
- (1) a method of forming a resin B layer by applying a varnish of an insulating material to the resin A layer, removing the solvent or performing surface treatment as necessary, and then heating the resin B layer, or (2) film-forming the insulating material.
- a method of laminating the resin A layer with an adhesive as needed.
- the method (1) is preferable because a resin composite film can be formed without using an adhesive, and thus stable thermal and electrical characteristics can be secured.
- the melt extrusion method or the solution casting method is used in the same manner as the method (1) described later.
- Apply by a method or the like remove the solvent or treat the surface if necessary, and then heat.
- the method (1) there is no particular limitation on the method of applying the insulating material to the resin A layer.
- the solution casting method is preferred.
- the coating may be performed by a method such as reverse roll coating, gravure coating, air knife coating, blade coating, dip coating, curtain coating, or die coating. Among these, lippers roll coating, gravure coating, and die coating are preferred from the viewpoint of easy control of the film thickness.
- drying is generally performed after the application to remove the solvent.
- the drying conditions at this time are appropriately selected depending on the type of the solvent, and the drying temperature is usually 20 to 300 ° C, preferably 30 to 200 ° C, and the drying time is Usually 30 seconds to 1 hour, preferably:! ⁇ 30 minutes.
- uncured or semi-cured resin layer is formed.
- a resin B layer is obtained.
- uncured refers to a state in which substantially the entire resin layer can be dissolved in a solvent capable of dissolving the insulating polymer used to form the resin layer.
- “Semi-cured” refers to a state in which the resin layer has been cured to such a degree that it can be further cured by heating.
- the resin layer is dissolved in a solvent capable of dissolving the insulating polymer used to form the resin layer. Part (about 1% by weight or more of the insulating polymer) is dissolved or when the resin layer is immersed in the solvent at room temperature for 24 hours, the swelling ratio of the resin layer is determined by the immersion. It means that it is at least 200% by volume.
- 5% by weight or more of the insulating polymer is dissolved in a solvent capable of dissolving the insulating polymer used for forming the resin layer, or the resin is contained in the solvent.
- the volume swelling ratio when the layer is immersed for 24 hours is not less than 300% by volume before immersion. Is preferred.
- the adhesion when a metal layer is laminated on the resin B layer later can be improved.
- Examples of such a surface treatment method include a method of contacting a compound having a structure capable of coordinating with a metal. By performing this surface treatment, excellent adhesion between the resin B layer and the metal layer can be obtained by forming the metal layer by plating while the surface of the resin B layer is smooth.
- a compound having a structure capable of coordinating with a metal is preferably a compound capable of coordinating with a metal such as an amino group, a thiol group, a carboxyl group, or a cyano group.
- a heterocyclic compound having a coordinating ability with a metal having a non-shared electron pair is particularly preferable, and a heterocyclic compound containing a nitrogen atom is particularly preferable.
- such a heterocyclic compound may further have a functional group that can coordinate to a metal.
- Heterocyclic compounds which also have a functional group capable of coordinating to a metal are preferred in that they provide higher pattern adhesion between the resin B layer and the metal layer.
- the solubility of the coordination structure-containing compound in water at 25 ° C. and in a hydrocarbon solvent is 0.1% by weight or more, preferably 1% by weight or more. More preferably, the amphiphilic compound is at least 5% by weight. In the case of such a compound, it is possible to select a solution that does not dissolve or swell the resin layer in the contact step with the uncured or semi-cured resin layer, and at the same time, to the uncured or semi-cured resin layer.
- Impregnation is possible and it is easy to obtain high adhesion strength with the metal layer
- a coordination structure-containing compound is used, the crosslinking density on the surface of the resin layer can be increased and the hydrophilicity can be enhanced when the resin layer is cured.
- Benzimidazole 21-etinole 4-imidazols, such as thiocanolebamoinole mida-zonole; pyrazole, 3-amino-1 _ siano
- Triazole 1-mercapto-1,2,4-triazoles such as triazole; 2—aminotriazine, 2,4-diamino _ 6-(6- (2- (2-Methyl-1- (imidazolyl) ethyl) triazine, 2,4,6-trimercapto_s—triazines and triazines such as trisodium umisolate; Preferred examples are given.
- the method for contacting such a coordination structure-containing compound with the uncured or semi-cured resin layer surface is not particularly limited. Specific examples include a dipping method in which a coordination structure-containing compound is dissolved in water or an organic solvent to form a solution, and the resin composite film having a resin layer formed thereon is immersed in the solution. Spray method for applying the solution to the surface of the resin composite film with resin layer formed by spraying, etc. For example, a method of coating by a method such as tinting may be used. The contact operation may be performed once or more than once.
- the temperature at the time of contact can be arbitrarily selected in consideration of the melting point of the coordination structure-containing compound, the boiling point of the solution, operability, productivity, and the like. Usually, 10 to: L 0 ° (: preferably Is 15 to 65 ° C.
- the contact time when contacting by the immersion method depends on the amount of the coordination structure-containing compound to be attached to the uncured or semi-cured resin layer surface, the concentration of the solution, and the production. It can be arbitrarily selected depending on the nature, etc., and is usually from 0.1 to 360 minutes, preferably from 0.1 to 60 minutes. ° C, preferably at 50 to 150 ° C for 10 seconds or more, preferably 30 seconds to 30 minutes, and removes the solvent by removing the solvent. It is preferable to react with the components in the semi-cured resin layer to prevent volatilization during curing of the resin.
- the coordination structure-containing compound is used by dissolving it in a solvent as necessary.
- the solvent to be used is not particularly limited, and one that does not easily dissolve the uncured or semi-cured resin layer after lamination on the resin A layer and dissolves the coordination structure-containing compound can be selected.
- water Ethers such as tetrahydrofuran, ethanol and isoprono
- Examples include polar solvents such as anolecols such as nonole, ketones such as acetone, and cello sonolebs such as ethylose sonolacetate.
- One type of solvent may be used alone, or two or more types may be used in combination.
- the concentration of the coordination structure-containing compound is not particularly limited. However, from the viewpoint of operability, it is usually 0.001 to 70% by weight, preferably 0.01 to 1% by weight. 5 ⁇ % by weight.
- the coordination structure-containing compound is liquid at the operating temperature and there is no problem with the operation of bringing the coordination structure-containing compound into contact with the uncured or semi-cured resin layer surface, the compound is not dissolved in the solvent and used as it is. This It is also possible.
- the solution of the coordination structure-containing compound is a component other than the coordination structure-containing compound, and improves the wetting between the uncured or semi-cured resin layer and the coordination structure-containing conjugated solution.
- Surfactants and other additives used for the purpose can be blended.
- the amount of the components other than the coordination structure-containing compound used is 10% by weight or less, preferably 5% by weight or less, and more preferably 1% by weight or less, based on the coordination structure-containing compound from the viewpoint of ensuring adhesion. % By weight or less.
- the surface of the resin layer can be washed with water or an organic solvent to remove an excessive surface treatment agent or neutralized before heating.
- the surface treating agent is a coordination structure-containing compound and is basic, it can be neutralized by contacting with an acidic compound.
- Heating for curing is usually performed by heating the uncured or semi-cured resin layer (or the entire film on which the resin layer is formed) on the resin A layer obtained by applying an insulating material to an oven and a hot plate. Or by heating using a heating furnace.
- the heating temperature is appropriately selected depending on various conditions such as the type of the insulating polymer and the curing agent, the thickness of the resin layer, the heating method, and the like.
- the heating temperature is usually 30 to 400 ° C., preferably 7 to 40 ° C. It is 0 to 350 ° C, more preferably 100 to 250 ° C.
- the heating time may be set in consideration of the heating method and the like, but is usually 30 seconds to 180 minutes, preferably 3 to 90 minutes.
- a resin composite film including the resin A layer and the resin B layer is obtained.
- the manufacturing process of the resin composite film can be performed by patching, It is preferable to perform the film continuously in the form of a roll at a low cost.
- the metal resin composite film of the present invention is obtained by forming a metal layer on the resin B layer of the resin composite film of the present invention. In particular, according to the plating method described in detail later, it is possible to form a metal layer having high adhesion on a smooth resin B layer.
- an opening is formed by a physical treatment such as drilling, laser etching, or plasma etching after forming a metal layer. It is also possible to form a part (via hole), form a conductive film on the wall of the opening, and connect the wiring.
- the resin composite film opening is formed by physical processing such as drilling, laser cutting, and plasma etching, and then the metal layer is formed by plating to form the opening.
- the metal layer can be collectively formed on the wall surface and the resin composite film surface, and an inexpensive double-sided wiring board can be manufactured.
- the metal layer may cover the entire resin B layer, but may be formed in a wiring pattern.
- the metal ⁇ composite film of the present invention is a metal used to construct the metal layer
- 2 0 ° resistance rate in C is 1 X 1 0- 2 ⁇
- Those with a diameter of less than cm are used, and specific examples include copper, aluminum, nickel, gold, silver, chromium, and alloys thereof.
- the metal layer may be a single layer or a laminate of two or more layers using the same or different metal species.
- the thickness of the metal layer there is no particular limitation on the thickness of the metal layer, and it is preferable that the thickness be in a range in which the metal layer can be wound into a roll in consideration of convenience during transportation.
- the thickness of the metal layer is usually 0.05 ⁇ ! 1100 ⁇ m. If the amount is less than the lower limit, the metal layer may be damaged due to friction or rubbing when wound into a roll. If the amount exceeds the upper limit, winding becomes difficult.
- the thickness of the metal layer is particularly preferably 0.05 ⁇ ! It is preferably about 9 ⁇ . Below this lower limit, the circuit may be damaged, and above the upper limit, it becomes difficult to control the etching accuracy in a wiring width of less than 20 ⁇ m.
- the metal layer is formed by a plating method
- the surface ten-point average roughness: R zjis is 3 ⁇ or less, preferably 2 ⁇ or less, and the surface average roughness Ra is 0.2 ⁇ .
- Ra is the center line average roughness shown in JISB0601 — 20001
- the surface ten-point average roughness Rzjis is JIS
- the surface of the resin B layer is oxidized using a gaseous medium or an oxidizing treatment solution, the surface becomes brittle, and it is difficult to obtain sufficient adhesion to metal, but as described above.
- a compound having a coordinating structure and through a surface treatment step a strong resin base material surface can be obtained.
- the oxidation treatment it is possible to remove a fragile layer made of a low molecular weight compound generated on the surface of the resin B layer and contaminants adhered from a curing atmosphere.
- a method of performing the oxidation treatment using a gaseous medium there is a known plasma treatment capable of turning the medium into a radicalized ion, such as reverse sputtering and open-ended discharge.
- the gaseous medium include air, oxygen, nitrogen, argon, water, carbon disulfide, carbon tetrachloride, and a mixed gas thereof. If the medium is liquid at the processing temperature, it is vaporized under reduced pressure and then oxidized.If the medium is a gas at the processing temperature, it is radial. Oxidation treatment is performed after the pressure is increased to a value that allows for chemical conversion or ionization.
- the temperature and time for bringing the plasma into contact with the surface of the resin B layer may be set arbitrarily in consideration of the type and flow rate of the gas, and the temperature is usually 10 to 250 ° C, preferably 20 to 25 ° C. At ⁇ 180 ° C, the time is usually between 0.5 and 60 minutes, preferably between 1 and 30 minutes.
- the surface of the resin B layer is oxidized using the oxidizing treatment liquid
- the surface of the resin B layer is brought into contact with the oxidizing treatment liquid (a liquid oxidizing compound or a solution of the oxidizing compound).
- oxidizing compound examples include inorganic peroxides and organic peroxides that can easily control the surface roughness of the resin B layer.
- Inorganic peroxy acids include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, Examples include periodate and ozone, and examples of organic peroxides include dicumyl peroxide, otatanyl peroxide, m-chloroperbenzoic acid, and peracetic acid.
- an oxidizing compound may be dissolved in a medium in which these can be dissolved as necessary.
- a general method such as a method in which the oxidizing treatment solution is brought into contact with the resin B layer.
- the medium used for dissolving inorganic peroxides and organic peroxides is neutral water, aqueous alkaline solutions such as aqueous sodium hydroxide, acidic aqueous solutions such as aqueous sulfuric acid, ethers and petroleum ethers. And non-polar organic solvents such as acetone and methanol.
- an inorganic peroxide or an organic peroxide or a solution thereof into contact with the surface of the resin B layer.
- a dipping method in which a resin composite film is immersed in an oxidizing treatment liquid
- a resin B layer A liquid filling method in which an oxidizing treatment liquid is placed on the surface using surface tension
- a spray method in which the oxidizing treatment liquid is sprayed on the surface of the resin B layer, etc. Any method may be used.
- the temperature at which these inorganic peroxides and organic peroxides are brought into contact with the surface of the resin B layer and the distance between the three layers are determined in consideration of the concentration and type of peroxide and the contact method.
- the contact temperature is usually from 10 to 250 ° C, preferably from 20 to 180 ° C, and the contact time is from 0.5 to 60 minutes, preferably from 1 to 30 minutes.
- the degree of surface roughening of the resin B layer can be easily controlled, brittle layers on the surface of the resin B layer and contaminants attached from the curing step can be easily removed, and the surface of the resin B layer can be easily removed. The tendency to become brittle can be suppressed.
- a resin which forms a curable resin composition and a fine sea-island structure and which can be dissolved in the selected type of the oxidizing solution may be appropriately selected.
- This resin can be used as a part of the insulating polymer.
- Specific examples of the texture include epoxy resin, polyester resin, bismaleidium triazine resin, silicone resin, polymethyl methacrylate, natural rubber, styrene rubber, isoprene rubber, butadiene. Rubbers, ethylene rubbers, propylene rubbers, urethane rubbers, butinole rubbers, silicone rubbers, trinole rubbers, fluoro rubbers, norbornolene rubbers, ether rubbers, and the like.
- the proportion of the resin soluble in the oxidizing treatment liquid is appropriately selected according to the degree of forming the fine sea-island structure with the insulating polymer constituting the resin layer, but usually the insulating polymer 1
- the amount is usually 1 to 100 parts by weight, preferably 3 to 50 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight. When it is in this range, a fine rough surface shape and uniform adhesion are easily obtained.
- Filters that can be dissolved in the selected oxidizing solution It can be selected as appropriate, and inorganic or organic fillers can be used.
- C, f, and filler include, for example, calcium carbonate, magnesium carbonate, parium silicate, zinc oxide, titanium oxide, magnesium oxide, magnesium gayate, potassium silicate, dinoconium silicate, and the like. Hydrated aluminum, alumina, magnesium hydroxide, aluminum hydroxide
- oxalic acid and sulphite are suitable for obtaining fine particles ⁇ and easy to be eluted with a filler-soluble aqueous solution, and for obtaining a fine rough surface shape.
- these inorganic filters may be those treated with an organic acid such as a silane coupling agent-treated stearyl acid.
- Organic fillers include phenolic resin, polyester resin, bismalein, terephthalate resin, silicone resin, polymethylmethacrylate, natural rubber, and styrene. Particles such as rubbers, isoprene rubbers, ethylene rubbers, propylene rubbers, urethane rubbers, butyl rubbers, silicone rubbers, trinole rubbers, fluoro rubbers, nonolebonorenene rubbers, phenol rubbers Compounds.
- the filler is preferably a non-conductive one which does not deteriorate the dielectric properties of the resin B layer.
- the shape of the filler is not particularly limited, and may be spherical, fibrous, plate-like, or the like.However, in order to make the resin B layer surface a fine rough surface, a fine powder It is preferable that Filler is in the range of the average particle diameter of usually 0 ⁇ 0 0 8 ⁇ 2 ⁇ ⁇ , preferably 0 0 1 ⁇ ; is 1 5 ⁇ ⁇ , particularly preferably 0 0 2 ⁇ 1 ⁇ ⁇ . .. .
- the proportion of the i-filler is appropriately selected according to the required degree of adhesion, but is usually 1 to 80 parts by weight, preferably 100 to 100 parts by weight of the insulating polymer. It is 3 to 60 parts by weight, more preferably 5 to 40 parts by weight. When it is in this range, a fine rough surface shape and uniform adhesion are easily obtained.
- a filler can be used as a flame retardant added to an insulating material, a ripening stabilizer, a dielectric property modifier, a part of a toughening agent, and the like.
- the surface of the resin B layer is usually washed with water to remove excess oxidizing compounds and processing residues. If there is a substance that cannot be washed with water alone, the substance can be further washed with a cleaning solution that can be dissolved, or contacted with another compound to chemically change it to a water-soluble substance, and then It can also be washed with.
- a aqueous alkaline solution such as an aqueous permanganate aqueous solution or an aqueous sodium permanganate solution is brought into contact with a resin substrate, the generated manganese dioxide is removed.
- a neutralization reduction treatment for the purpose of removing the film, there is a method of performing a neutralization reduction treatment with an acidic aqueous solution such as a mixture of hydroxyamine sulfate and sulfuric acid.
- an acidic aqueous solution such as a mixture of hydroxyamine sulfate and sulfuric acid.
- a method of eluting with an acidic solution such as hydrochloric acid or sulfuric acid, followed by washing with water may be used.
- a surfactant and a polarity adjusting agent such as alcohol and ether may be used in order to make the cleaning sufficient.
- a surfactant or a polarity adjusting agent it is preferable to further wash them so that they do not remain.
- Examples of the method for forming the metal layer include a method of laminating a metal film while the resin B layer is heated to a temperature of Tg or higher, and a method of applying a solution containing conductive particles and a dispersant, followed by drying by heating and drying. There is a method of forming by removing the agent, but plating is a method of controlling the thickness of the metal layer and adhesion It is preferable from the point of view.
- a metal layer is formed by electrolytic plating using this thin film layer.
- a conductive polymer film is formed by oxidative polymerization of a monomer capable of forming a conductive polymer in the presence of the oxidizing film formed by the salt treatment, and then the conductive polymer is formed.
- a method of forming a metal layer by electroplating using a conductive film are employed.
- a metal thin film is formed by electroless plating, which is a wet plating because it is inexpensive and can achieve high adhesion stably, and then electrolytic plating using this thin film layer is performed.
- a method of forming a metal layer is preferred.
- metal thin film layer is formed by wet electroless plating
- silver or palladium serving as a reducing catalyst is formed on the resin layer.
- adsorb catalyst nuclei such as zinc, cobalt, gold, platinum, iridium, ruthenium, and osmium.
- the method for attaching the catalyst nuclei to the resin B layer is not particularly limited, and a metal compound such as silver, palladium, zinc, cobalt, gold, platinum, iridium, ruthenium, or osmium, or a salt complex thereof is treated with water. Or 0.01 to 10% by weight in an organic solvent such as alcohol or black mouth form After immersion in a solution dissolved at a concentration of% (which may contain acids, alkalis, complexing agents, reducing agents, etc. if necessary), a method of reducing the metal is required.
- a metal compound such as silver, palladium, zinc, cobalt, gold, platinum, iridium, ruthenium, or osmium, or a salt complex thereof is treated with water. Or 0.01 to 10% by weight in an organic solvent such as alcohol or black mouth form After immersion in a solution dissolved at a concentration of% (which may contain acids, alkalis, complexing agents, reducing agents, etc. if necessary), a method of reducing the metal
- the electroless plating solution used in the electroless plating method a known self-catalytic electroless plating solution may be used, and the metal species contained in the plating solution, the reduction species j, and the complexation
- the type of agent, hydrogen ion concentration, dissolved oxygen concentration, etc. are not particularly limited.
- Electrolytic palladium-line plating solution, electroless gold plating solution, electroless silver plating solution, electroless nickel-copartoline plating solution with sodium hypophosphite reduced IJ Can be used.
- the electroless plating may be performed by repeating the same kind of metal a plurality of times, or by stacking a plurality of different kinds of metals.
- the thickness formed by the electroless plating method can be arbitrarily determined in consideration of the thickness of the metal. Generally, in consideration of growing the next electroplating metal layer, the thickness is preferably from 0.1 to 0.5 ⁇ , more preferably from 0.3 to 0.3 m, and particularly preferably. Is set to 0.05 to 0.15 ⁇ . Above this range, electroless plating has problems such as a decrease in adhesion due to high film stress, and a problem that is time consuming and low in economy. If the thickness is less than the above range, there is a problem that a thin metal film is eluted in a pretreatment or a processing step when performing electroplating using an electroless plating film, and it is difficult to form a uniform metal layer. After the formation of the metal thin film layer, the surface of the resin composite film can be subjected to a protection treatment by contacting the surface with a protection agent.
- the metal-resin composite film is completed by growing plating on the metal thin film layer obtained in this way, if necessary.
- a method that utilizes an electrodeposition reaction of a metal in an aqueous solution may be employed, and a copper sulfate plating solution, a copper pyrophosphate plating solution, an electrolytic nickel plating solution, or the like may be used.
- Electrolytic plating may be performed according to a conventional method. Further, the electrolytic plating solution may contain additives such as a complexing agent, a brightener, a stabilizer, and a buffering agent, if necessary.
- the surface of the resin composite film can be subjected to a protection treatment by bringing the surface into contact with a protection agent.
- a plating resist is formed in a desired pattern on the metal thin film, and then the metal thin film layer is used as a power feeder.
- a metal layer is grown by electroplating on the unformed portion of the plating resist, then the plating resist is removed, and a portion where the metal layer is not grown by electroplating by etching.
- a method of etching the metal thin film layer in a pattern can be performed.
- a resin composite film in which the metal is partially formed can also be obtained by a method of etching the metal in a pattern using a plating resist.
- the metal-resin composite film is usually heated to 50 to 350, preferably 80 to 250 ° C using an oven or the like. It is preferable to perform the heating (anneal) treatment for 0.1 to 10 hours, preferably 0.1; At this time, it is preferable to heat in an atmosphere of an inert gas such as nitrogen or argon. Further, if necessary, the metal-resin composite film may be pressed by a press plate, a pressure roll, or the like during heating.
- the metal-resin composite film (hereinafter, referred to as “wiring film”) of the present invention in which a metal layer is formed in a pattern by the above-described method is used for forming a terminal film and a protective film for use as a circuit board. By doing so, it is suitably used as a wiring film for a semiconductor package or a film for a flexible printed wiring board. Further, the metal-resin composite film of the present invention, in which a metal layer is formed in a pattern by the above-described method, can be suitably used as a multilayer circuit board by using it as an inner layer circuit. Mounting passive passive active devices is effective as highly reliable circuit components.
- More specific uses include flexible printed wiring for connecting printed circuit boards used in personal digital assistants, personal computers, mobile phones, portable information devices such as PHS, digital cameras, camcorders, and other devices.
- a board As a board (FPC); as a tape for tape-automated bonding (TAB); and as a high-density flexible wiring board such as a chip-on-film (COF) or system-on-film (SOF).
- the ratio of the hydrogenation ratio to the number of moles of unsaturated bonds in the polymer and the ratio of the number of moles of maleic anhydride residues to the total number of monomer units in the polymer were determined by 1 H-NMR spectrum. Was measured.
- the ten-point average roughness R zjis of the surface of the resin B layer was measured by using a non-contact optical surface shape measuring device (Keyence Corp., color laser microscope VK-850) to obtain 20 ⁇ ⁇ ⁇ 20. measuring the roughness of the surface for a short-form region of mu Ie, determine the ten-point average roughness, performs the measurement at five locations were evaluated and the average and R Z jis.
- a non-contact optical surface shape measuring device Keyence Corp., color laser microscope VK-850
- the average roughness Ra of the surface of the resin B layer was evaluated by using a non-contact type optical surface profile measuring device (Color Laser Microscope VK-8500, manufactured by KEYENCE CORPORATION) with 20 ⁇ ⁇ ⁇ 2 The measurement was performed at five locations in a rectangular area of 0 ⁇ m, and the average was evaluated as the average roughness Ra of the resin surface.
- a non-contact type optical surface profile measuring device Color Laser Microscope VK-8500, manufactured by KEYENCE CORPORATION
- the resin B layer surface of the composite film is positioned outside the masonry mandrel. And bent to 18'0 ° The appearance was evaluated with an optical microscope. The case where no cracking or peeling was confirmed in the resin B layer was marked with ⁇ , and the case where cracking or peeling was confirmed was marked with X.
- a wiring film with a wiring width of 30 ⁇ m, a wiring distance of 30 ⁇ m, a wiring length of 5 cm, and a wiring film having 50 wiring patterns is formed. Those having a disorder in the shape but no defect were evaluated as ⁇ , and those having the defect were evaluated as X.
- a wiring film having a comb pattern with a wiring width of 20 m, a wiring distance of 20 ⁇ , and a length of lcm was formed. It was left in a thermo-hygrostat maintained at 5% RH for 100 hours continuously. 1 0 0 0 hours elapsed even electric resistance is more than 1 0 9 ohm ⁇ , those of less than 1 0 9 ohm at 1 0 8 ohm or more ⁇ , was evaluated as X of less than 1 0 8 ohm .
- a Ni—Au plated bump-formed semiconductor chip with a width and length of 35 ⁇ m and a thickness of 16 ⁇ is mounted on an inner lead bonder (Shinkawa; ILT — 11) 0), a lead (wiring) pattern with a wiring width of 20 m and a wiring length of 500 ⁇ m was applied to a wiring film formed with 300 wires with a wiring distance of 20 ⁇ m.
- the bump is overlapped at a position where 5 ⁇ m protrudes from the end of the lead pattern, and the bump is applied for 0.5 seconds. It was hot pressed.
- the heating temperature is 300 ° C for the tool temperature and 300 ° C for the stage temperature.
- the applied pressure was 18 mg / m 2 per area where the lead pattern and the bump contacted each other.
- the lead pattern that has protruded or has no or no peeling, and has a peeling of 0.5 ⁇ m or less from the film surface is marked with ⁇ , and the floating and peeling of the lead pattern is 0 or less from the film surface.
- a sample exceeding 5 / xm and not more than ⁇ was designated as ⁇ , and a sample whose lead floating and peeling exceeded 1 ⁇ m from the film surface was designated as X.
- test piece formed into a film with a thickness of 10 ⁇ and 3 cm x 3 cm was dried in an oven at 105 ° C for 2 hours, and then cooled to room temperature in a desiccator to obtain a weight of W0.
- this sample was immersed in distilled water at 25 ° C, pulled out of the water 24 hours later, wiped with a dry cloth, weighed immediately, and expressed as W 1 by the following equation 1.
- test piece of type 2 shape (length, thickness 10 / zm, width 5 mm, length 70 mm), distance between marked lines 50 mm, initial distance between chucks 50 mm, test speed Is the value measured by the test method specified in JISK 7127-199 9 at 20 ⁇ 2.0 mmZ.
- the rate of change in mass after immersing the modified hydrogenated polymer in an aqueous sodium hydroxide solution was measured by the method described above in accordance with JISK711: 200. As a result, the rate of change of the mass of the resulting modified hydrogenated polymer was in the range of 0.05 to 0.3%.
- the varnish was plasma-treated using a Microgravia Coater, and was coated with a polyimid fuinorem with a width of 400 mm and a thickness of 37.5 / zm (trade name Kapton 150 EN, manufactured by Toray Dupont Co., Ltd.). ) Continuously at a speed of 2 minutes in a 110 ° C zone while coating Drying was carried out to obtain a resin A layer having a resin layer.
- the resin A layer obtained at this time was wound into a roll.
- the resin layer formed on the resulting composite film was immersed in a mixed solvent consisting of 80 parts of xylene and 20 parts of cyclopentanone at room temperature for 24 hours, and the resin layer was completely dissolved. It was confirmed that the resin layer was an uncured resin layer.
- the obtained resin A layer having the resin layer is immersed in a 1% aqueous solution of 11- (2-aminoethyl) -2-methylimidazole at 30 ° C. for 10 minutes by immersion (surface treatment). Process), then immersed in water at 25 ° C for 1 minute (cleaning process), and then the excess solution was removed with an air knife, and this was further flushed with nitrogen to replace the inside with a superheated furnace.
- the resin A layer and the resin B layer with a thickness of 3 ⁇ m are continuously treated so that they are exposed at 60 ° C for 10 minutes and then at 180 ° C for 30 minutes. Was obtained.
- the obtained resin composite film was rolled up in a roll shape. A bending test was performed using a part of this resin composite film. The results are shown in Table 1.
- the resin composite film after washing was washed with PC-65H (manufactured by Ebara-Uji Lighting Co., Ltd.) for 250 m1 no. (Manufactured by Gillite Co., Ltd.) was immersed for 5 minutes in a plating solution containing Pd salt containing 0.8 m 1 Z liter at 50 ° C. .
- PC-65H manufactured by Ebara-Uji Lighting Co., Ltd.
- PC-BA manufactured by EBARA Ujilight Co., Ltd.
- the ten-point average roughness Rz ⁇ is and the average surface roughness: Ra were measured on the surface of the resin B layer of the resin composite film on which the pre-coating treatment was completed. Table 1 shows the results.
- PB-556 MU manufactured by EBARA Uji Light Co., Ltd.
- PB-556 A manufactured by EBARA Uji Light Co., Ltd.
- PB-556B Ebara Ujilight Co., Ltd.
- PB-556C Ebara Ujilight Co., Ltd.
- the resin composite film after plating pretreatment is immersed for 4 minutes while blowing air into the electroless plating solution at 35 ° C, which is a little, to form a 0.1 ⁇ m thick metal thin film layer.
- the film on which the metal thin film layer was formed by the electroless plating treatment was washed with water, subjected to a water-proof treatment, further washed with water, and blow-dried to obtain a film on which the metal thin film layer was formed. .
- the film on which the metal thin film layer has been formed is subjected to a heat treatment at 25 ° C. for 1 minute in a solution of 100 g / liter of sulfuric acid to remove the heat inhibitor.
- Superslow 2000 for copper sulfate plating (manufactured by Ensembapan Co., Ltd.) is 985 m1 and has a gloss for copper sulfate plating.
- Super Slow 2000 (manufactured by Enson Japan Co., Ltd.) is 3 A / dm 3 via a feed roll in a copper sulfate plating solution at 23 ° C, which is 15 m 1 / liter.
- Electrolytic copper plating was performed while power was supplied to form an electrolytic copper plating film with a thickness of 8 ⁇ m.
- the film on which the metal layer is completed by electrolytic copper plating is washed with water, subjected to a water-proof treatment, further washed with water, blow-dried, and retained in a heating furnace at 170 ° C. for 30 minutes for annealing.
- a metal-resin composite film was obtained after the treatment. From the removal of the protective agent to the annealing treatment, the film obtained in the previous process was continuously pulled out from the mouth, and the metal-resin composite film was processed after the annealing treatment. By winding the film, a metal / resin composite film having a mouth-like shape was obtained.
- the metal-resin composite film obtained in this way is necessary for evaluating the pattern shape of each obtained wiring film, the adhesion after high-temperature ⁇ 0 humidity, the insulation reliability, and the high-temperature mounting characteristics. Cut to size.
- a dry film of a commercially available photosensitive resist is thermocompression-bonded to the cut metal layer surface of the metal resin composite film, and masks for various evaluation patterns are densely formed on the dry film.
- the resist was developed to obtain a resist pattern. Next, it was immersed in a solution of 100 g / liter of sulfuric acid at 25 ° C. for 1 minute to remove the protective agent, and the copper in the resist-free portion was etched with a mixed solution of cupric chloride and hydrochloric acid. Ching treatment was performed. Next, the resist pattern was peeled off with a peeling liquid, washed with water, and dried to obtain a wiring film. Each evaluation was performed using the obtained wiring film. Table 1 shows the evaluation results.
- the varnish of the insulating material was applied on polytetrafluoroethylene, dried, and further cured by heating. Thereafter, the film was peeled off from the polytetrafluoroethylene and 1 ⁇ A thick film was obtained. Using this as a test piece, water absorption and tensile elongation at break were evaluated. The evaluation results are shown in Wheat 1.
- a resin composite film, a metal-resin composite film, various wiring films and test pieces were prepared in the same manner as in Example 1 except that a resin layer having a thickness of 1 ⁇ was formed by changing the conditions of the microgravure coater. And made various evaluations. Table 1 shows the evaluation results.
- a resin composite film, a metal-resin composite film, various wiring films and test pieces were prepared in the same manner as in Example 1 except that a resin B layer having a thickness of 5 zm was formed by changing the conditions of the Microloadervia coater. Created and evaluated variously. Table 1 shows the evaluation results.
- Comparative Example 3 When the water absorption of the resin B layer is too low, a plasma-treated polyimide film with a width of 400 m and a thickness of 40 / 'm (Product name: Kapton 200 EN, Toray Dupont Co., Ltd.) to form a 0.2 ⁇ m silicon oxide film by sputtering. A composite film comprising a mid and an inorganic insulating film was obtained.
- This inorganic insulating film was determined by forming a 10 / m thick silicon oxide film on a 0.1 mm thick copper plate by sputtering, The copper was removed from the ammonium persulfate solution, washed with water, and dried, and the measurement was performed by the method described above. Table 1 shows the evaluation results. In addition, Rzjis and Ra of the surface of the inorganic insulating film of the obtained composite film were measured. The results are shown in Table 1.
- copper was sputtered on the surface of the inorganic resin B layer of the composite film composed of the polyimide and the inorganic insulating film to form a copper thin film layer of 0.1 / m.
- electrolytic copper plating was performed to form an electrolytic copper plating film with a thickness of 8 ⁇ m, A metal-resin composite film comprising a metal, an inorganic insulating film and a metal layer was obtained.
- the resin composite film of the present invention is excellent in flexibility, insulation reliability, and balance of high-temperature mounting characteristics, and a flexible printed wiring board and a semiconductor package substrate manufactured using the film can form a high-density circuit. It was possible, and furthermore, it was found that an electronic component manufactured using the wiring film had excellent reliability.
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/571,135 US20060257625A1 (en) | 2003-09-10 | 2004-09-06 | Resin composite film |
JP2005513930A JPWO2005025857A1 (ja) | 2003-09-10 | 2004-09-06 | 樹脂複合フィルム |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2003-319031 | 2003-09-10 | ||
JP2003319031 | 2003-09-10 |
Publications (1)
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WO2005025857A1 true WO2005025857A1 (ja) | 2005-03-24 |
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PCT/JP2004/013271 WO2005025857A1 (ja) | 2003-09-10 | 2004-09-06 | 樹脂複合フィルム |
Country Status (3)
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US (1) | US20060257625A1 (ja) |
JP (2) | JPWO2005025857A1 (ja) |
WO (1) | WO2005025857A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010073903A1 (ja) * | 2008-12-26 | 2010-07-01 | 富士フイルム株式会社 | 表面金属膜材料、表面金属膜材料の作製方法、金属パターン材料の作製方法、及び金属パターン材料 |
JP2011134907A (ja) * | 2009-12-24 | 2011-07-07 | Nippon Zeon Co Ltd | 多層プリント回路基板用フィルム |
JP6142961B1 (ja) * | 2016-03-08 | 2017-06-07 | 東洋インキScホールディングス株式会社 | 積層体およびその製造方法、並びに接着層付樹脂フィルム |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007285598A (ja) * | 2006-04-17 | 2007-11-01 | Matsushita Electric Ind Co Ltd | 熱交換器 |
US7678959B2 (en) * | 2007-02-27 | 2010-03-16 | Nitto Denko Corporation | Film base material for adhesive skin patch and adhesive skin patch |
JP4464990B2 (ja) | 2007-05-22 | 2010-05-19 | トヨタ自動車株式会社 | 配線基板及びその製造方法 |
US20110003914A1 (en) * | 2008-01-31 | 2011-01-06 | Sekisui Chemical Co., Ltd. | Resin composition and multilayer resin film employing the same |
CN102137758B (zh) * | 2008-09-01 | 2014-08-06 | 积水化学工业株式会社 | 层叠体及层叠体的制造方法 |
TWI383950B (zh) * | 2009-04-22 | 2013-02-01 | Ind Tech Res Inst | 奈米點狀材料的形成方法 |
US8632864B2 (en) * | 2009-08-24 | 2014-01-21 | Lacks Industries, Inc. | Decorative surface finish and method of forming same |
US9615465B2 (en) * | 2010-09-30 | 2017-04-04 | Zeon Corporation | Method of production of multilayer circuit board |
TWI471072B (zh) * | 2010-12-30 | 2015-01-21 | Ind Tech Res Inst | 具有導電膜層的基板組合及其製造方法 |
JP5691977B2 (ja) * | 2011-09-30 | 2015-04-01 | 日本ゼオン株式会社 | 絶縁性接着フィルム、プリプレグ、積層体、硬化物、及び複合体 |
WO2013047726A1 (ja) * | 2011-09-30 | 2013-04-04 | 日本ゼオン株式会社 | 絶縁性接着フィルム、プリプレグ、積層体、硬化物、及び複合体 |
KR20170023202A (ko) * | 2012-06-05 | 2017-03-02 | 엔씨씨 나노, 엘엘씨 | 기재막 및 소결 방법 |
CN106553360B (zh) | 2015-09-25 | 2020-03-31 | 比亚迪股份有限公司 | 一种金属树脂复合体及其制备方法 |
US11797119B2 (en) * | 2017-04-14 | 2023-10-24 | Sensel, Inc. | Selectively adhered resistive force sensor |
CN109454955B (zh) * | 2018-12-19 | 2021-07-06 | 广东生益科技股份有限公司 | 一种封装载带基材及其制备方法 |
TW202224929A (zh) * | 2020-12-25 | 2022-07-01 | 律勝科技股份有限公司 | 積層板及其製造方法 |
JPWO2023053620A1 (ja) * | 2021-09-29 | 2023-04-06 | ||
JPWO2023053619A1 (ja) * | 2021-09-29 | 2023-04-06 |
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WO1999022936A1 (fr) * | 1997-10-31 | 1999-05-14 | Nippon Zeon Co., Ltd. | Feuille multicouche |
JP2003158373A (ja) * | 2001-09-05 | 2003-05-30 | Nippon Zeon Co Ltd | 多層回路基板の製造方法 |
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JPS5278069A (en) * | 1975-12-24 | 1977-07-01 | Fuji Kinzoku Kakou Kk | Printed circuit board |
DE69836911T2 (de) * | 1997-07-18 | 2007-10-31 | Nippon Zeon Co., Ltd. | Modifiziertes cycloolefin-additionspolymer und härtbare harzzusammensetzung die dieses enthält |
EP1121008B1 (en) * | 1998-09-03 | 2008-07-30 | Ibiden Co., Ltd. | Multilayer printed wiring board and method for manufacturing the same |
JP3527694B2 (ja) * | 2000-08-11 | 2004-05-17 | 新光電気工業株式会社 | 配線基板の製造方法 |
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2004
- 2004-09-06 WO PCT/JP2004/013271 patent/WO2005025857A1/ja active Application Filing
- 2004-09-06 US US10/571,135 patent/US20060257625A1/en not_active Abandoned
- 2004-09-06 JP JP2005513930A patent/JPWO2005025857A1/ja active Pending
-
2010
- 2010-10-01 JP JP2010224291A patent/JP2011000892A/ja active Pending
Patent Citations (2)
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WO1999022936A1 (fr) * | 1997-10-31 | 1999-05-14 | Nippon Zeon Co., Ltd. | Feuille multicouche |
JP2003158373A (ja) * | 2001-09-05 | 2003-05-30 | Nippon Zeon Co Ltd | 多層回路基板の製造方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010073903A1 (ja) * | 2008-12-26 | 2010-07-01 | 富士フイルム株式会社 | 表面金属膜材料、表面金属膜材料の作製方法、金属パターン材料の作製方法、及び金属パターン材料 |
JP2011134907A (ja) * | 2009-12-24 | 2011-07-07 | Nippon Zeon Co Ltd | 多層プリント回路基板用フィルム |
JP6142961B1 (ja) * | 2016-03-08 | 2017-06-07 | 東洋インキScホールディングス株式会社 | 積層体およびその製造方法、並びに接着層付樹脂フィルム |
WO2017154995A1 (ja) * | 2016-03-08 | 2017-09-14 | 東洋インキScホールディングス株式会社 | 積層体およびその製造方法、並びに接着層付樹脂フィルム |
JP2017163131A (ja) * | 2016-03-08 | 2017-09-14 | 東洋インキScホールディングス株式会社 | 積層体およびその製造方法、並びに接着層付樹脂フィルム |
Also Published As
Publication number | Publication date |
---|---|
US20060257625A1 (en) | 2006-11-16 |
JP2011000892A (ja) | 2011-01-06 |
JPWO2005025857A1 (ja) | 2006-11-16 |
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