WO2009107760A1 - 多層プリント配線板の製造方法 - Google Patents
多層プリント配線板の製造方法 Download PDFInfo
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- WO2009107760A1 WO2009107760A1 PCT/JP2009/053636 JP2009053636W WO2009107760A1 WO 2009107760 A1 WO2009107760 A1 WO 2009107760A1 JP 2009053636 W JP2009053636 W JP 2009053636W WO 2009107760 A1 WO2009107760 A1 WO 2009107760A1
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- metal film
- film
- resin composition
- curable resin
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Classifications
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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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1152—Replicating the surface structure of a sacrificial layer, e.g. for roughening
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
- H05K3/0035—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material of blind holes, i.e. having a metal layer at the bottom
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
- H05K3/0038—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material combined with laser drilling through a metal layer
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
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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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49126—Assembling bases
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49155—Manufacturing circuit on or in base
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/49155—Manufacturing circuit on or in base
- Y10T29/49165—Manufacturing circuit on or in base by forming conductive walled aperture in base
Definitions
- the present invention relates to a method for manufacturing a multilayer printed wiring board.
- Multilayer printed wiring boards widely used in various electronic devices are required to have thinner layers and finer circuit wiring in order to reduce the size and increase the functionality of electronic devices.
- a manufacturing technique of a multilayer printed wiring board a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on a core substrate is known.
- a curable resin composition is laminated on an inner layer circuit board with an adhesive film, and the curable resin composition is cured to form an insulating layer.
- the insulating layer is roughened with an oxidizing agent such as an alkaline potassium permanganate solution, and a plating seed layer is formed by electroless plating on the rough surface by a semi-additive method, and then a conductor layer is formed by electrolytic plating.
- an oxidizing agent such as an alkaline potassium permanganate solution
- a plating seed layer is formed by electroless plating on the rough surface by a semi-additive method
- a conductor layer is formed by electrolytic plating.
- the surface of the insulating layer is roughened with an oxidizing agent as described above (the surface is made uneven). It is necessary to obtain an anchor effect.
- Patent Documents 1 and 2 a film with a metal film in which a metal film layer is formed by vapor deposition or the like on a support layer via a release layer is produced, and the metal film layer of the film with a metal film is formed on a substrate.
- a method is disclosed in which a conductor layer is formed by plating or the like on a transferred metal film layer after being transferred to the surface of the insulating layer or the surface of the prepreg.
- Patent Document 1 is a method using a film with a metal film using a fluororesin, polyolefin resin, or polyvinyl alcohol resin as a release layer.
- the method of Patent Document 2 is an acrylic resin or melamine as a release layer. It is a method using a film with a metal film using an adhesive containing an adhesive resin such as a resin.
- Patent Document 3 discloses an adhesive film in which a metal film layer is directly formed on a support layer by vapor deposition or the like, and a resin composition layer is formed thereon. JP 2004-230729 A JP 2002-324969 A JP-A-9-296156
- the method of transferring the copper film to the adherend with the metal film-transferred film for transferring the metal film is considered to be an advantageous method for miniaturization because the conductor layer is formed on the smooth insulating layer surface. .
- there are blind via sometimes referred to as “via” in this specification
- the transferred copper film is damaged.
- it is easy to receive For example, when blind via formation is performed with a laser or the like, the copper film around the blind via is easily damaged.
- the present inventors are surprised when the transferred copper film is removed by etching and a copper film layer serving as a plating seed layer is formed again by electroless plating. Then, the present inventors have found that the conductor layer formed by electrolytic plating has high peel strength, and completed the present invention. After removing the transferred copper film by etching, the copper film is formed by electroless plating on the via wall, etc., and at the same time, the copper film is formed again by electroless plating on the surface of the insulating layer. In addition, since a thin and uniform plating seed layer can be formed, the plating seed layer can be easily removed by etching when circuit formation is performed by a semi-additive method or the like, thereby suppressing dissolution of the wiring pattern. can do.
- a method for producing a multilayer printed wiring board comprising the following steps (A) to (E); (A) A film with a metal film in which a metal film layer is formed on a support layer is laminated on an inner circuit board via a curable resin composition layer, or on the metal film layer of the film with a metal film A step of laminating an adhesive film with a metal film on which an curable resin composition layer is formed on an inner circuit board, (B) a step of curing the curable resin composition layer to form an insulating layer; (C) removing the support layer, (D) A step of removing the metal film layer, and (E) a step of forming the metal film layer on the surface of the insulating layer by electroless plating.
- the metal film layer in the film with metal film or the adhesive film with metal film is formed by one or more methods selected from a vapor deposition method, a sputtering method and an ion plating method. the method of.
- the release layer is formed from one or more water-soluble polymers selected from water-soluble cellulose resins, water-soluble polyester resins, and water-soluble acrylic resins.
- the water-soluble polyester resin is a water-soluble polyester having a sulfo group or a salt thereof and / or a carboxyl group or a salt thereof
- the water-soluble acrylic resin is a water-soluble acrylic resin having a carboxyl group or a salt thereof.
- the method described. The method according to any one of (10) to (12), further comprising (I) a step of removing the release layer after the step of (C) removing the support layer.
- the support layer is a polyethylene terephthalate film.
- the curable resin composition contains a component containing a hetero atom in the molecule.
- the curable resin composition contains a component containing a nitrogen atom in the molecule.
- the curable resin composition contains an epoxy resin and a curing agent.
- the curing agent is a curing agent containing a nitrogen atom in the molecule.
- the curing agent is a triazine skeleton-containing phenol novolac resin and / or a triazine skeleton-containing cresol novolak resin.
- the curable resin composition further contains a thermoplastic resin.
- the curable resin composition further contains an inorganic filler.
- the curable resin composition layer is a prepreg obtained by impregnating a curable resin composition into a sheet-like reinforcing substrate made of fibers.
- the conductor layer is formed on the surface of the insulating layer having an arithmetic average roughness (Ra) of 200 nm or less, and when measured with an X-ray photoelectron spectrometer
- Ra arithmetic average roughness
- a conductor layer having excellent peel strength can be formed on a flat insulating layer surface by electroless plating or electroless plating and electrolytic plating. Further, since the plating seed layer can be removed by etching under a mild condition by forming the conductor layer on a flat surface, dissolution of the wiring pattern can be suppressed, and an excellent method for forming fine wiring can be realized.
- a film with a metal film in which a metal film layer is formed on a support layer, or a metal film layer is formed on a support layer. Furthermore, an adhesive film with a metal film in which a curable resin composition layer is formed on the metal film layer is used.
- the support layer is a film or sheet having a self-supporting property, and a metal foil, a plastic film, or the like can be used, and a plastic film is particularly preferably used.
- the metal foil include aluminum foil and copper foil.
- a metal foil made of a metal different from the metal film layer to be formed is employed.
- the plastic film include polyethylene terephthalate film, polyethylene naphthalate, polyimide, polyamideimide, polyamide, polytetrafluoroethylene, polycarbonate, and the like.
- Polyethylene terephthalate film and polyethylene naphthalate film are preferable, and inexpensive polyethylene terephthalate is particularly preferable. preferable.
- the surface of the support layer may be subjected to surface treatment such as corona treatment. Further, the surface of the support layer film on the side where no metal film layer or release layer is present may be subjected to surface treatment such as mat treatment or corona treatment.
- the support layer surface on the side where the release layer is formed has an arithmetic average roughness (Ra) of 50 nm or less (0 or more and 50 nm or less), and further 40 nm from the viewpoint of preventing cracks when producing a film with a metal film.
- the arithmetic average roughness of the surface of the support layer on the side where the release layer is not formed is preferably within the same range as described above.
- the arithmetic average roughness (Ra value) can be measured by using a known method, for example, by using a device such as a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Beec Instruments). Can do.
- a commercially available support can also be used.
- T60 manufactured by Toray Industries, Inc., polyethylene terephthalate film
- A4100 manufactured by Toyobo Co., Ltd., polyethylene terephthalate film
- Q83 manufactured by Teijin DuPont Films Ltd.
- Polyethylene naphthalate film Polyethylene naphthalate film
- Diafoil OB100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate film
- linquid mold release agent AL-5, manufactured by Lintec Co., Ltd.
- the layer thickness of the support layer is usually 10 to 70 ⁇ m, preferably 15 to 70 ⁇ m.
- the layer thickness is too small, there are problems such as poor handleability, a decrease in peelability of the support layer, and a problem in forming a smooth metal film layer.
- the layer thickness is too large, it is disadvantageous in terms of cost and is not practical.
- the film with a metal film and the adhesive film with a metal film in the present invention preferably have a release layer between the support layer and the metal film layer in order to efficiently transfer the metal film to the surface of the adherend.
- the release layer can be formed using a polymer release layer such as a fluororesin, alkyd resin, silicone resin, polyolefin resin, polyvinyl alcohol resin, acrylic resin, polyester resin, melamine resin, or cellulose.
- a polymer release layer such as a fluororesin, alkyd resin, silicone resin, polyolefin resin, polyvinyl alcohol resin, acrylic resin, polyester resin, melamine resin, or cellulose.
- a metal film or metal foil formed by vapor deposition, sputtering, ion plating, or the like can be used as the release layer.
- the metal include aluminum, zinc, lead, and nickel, but aluminum is preferable.
- the release layer one or more water-soluble substances selected from water-soluble cellulose resin, water-soluble acrylic resin and water-soluble polyester resin are used from the viewpoint of uniformly transferring the metal film and the cost of forming the release layer.
- the polymer is preferably formed. These water-soluble polymer release layers are easier to form on the support layer than the metal release layer, and are advantageous in terms of cost. Further, after the curable resin composition as the adherend is cured, the support layer can be peeled off between the support layer and the release layer, the metal film layer is not easily damaged, and the release layer remaining on the metal film layer is Since it is easily removed with an aqueous solution, a metal film can be uniformly formed on the adherend.
- a water-soluble cellulose resin and a water-soluble polyester resin are more preferable, and a water-soluble cellulose resin is particularly preferable.
- any water-soluble polymer is used alone in the water-soluble polymer release layer, but two or more water-soluble polymers can be mixed and used.
- the water-soluble polymer release layer is usually formed as a single layer, but it may have a multilayer structure formed of two or more different types of water-soluble polymers used.
- silicone resin, alkyd resin, fluororesin is used between the water-soluble polymer release layer and the support layer in order to improve the peelability between these layers.
- Other release layers such as may be present. That is, when a water-soluble polymer is applied to the release layer, it is sufficient that at least the surface of the release layer that adheres to the metal film is formed of the water-soluble polymer. It is possible to form a two-layer structure of a water-soluble polymer release layer and another release layer so that the surface to be bonded to the metal film is formed of a water-soluble polymer. it can.
- the support can be peeled between the support layer and the release layer after the curable resin composition as the adherend is cured. Thereafter, the release layer remaining on the metal film layer is easily removed with an aqueous solution, so that a metal film having excellent uniformity can be formed on the adherend.
- the release layer is formed only from the water-soluble resin, peeling of the support between the support layer and the release layer is performed at the interface between the support and the release layer, and the release layer is an alkyd resin or the like.
- the other release layer and the water-soluble resin release layer it is carried out at the interface between the other release layer and the water-soluble resin release layer.
- the layer thickness of the release layer is usually 0.01 ⁇ m or more and 20 ⁇ m or less (0.01 to 20 ⁇ m), more preferably 0.05 ⁇ m or more and 10 ⁇ m or less, further preferably 0.1 ⁇ m or more and 5 ⁇ m or less, and more preferably 0. It is 1 ⁇ m or more and 3 ⁇ m or less, more preferably 0.1 ⁇ m or more and 2 ⁇ m or less, further preferably 0.1 ⁇ m or more and 1 ⁇ m or less, and further preferably 0.2 ⁇ m or more and 1 ⁇ m or less.
- the “layer thickness” here is the thickness when the release layer is a single layer, and the total thickness of the multilayer when it is a multilayer.
- the layer thickness of the release layer other than the water-soluble resin release layer is preferably in the range of 0.01 to 0.2 ⁇ m. If the release layer is too thick, when the curable resin composition layer is thermally cured, the metal film layer may be cracked or scratched due to the difference in thermal expansion coefficient between the metal film layer and the release layer. There is a risk of malfunction. On the other hand, when the layer thickness is too thin, the peelability of the support layer may be lowered.
- Water-soluble cellulose resin refers to a cellulose derivative that has been subjected to a treatment for imparting water-solubility to cellulose, and preferred examples include cellulose ether and cellulose ether ester.
- Cellulose ether is an ether formed by conversion of one or more hydroxyl groups present in one or more anhydroglucose repeat units of a cellulose polymer to provide one or more ether linking groups to the cellulose polymer.
- the group is usually an alkyl optionally substituted by one or more substituents selected from a hydroxyl group, a carboxyl group, an alkoxy group (1 to 4 carbon atoms) and a hydroxyalkoxy group (1 to 4 carbon atoms). Group (having 1 to 4 carbon atoms).
- hydroxyalkyl groups such as 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl (1 to 4 carbon atoms); 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 2-ethoxy Alkoxy (C1-4) alkyl group (C1-4) such as ethyl; hydroxyalkoxy (C1-4) such as 2- (2-hydroxyethoxy) ethyl or 2- (2-hydroxypropoxy) propyl )
- An alkyl group (having 1 to 4 carbon atoms), a carboxyalkyl group such as carboxymethyl (having 1 to 4 carbon atoms), and the like.
- the ether linking group in the polymer molecule may be a single species or a plurality of species. That is, it may be a cellulose ether having a single type of ether linking group or a cellulose ether having a plurality of types of ether linking groups.
- cellulose ether examples include, for example, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, carboxymethyl cellulose, and water-soluble salts thereof (for example, alkali metal salts such as sodium salt). Is mentioned.
- the average number of moles of ether groups substituted per unit glucose ring in cellulose ether is not particularly limited, but 1-6 is preferable.
- the molecular weight of the cellulose ether is preferably about 20000 to 60000 in weight average molecular weight.
- Cellulose ether esters are formed between one or more hydroxyl groups present in cellulose and one or more suitable organic acids or reactive derivatives thereof, thereby forming ester linking groups in the cellulose ether. That is.
- the “cellulose ether” used herein is as described above, and the “organic acid” includes an aliphatic or aromatic carboxylic acid (preferably having 2 to 8 carbon atoms). It may be branched or unbranched) or cyclic and may be saturated or unsaturated.
- aliphatic carboxylic acid examples include substituted or unsubstituted acyclic aliphatic dicarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid.
- acyclic hydroxy-substituted carboxylic acids such as glycolic acid or lactic acid
- acyclic aliphatic hydroxy-substituted di- or tri-carboxylic acids such as malic acid, tartaric acid, and citric acid.
- the aromatic carboxylic acid is preferably an aryl carboxylic acid having 14 or less carbon atoms, and includes an aryl group such as a phenyl or naphthyl group having one or more carboxyl groups (for example, 1, 2 or 3 carboxyl groups).
- Aryl carboxylic acids are particularly preferred.
- the aryl group is substituted with one or more (eg, 1, 2 or 3) groups which may be the same or different and selected from hydroxy, alkoxy having 1 to 4 carbon atoms (eg, methoxy) and sulfonyl. May be.
- Preferable examples of the arylcarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid (1,2,4-benzenetricarboxylic acid) and the like.
- the organic acid has one or more carboxyl groups
- preferably only one carboxyl group of the acid forms an ester linkage to the cellulose ether.
- one carboxyl group of each succinate group forms an ester linkage with cellulose and the other carboxy group is present as a free acid.
- An “ester linking group” is formed by reaction of cellulose or cellulose ether with a suitable organic acid as described above or a reactive derivative thereof. Suitable reactive derivatives include, for example, acid anhydrides such as phthalic anhydride.
- the ester linking group in the polymer molecule may be single type or multiple types. That is, it may be a cellulose ether ester having a single type of ester linking group or a cellulose ether ester having a plurality of types of ester linking groups.
- hydroxypropyl methylcellulose acetate succinate is a mixed ester of hydroxypropyl methylcellulose having both succinate and acetate groups.
- Suitable cellulose ether esters are hydroxypropylmethylcellulose or esters of hydroxypropylcellulose, specifically hydroxypropylmethylcellulose acetate, hydroxypropylmethylcellulose succinate, hydroxypropylmethylcellulose acetate succinate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose Trimellitate, hydroxypropyl methylcellulose acetate phthalate, hydroxypropyl methylcellulose acetate trimellitate, hydroxypropyl cellulose acetate phthalate, hydroxypropyl cellulose butyrate phthalate, hydroxypropyl cellulose acetate phthalate succinate and Mud hydroxypropyl cellulose acetate trimellitate succinate, etc. These may be used alone or in combination.
- hydroxypropylmethylcellulose phthalate hydroxypropylmethylcellulose acetate succinate, and hydroxypropylmethylcellulose acetate phthalate are preferable.
- the average number of moles of ester groups substituted per unit glucose ring in the cellulose ether ester is not particularly limited, but is preferably about 0.5% to 2%, for example.
- the molecular weight of the cellulose ether ester is preferably about 20000 to 60000 in weight average molecular weight.
- Cellulose ethers and cellulose ether esters are well known in the art, and can be obtained by reacting an etherifying agent and an esterifying agent in accordance with a conventional method using natural cellulose (pulp) as a raw material. May be used.
- a conventional method using natural cellulose (pulp) as a raw material.
- Pulp natural cellulose
- HP-55 “HP-55” (both hydroxypropylmethylcellulose phthalate), “60SH-06” (hydroxypropylmethylcellulose) manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.
- the “water-soluble polyester resin” as used in the present invention is synthesized by an ordinary polycondensation reaction using a polyvalent carboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol or an ester-forming derivative thereof as main raw materials. It is a polyester resin made of a substantially linear polymer, and has a hydrophilic group introduced in the molecule or at the molecular end.
- examples of the hydrophilic group include an organic acid group such as a sulfo group, a carboxyl group, and a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof is preferable.
- the water-soluble polyester resin those having a sulfo group or a salt thereof and / or a carboxyl group or a salt thereof are particularly preferable.
- polyvalent carboxylic acid component of the polyester resin include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, and the like. These may be used alone or in combination of two or more.
- hydroxycarboxylic acids such as p-hydroxybenzoic acid
- unsaturated carboxylic acids such as maleic acid, fumaric acid or itaconic acid may be used in a small amount.
- polyhydric alcohol component of the polyester resin include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexane glycol, 1,4-cyclohexane methanol, and xylylene.
- examples thereof include glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, and poly (tetramethylene oxide) glycol. These may be used alone or in combination of two or more.
- the introduction of a hydrophilic group into the molecule or the molecular end of the polyester resin may be carried out by a known and conventional method, but an ester-forming compound containing a hydrophilic group (for example, an aromatic carboxylic acid compound, a hydroxy compound, etc.) A mode of polymerization is preferred.
- an ester-forming compound containing a hydrophilic group for example, an aromatic carboxylic acid compound, a hydroxy compound, etc.
- 5-sulfonic acid sodium isophthalic acid when introducing a sulfonate group, 5-sulfonic acid sodium isophthalic acid, 5-sulfonic acid ammonium isophthalic acid, 4-sulfonic acid sodium isophthalic acid, 4-methylsulfonic acid ammonium isophthalic acid, 2-sulfonic acid sodium terephthalic acid
- a carboxylic acid group for example, one or two kinds selected from trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid and the like. It is preferable to copolymerize the above, and the carboxylate group can be introduced into the molecule by neutralization with an amino compound, ammonia or an alkali metal salt after a copolymerization reaction in the art.
- the molecular weight of the water-soluble polyester resin is not particularly limited, but the weight average molecular weight is preferably about 10,000 to 40,000. If the weight average molecular weight is less than 10,000, the layer formability tends to decrease, and if it exceeds 40000, the solubility tends to decrease.
- the water-soluble polyester resin a commercially available product can be used.
- “Plus Coat Z-561” weight average molecular weight: about 27000
- “Plus Coat Z— 565” weight average molecular weight: about 25000
- Water-soluble acrylic resin The “water-soluble acrylic resin” referred to in the present invention is an acrylic resin that is dispersed or dissolved in water by containing a carboxyl group-containing monomer as an essential component.
- the acrylic resin is a monomer component in which a carboxyl group-containing monomer and a (meth) acrylic ester are essential, and if necessary, other unsaturated monomers as monomer components.
- Acrylic polymer is a monomer component in which a carboxyl group-containing monomer and a (meth) acrylic ester are essential, and if necessary, other unsaturated monomers as monomer components.
- examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate , Monomethyl itaconate, monobutyl itaconate and the like, and one or more of them can be used.
- (meth) acrylic acid is preferable.
- Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
- alkyl methacrylates having 1 to 18 carbon atoms such as nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc. Species or two or more can be used.
- unsaturated monomers include, for example, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, hydroxyl group-containing monomers, and the like.
- aromatic alkenyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene and the like.
- vinyl cyanide compound include acrylonitrile and methacrylonitrile.
- conjugated diene compound include butadiene and isoprene.
- Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
- Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. Examples thereof include acrylate, 4-hydroxybutyl methacrylate, ⁇ -hydroxymethylethyl (meth) acrylate and the like. These can use 1 type (s) or 2 or more types.
- the release layer is preferably formed by a method in which a coating liquid containing water-soluble cellulose, water-soluble polyester or water-soluble acrylic resin is applied to the support layer and dried.
- a coating liquid containing water-soluble cellulose, water-soluble polyester or water-soluble acrylic resin is applied to the support layer and dried.
- the coating solution can be used in an emulsion form or an aqueous solution form.
- a core-shell type emulsion is preferable, and in the core-shell type emulsion, it is important that a carboxyl group is present in the shell of the core-shell particle.
- an acrylic resin containing a (meth) acrylic acid ester is preferable, and in the core-shell type emulsion, it is important that a carboxyl group is present in the shell of the core-shell particle.
- an acrylic resin containing a (meth) acrylic acid ester is an acrylic resin containing a (meth) acrylic acid ester.
- a commercially available product (emulsion) of such core-shell particles can be used.
- Jonkrill 7600 Tg: about 35 ° C.
- 7630A Tg: about 53 ° C.
- 538J Tg: about 66 ° C.
- 352D Tg: about 56 ° C.
- the acrylic resin is an acrylic resin containing a carboxyl group-containing monomer and a (meth) acrylic acid ester, and it is important that the molecular weight is relatively low. Therefore, it is preferable that the weight average molecular weight is 1000 to 50,000. If the weight average molecular weight is less than 1000, the layer formability tends to decrease. If the weight average molecular weight exceeds 50000, the adhesion to the support layer is high. It becomes the tendency for the peelability of the support body layer after hardening to fall.
- a commercially available product can be used as such an aqueous solution of the water-soluble acrylic resin, and examples thereof include Jonkrill 354J (manufactured by BASF Japan Ltd.).
- a water-soluble acrylic resin emulsion is preferred.
- the metal used for the metal film layer is a single metal such as gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium, or two or more metals such as nickel / chromium alloy.
- copper is particularly preferable from the viewpoint of versatility of metal film formation, cost, ease of removal by etching, and the like.
- the metal film layer may be a single layer or a multilayer structure in which two or more different metals are laminated.
- the metal film layer is preferably formed by one or more methods selected from a vapor deposition method, a sputtering method, and an ion plating method.
- a metal foil such as a copper foil is used instead of the metal film layer, it is difficult to form a conductor layer having excellent peel strength on the smooth insulating layer surface.
- the smooth surface such as the glossy surface of the metal foil is transferred to the adherend and the metal foil is removed by etching, sufficient conductor peeling is possible even if the conductor layer is formed by electroless plating and electrolytic plating. It is difficult to obtain strength, and the surface of the insulating layer is inferior in smoothness to the present invention.
- the insulating layer surface becomes a roughened rough surface, and even if sufficient conductor peel strength is obtained, This is disadvantageous for miniaturization.
- the thickness of the metal film layer is not particularly limited, but is usually 25 nm to 5000 nm, preferably 25 nm to 3000 nm, more preferably 100 nm to 3000 nm, and particularly preferably 100 nm to 1000 nm.
- the layer thickness is too small, the metal film tends to crack after the production of the film with the metal film.
- the layer thickness is too large, it takes a long time to form the metal film, which is not preferable from the viewpoint of cost.
- a two-layer structure of copper layer / chromium layer, nickel / chromium alloy layer or titanium layer is used from the viewpoints of versatility and adhesion to the resin (peel strength after formation of the conductor layer).
- the side in contact with the curable resin composition layer is a chromium layer, a nickel-chromium alloy layer, or a titanium layer.
- the total layer thickness in the case of such a two-layer structure is the same as described above, and the thickness of the chromium layer, nickel-chromium layer or titanium layer is preferably 5 nm to 100 nm, more preferably 5 nm to 50 nm, especially Preferably, it is 5 nm to 30 nm, and most preferably 5 to 20 nm.
- the adhesive film with a metal film in the present invention has a structure in which a curable resin composition layer is formed on the metal film layer of the metal film layer transfer film described above. That is, the adhesive film with a metal film in the present invention has a cured resin composition layer in addition to the support layer and the metal film layer. Moreover, it is preferable to have a release layer between a support body layer and a metal film layer like a film with a metal film.
- the curable resin composition used for the curable resin composition layer can be used without particular limitation as long as the cured product has sufficient hardness and insulation, for example, epoxy
- a composition in which at least the curing agent is blended with a curable resin such as a resin, a cyanate ester resin, a phenol resin, a bismaleimide-triazine resin, a polyimide resin, an acrylic resin, or a vinylbenzyl resin is used.
- a composition containing an epoxy resin as the curable resin is preferable.
- a composition containing at least (a) an epoxy resin, (b) a thermoplastic resin, and (c) a curing agent is preferable.
- epoxy resin examples include bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, and alicyclic ring Epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin having butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl ether of naphthalenediol , Glycidyl etherified products of phenols, diglycidyl etherified products of alcohols, and alkyl-substituted products, halides and hydrogenated products of these epoxy resins, etc. And the like. These epoxy resins may be used alone or in combination of two or more.
- the epoxy resin has a bisphenol A type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a butadiene structure from the viewpoint of heat resistance, insulation reliability, and adhesion to a metal film.
- Epoxy resins are preferred.
- liquid bisphenol A type epoxy resin (“JER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by DIC Corporation), naphthalene type 4 Functional epoxy resin (“HP4700” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), anthraquinone type epoxy resin (“YX8800” manufactured by Japan Epoxy Resin Co., Ltd.), butadiene Epoxy resin having a structure ("PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having a biphenyl structure ("NC3000H", “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), "manufactured by Japan Epoxy Resins Co., Ltd.” YX4000 ”) and the like.
- JER828EL liquid bisphenol A type epoxy resin
- HP4032 naphthalene type bifunctional epoxy
- thermoplastic resin is blended for the purpose of imparting appropriate flexibility to the cured composition, for example, phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone. And polysulfone. These may be used alone or in combination of two or more.
- the thermoplastic resin is preferably blended in a proportion of 0.5 to 60% by weight, more preferably 3 to 50% by weight, when the nonvolatile component of the curable resin composition is 100% by weight.
- thermoplastic resin When the blending ratio of the thermoplastic resin is less than 0.5% by weight, since the resin composition viscosity is low, it tends to be difficult to form a uniform curable resin composition layer, and when it exceeds 60% by weight, Since the viscosity of the resin composition becomes too high, embedding in the wiring pattern on the substrate tends to be difficult.
- phenoxy resin examples include, for example, FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100 manufactured by Japan Epoxy Resin Co., Ltd., YL6954, YL6974, YL7213, YL6794, YL7482, YL7553, YL7290, and the like.
- the polyvinyl acetal resin is preferably a polyvinyl butyral resin, and specific examples of the polyvinyl acetal resin include: Denshi Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. ) Made S-Rec BH series, BX series, KS series, BL series, BM series and the like.
- polyimide examples include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Further, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton-containing polyimide (JP-A 2002-2002). Modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386).
- polyamideimide examples include polyamideimides “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd.
- modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned. *
- polyethersulfone examples include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
- polysulfone examples include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.
- Examples of the curing agent include an amine curing agent, a guanidine curing agent, an imidazole curing agent, a triazine skeleton-containing phenol curing agent, a phenol curing agent, a triazine skeleton-containing naphthol curing agent, and a naphthol curing agent. And acid anhydride curing agents or epoxy adducts or microencapsulated ones thereof, active ester curing agents, benzoxazine curing agents, cyanate ester resins, and the like.
- curing agent may be 1 type, or may use 2 or more types together.
- a triazine skeleton-containing phenolic curing agent and a naphtholic curing agent may be used in combination.
- phenol-based curing agent and naphthol-based curing agent include, for example, MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.) ), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Toto Kasei Co., Ltd.), TD2090 (manufactured by DIC Corporation), and the like.
- triazine skeleton-containing phenolic curing agent examples include LA3018 (manufactured by DIC Corporation).
- triazine skeleton-containing phenol novolak curing agent examples include LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like.
- the active ester compound functions as a curing agent for epoxy resins, and generally contains ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds in one molecule.
- a compound having two or more in the above is preferably used.
- the active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
- an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound is preferable.
- Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
- Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl
- active ester compounds Two or more active ester compounds may be used in combination.
- an active ester compound disclosed in JP-A No. 2004-427761 may be used, or a commercially available one may be used.
- commercially available active ester compounds include, for example, EXB-9451, EXB-9460 (manufactured by DIC Corporation), those containing a dicyclopentadienyl diphenol structure, DC808, phenol novolac as an acetylated product of phenol novolac.
- YLH1026 manufactured by Japan Epoxy Resin Co., Ltd.
- benzoylated compounds can benzoylated compounds.
- benzoxazine compound examples include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.
- the blending ratio of (a) epoxy resin and (c) curing agent is such that the epoxy equivalent of epoxy resin in the case of triazine skeleton-containing phenolic curing agent, phenolic curing agent, triazine skeleton-containing naphthol curing agent, and naphthol curing agent.
- a ratio in which the phenolic hydroxyl group equivalent of these curing agents is in the range of 0.4 to 2.0 is preferable, and a ratio in the range of 0.5 to 1.0 is more preferable.
- the reactive group equivalent ratio is outside this range, the mechanical strength and water resistance of the cured product tend to be lowered.
- the curable resin composition may further contain (d) a curing accelerator in addition to (c) the curing agent.
- a curing accelerator examples include imidazole compounds and organic phosphine compounds, and specific examples include 2-methylimidazole and triphenylphosphine.
- a curing accelerator When a curing accelerator is used, it is preferably used in the range of 0.1 to 3.0% by weight based on the epoxy resin.
- the curable resin composition may contain (e) an inorganic filler in order to reduce the thermal expansion of the cured composition.
- an inorganic filler examples include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide and the like, and silica and alumina are preferable, and amorphous silica, fused silica, crystalline silica, Silica such as synthetic silica is preferred.
- the silica is preferably spherical.
- the inorganic filler preferably has an average particle size of 3 ⁇ m or less and more preferably 1.5 ⁇ m or less from the viewpoint of insulation reliability.
- the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter.
- an inorganic filler dispersed in water by ultrasonic waves can be preferably used.
- LA-500 manufactured by Horiba, Ltd. can be used as a laser diffraction particle size distribution measuring apparatus.
- Inorganic fillers include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (aminoethyl) amino to improve moisture resistance and dispersibility.
- Aminosilane coupling agents such as probil trimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxy (Cyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilane coupling agents such as mercatopropyltrimethoxysilane, mercatopropyltriethoxysilane, methyltrimethoxysilane, Silane coupling agents such as octadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane
- the content of the inorganic filler in the curable resin composition is preferably 20 to 80% by weight, more preferably 20 to 70% by weight when the nonvolatile component of the curable resin composition is 100% by weight. is there.
- the content of the inorganic filler is less than 20% by weight, the effect of lowering the thermal expansion coefficient tends not to be sufficiently exhibited.
- the content of the inorganic filler exceeds 80% by weight, the mechanical strength of the cured product decreases. It becomes a tendency to do.
- the curable resin composition of the present invention may contain solid rubber particles for the purpose of increasing the mechanical strength of the cured product and for stress relaxation effect.
- the rubber particles are not dissolved in the organic solvent when preparing the resin composition, are not compatible with components in the resin composition such as an epoxy resin, and exist in a dispersed state in the varnish of the resin composition. preferable.
- Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.
- the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles.
- the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
- the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer.
- Examples include a three-layer structure in which the shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer.
- the glass layer is made of, for example, a polymer of methyl methacrylate
- the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
- Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, (Ganz Kasei Co., Ltd.
- NBR acrylonitrile butadiene rubber
- SBR styrene butadiene rubber
- acrylic rubber particles include Methbrene W300A (average particle size 0.1 ⁇ m), W450A (average particle size 0.5 ⁇ m) (manufactured by Mitsubishi Rayon Co., Ltd.).
- the average particle size of the rubber particles to be blended is preferably in the range of 0.005 to 1 ⁇ m, more preferably in the range of 0.2 to 0.6 ⁇ m.
- the average particle diameter of the rubber particles in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the rubber particles is created on a mass basis, and the median diameter is determined. The average particle size can be measured.
- the content is preferably in the range of 1 to 10% by mass and more preferably in the range of 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. .
- the curable resin composition of the present invention has a thermosetting property other than an epoxy resin such as a maleimide compound, a bisallyl nadiimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin as long as the effects of the present invention are exhibited as necessary.
- a resin can also be blended.
- Such thermosetting resins may be used in combination of two or more.
- BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (all manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (all manufactured by KAI Kasei Co., Ltd.), ANILIX -MI (manufactured by Mitsui Chemical Fine Co., Ltd.), BANI-M as the bisallyl nadiimide compound, BANI-X (both from Maruzen Petrochemical Co., Ltd.)
- V1000X and V1100X both manufactured by Showa Polymer Co., Ltd.
- the curable resin composition of the present invention may contain a flame retardant as long as the effects of the present invention are exhibited.
- Two or more flame retardants may be mixed and used.
- the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
- organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno.
- organic nitrogen-containing phosphorus compound examples include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd.
- metal hydroxide magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd.
- aluminum hydroxide such as B-303 and UFH-20.
- the curable resin composition of the present invention may optionally contain various resin additives other than those described above as long as the effects of the present invention are exhibited.
- the resin additive include organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based and polymer-based antifoaming agents or leveling agents, and silane coupling.
- adhesion-imparting agents such as an agent, a triazole compound, a thiazole compound, a triazine compound, and a porphyrin compound, and a colorant such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.
- the curable resin composition layer may be a prepreg obtained by impregnating the above-described curable resin composition in a sheet-like reinforcing base made of fibers.
- a fiber of the sheet-like reinforcing substrate for example, a glass cloth or an aramid fiber, which is commonly used as a prepreg fiber, can be used.
- the prepreg can be formed by impregnating a curable resin composition by a sheet-like reinforcing base material hot melt method or a solvent method and semi-curing by heating.
- the hot melt method without dissolving the resin composition in an organic solvent, once coated the resin composition on the resin composition and good peelable coated paper, and laminate it on a sheet-like reinforcing substrate, Or it is the method of manufacturing a prepreg by coating directly with a die coater.
- the solvent method is a method in which a sheet-like reinforcing base material is immersed in a varnish obtained by dissolving a resin composition in an organic solvent, the varnish is impregnated into the sheet-like reinforcing base material, and then dried.
- the thickness of the curable resin composition layer varies depending on the thickness of the inner circuit conductor layer, etc., but is about 10 to 150 ⁇ m from the viewpoint of insulation reliability between layers. And more preferably 15 to 80 ⁇ m.
- the production method of the film with metal film and the adhesive film with metal film of the present invention is not particularly limited, but the following method is suitable.
- a metal film layer is formed on the support layer.
- the release layer is formed on the surface of the support layer prior to the formation of these metal layers.
- a metal film layer is formed on the release layer surface.
- the method for forming the release layer is not particularly limited, and a known lamination method such as hot pressing, hot roll lamination, extrusion lamination, coating / drying of a coating solution can be adopted, but a simple and highly uniform layer can be formed. From the viewpoint of easy formation, a method of applying and drying a coating liquid containing a material used for the release layer is preferable.
- the metal film is preferably formed by one or more methods selected from a vapor deposition method, a sputtering method, and an ion plating method, and particularly preferably formed by a vapor deposition method and / or a sputtering method. These methods can be used in combination, but usually any one method is used alone.
- vapor deposition method vacuum vapor deposition method
- the support is placed in a vacuum vessel and the metal is heated and evaporated to release the metal on the support (if a release layer is provided, the release layer). Film formation can be performed on the top).
- a known method can be used. For example, a support is placed in a vacuum vessel, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas is applied to the target metal. Film formation can be performed on the support (on the release layer in the case of having a release layer) by the metal that has been struck and struck.
- an inert gas such as argon
- a DC voltage is applied
- the ionized inert gas is applied to the target metal.
- Film formation can be performed on the support (on the release layer in the case of having a release layer) by the metal that has been struck and struck.
- a well-known method can also be used for the ion plating method.
- the support is placed in a vacuum vessel, the metal is heated and evaporated in a glow discharge atmosphere, and the ionized evaporated metal is used on the support (release layer). Can be formed on the release layer.
- the adhesive film with a metal film can be produced by forming a curable resin composition layer on the surface of the metal film layer after the formation process of the metal film layer of the film with the metal film.
- a known method can be used as a method for forming the curable resin composition layer.
- a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and this resin varnish is attached to a metal film using a die coater or the like. It can be produced by coating on a metal film layer of the film and further drying the organic solvent by heating or blowing hot air to form a resin composition layer.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
- ketones such as acetone, methyl ethyl ketone and cyclohexanone
- acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate
- carbitols such as cellosolve and butyl carbitol.
- Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents
- Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by weight or less, preferably 5% by weight or less.
- a resin composition layer is formed by drying a varnish containing 30 to 60% by weight of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. Is done.
- the adhesive film with a metal film is an adhesive film in which a curable resin composition layer is formed on a support layer separately from the film with a metal film, and the film with the metal film and the adhesive film are curable resin. It can also be produced by a method in which the composition layer and the metal film layer are bonded together under heating conditions.
- An adhesive film can be manufactured by a well-known method, The above-mentioned thing is applied to the support body layer and curable resin composition layer.
- the adhesive film may be produced by laminating the prepreg on the support layer by, for example, a vacuum laminating method.
- the film with the metal film and the adhesive film are bonded to each other so that the metal film layer of the film with the metal film and the curable resin composition layer of the adhesive film face each other, and heated with a hot press, a heat roll, or the like.
- the heating temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- the pressing pressure is preferably in the range of 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ), and 2 to 7 kgf / cm 2 (19.6 ⁇ 10 4 to 68.68. A range of 6 ⁇ 10 4 N / m 2 ) is particularly preferred.
- the method for producing a multilayer printed wiring board using a film with a metal film in the present invention is a method that undergoes at least the following steps (A) to (E).
- a film with a metal film in which a metal film layer is formed on a support layer is laminated on an inner circuit board via a curable resin composition layer, or on the metal film layer of the film with a metal film
- a step of laminating an adhesive film with a metal film on which an curable resin composition layer is formed on an inner circuit board (B) a step of curing the curable resin composition layer to form an insulating layer; (C) removing the support layer, (D) A step of removing the metal film layer, and (E) a step of forming the metal film layer on the surface of the insulating layer by electroless plating.
- the “inner layer circuit board” in the present invention is a pattern processed on one or both sides of a glass epoxy board, metal board, polyester board, polyimide board, BT resin board, thermosetting polyphenylene ether board (circuit formation).
- An intermediate product having a conductor layer and having an insulating layer and a conductor layer further formed when the circuit board is manufactured.
- step (A) when an adhesive film with a metal film is used, the curable resin composition layer may be laminated on the inner circuit board as an adhesive surface.
- the curable resin composition layer when using a film with a metal film, it laminates
- a known method can be used to form the curable resin composition layer on the inner layer circuit board.
- the lamination conditions of the adhesive film in this case are the same as the lamination conditions of the adhesive film with a metal film described later.
- the prepreg is a single-sided or double-sided surface layer of a laminate in which a single prepreg or a multilayer prepreg obtained by stacking a plurality of prepregs is laminated on an inner circuit board.
- the film with a metal film can be laminated
- the film is laminated on the surface of the adherend by a roll or press-bonding from the viewpoint of easy workability and uniform contact. Especially, it is suitable to laminate
- the lamination method may be a batch method or a continuous method using a roll.
- the heating temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- the pressing pressure is preferably in the range of 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ), and 2 to 7 kgf / cm 2 (19.6 ⁇ 10 4 to 68.68. A range of 6 ⁇ 10 4 N / m 2 ) is particularly preferred.
- the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
- Vacuum lamination can be performed using a commercially available vacuum laminator.
- Commercially available vacuum laminators include, for example, batch type vacuum press laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., vacuum applicator manufactured by Nichigo Morton Co., Ltd., roll dry coater manufactured by Hitachi Industries, Ltd. Examples include a vacuum laminator manufactured by Hitachi IC Corporation.
- Step (B) is a step of curing the curable resin composition layer to form an insulating layer, and is usually performed by thermosetting.
- the curing conditions vary depending on the type of curable resin, but generally the curing temperature is 120 to 200 ° C. and the curing time is 15 to 90 minutes.
- the curing is performed in a stepwise manner from a relatively low curing temperature to a high curing temperature.
- the removal of the support layer in the step (C) is generally performed by mechanical peeling with a manual or automatic peeling device.
- the support layer can also be removed by etching.
- the support layer is peeled off after the insulating layer is formed by the curing treatment of the curable resin composition layer.
- problems such as the metal film layer not being sufficiently transferred and cracks in the metal film layer after the curable resin composition is cured are likely to occur.
- the release layer is removed.
- the removal of the support layer (if the release layer remains on the metal film layer, the removal of the support layer and the release layer) is performed before the step of forming the blind via. Alternatively, it may be either later, but in general, before the formation of blind vias is preferred.
- the release layer can be removed, for example, with a metal release layer using an etching solution that dissolves the metal, or with a water-soluble polymer release layer using an aqueous solution.
- the water-soluble polymer which consists of 1 or more types selected from water-soluble cellulose resin, water-soluble acrylic resin, and water-soluble polyester resin is employ
- adopted as a mold release layer curable resin which is a to-be-adhered body
- the support layer can be peeled between the support layer and the release layer, and then the release layer remaining on the metal film layer can be easily removed with an aqueous solution.
- the aqueous solution for dissolving and removing the release layer is preferably an alkaline aqueous solution in which sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like are dissolved in water at a concentration of 0.5 to 10% by weight. Etc.
- the aqueous solution may contain an alcohol such as methanol, ethanol, isopropyl alcohol or the like as long as there is no problem in manufacturing a circuit board or the like.
- the method of dissolving and removing is not particularly limited, and examples thereof include a method of removing the support layer by immersing the substrate in the aqueous solution and dissolving and removing, and a method of dissolving and removing the aqueous solution by spraying it in a spray or mist form.
- the temperature of the aqueous solution is usually about room temperature to 80 ° C., and the treatment time can be usually 10 seconds to 10 minutes with an aqueous solution such as water immersion or spraying.
- alkaline aqueous solution examples include an alkaline developing solution (for example, 0.5 to 2 wt% sodium carbonate aqueous solution, 25 ° C. to 40 ° C.) used in the manufacture of multilayer printed wiring boards, and a dry film peeling machine.
- Stripping solution for example, 1 to 5 wt% sodium hydroxide aqueous solution, 40 to 60 ° C.
- swelling solution used in desmear process for example, alkaline aqueous solution containing sodium carbonate, sodium hydroxide, etc., 60 to 80 ° C.
- the removal of the metal film layer in the step (D) is performed by etching away with a solution that dissolves the metal forming the metal film layer.
- the metal film layer is usually removed by etching after a drilling step and, if necessary, a desmear step. Etching is selected according to the selected metal layer.
- an acidic etching solution such as an aqueous solution of ferric chloride, an aqueous solution of sodium peroxodisulfate and sulfuric acid, or CF- An alkaline etching solution such as 6000, E-Process-WL manufactured by Meltex Co., Ltd. can be used.
- an etching solution mainly composed of nitric acid / sulfuric acid can be used, and commercially available products include NH-1865 manufactured by Mec Co., Ltd. and Melstrip N-950 manufactured by Meltex Co., Ltd. Is mentioned.
- the release layer remains on the metal film layer and the release layer and the metal film layer can be removed at the same time, they may be removed at the same time.
- the arithmetic average roughness (Ra) on the surface of the insulating layer after removing the metal film layer is preferably 200 nm or less, more preferably 80 nm or less, more preferably 70 nm or less, and more preferably 60 nm or less from the viewpoint of fine wiring.
- the arithmetic average roughness (Ra value) can be measured by using a known method, for example, using a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Becoins Instruments Co., Ltd.) or the like. Can do.
- a non-contact type surface roughness meter for example, WYKO NT3300 manufactured by Becoins Instruments Co., Ltd.
- the step of forming the metal film layer on the surface of the insulating layer by electroless plating can be performed by a known method.
- the surface of the insulating layer is treated with a surfactant or the like to provide a plating catalyst such as palladium.
- the metal film layer can be formed by impregnating the electroless plating solution.
- the metal film layer include copper, nickel, gold, palladium and the like, but copper is preferable.
- the thickness is preferably 0.1 to 5.0 ⁇ m. From the viewpoint of sufficient coating on the resin surface and cost, it is usually about 0.2 to 2.5 ⁇ m, preferably about 0.2 to 1.5 ⁇ m.
- the metal film layer may be formed by a direct plating method which is a kind of electroless plating.
- a conductor layer is formed by electrolytic plating using the metal film layer.
- Such conductor layer formation can be performed by a known method such as a semi-additive method.
- a plating resist is formed, and the conductor layer is formed by electrolytic plating using the metal film layer formed by electroless plating as a plating seed layer (step (H)).
- the electroplating conductor layer is preferably copper, and the thickness is generally 3 to 35 ⁇ m, preferably 5 to 30 ⁇ m, depending on the desired multilayer printed wiring board design.
- the plating resist is removed with a plating resist remover such as an alkaline aqueous solution, and then the plating seed layer is removed to form a wiring pattern.
- a plating resist remover such as an alkaline aqueous solution
- the method for removing the plating seed layer can be performed in the same manner as the above-described removal of the metal film (removal of the metal film layer in the step (D)).
- blind vias and through holes may be formed by a known method.
- conduction between layers is generally performed by a blind via.
- the through hole is generally formed in the core substrate, but the through hole may be formed after the insulating layer is formed.
- the same treatment as the desmear process for example, desmear treatment with an oxidizing agent described later
- a mechanical drill is generally used for forming the through hole, and a laser such as a carbon dioxide laser or a YAG laser is generally used for forming the blind via.
- the step of forming the blind via can be performed from the support layer before removing the support layer (that is, (B) After the step of curing the curable resin composition layer and forming the insulating layer, C) can be performed before the step of removing the support layer). Further, when the release layer remains after the support layer is removed, it can also be performed from above the release layer (that is, it can be performed after the step of removing the support layer).
- the blind via is preferably formed before removing the metal film layer.
- Blind vias may be formed after removal of the metal film, but the surface of the insulating layer is roughened when the desmear of the blind via is performed by an oxidizing agent treatment such as an alkaline permanganate solution. It is not preferable to form a blind via in terms of fine wiring.
- an oxidizing agent treatment such as an alkaline permanganate solution. It is not preferable to form a blind via in terms of fine wiring.
- a support material layer and / or a mold release layer contain a laser absorptive component. Examples of the laser absorbing component include metal compound powder, carbon powder, metal powder, and black dye.
- the blending amount of the laser energy absorbing component is usually 0.05 to 40% by weight, preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on all the components constituting the layer containing the component. It is.
- the component when the component is contained in a release layer formed from a water-soluble resin, the total content including the water-soluble resin and the component is set to 100% by weight, and the above content is preferably blended.
- the carbon powder include carbon black powder such as furnace black, channel black, acetylene black, thermal black, and anthracene black, graphite powder, and a powder of a mixture thereof.
- titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, Aluminum oxide, rare earth oxide, cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, sulfuric acid Examples thereof include powders of barium, rare earth oxysulfides, or mixtures thereof.
- metal powders include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or alloys or mixtures thereof. Is mentioned.
- Black dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketone imine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine dyes, perylenes And dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, or mixtures thereof.
- azo monoazo, disazo, etc.
- the black dye is preferably a solvent-soluble black dye in order to improve dispersibility in a water-soluble resin.
- These laser energy absorbing components may be used alone or in combination with different types.
- the laser energy absorbing component is preferably carbon powder, particularly carbon black, from the viewpoint of conversion efficiency of laser energy into heat, versatility, and the like.
- the desmear process of the process (G) can be performed by a known method such as a dry method such as plasma or a wet method using an oxidizing agent treatment such as an alkaline permanganate solution.
- the desmear process is a process mainly for removing a via bottom residue generated by blind via formation, and may be performed for the purpose of roughening the via wall surface.
- desmear with an oxidizing agent is preferable in that it can remove smear on the bottom of the via and at the same time roughen the via wall surface with the oxidizing agent and improve the plating adhesion strength.
- the desmear process can be performed before peeling the support layer when the blind via is formed on the support layer, but usually after peeling the support layer (if the release layer remains, further release Preferably after the removal of the layer.
- the desmear process is preferably performed at least before the process of removing the metal film layer.
- the desmear process with an oxidizing agent is usually performed by performing a swelling process with a swelling liquid, a roughening process with an oxidizing agent, and a neutralizing process with a neutralizing liquid in this order.
- the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable.
- Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
- Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd. be able to.
- Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
- the roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is usually performed by applying the oxidizing agent solution heated to about 60 to 80 ° C. for about 10 to 30 minutes.
- the concentration of permanganate in the alkaline permanganate solution is generally about 5 to 10% by weight.
- Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd.
- As the neutralizing solution an acidic aqueous solution is preferable, and as a commercial product, reduction solutionin securigant P (neutralizing solution) manufactured by Atotech Japan Co., Ltd. can be mentioned.
- a part where the metal film layer does not exist is formed around the via, but in the desmear process, the uneven part is roughened by a roughening process in the part where the metal film layer around the via does not exist.
- a surface can be formed. It is not necessary to etch the periphery of the via at the time of circuit formation. By making the periphery of the via a roughened surface, the adhesion with the subsequent electroless plating becomes stronger and the connection reliability of the blind via can be improved.
- the surface of the base metal layer at the bottom of the via can be etched at the same time.
- the smear at the bottom of the via can be more completely removed.
- the metal of the metal film layer and the via bottom metal layer is copper
- smear removal by etching of the via bottom base copper layer surface can be performed simultaneously with the etching of the copper film layer by the copper etching solution.
- the curable resin composition in the present invention preferably contains a component containing a hetero atom in the molecule, and particularly preferably contains a component containing a nitrogen atom.
- the curable resin composition containing an epoxy resin and a curing agent usually contains a component containing a hetero atom as an epoxy resin and / or a curing agent.
- an amine-based curing is used as the curing agent.
- Agent guanidine-based curing agent, imidazole-based curing agent, triazine skeleton-containing phenol-based curing agent, triazine skeleton-containing naphthol-based curing agent, or epoxy adducts or microcapsules thereof, benzoxazine-based curing agent, cyanate ester resin, etc.
- a curing agent containing a nitrogen atom in the molecule and it is particularly preferable to use a triazine skeleton-containing phenol novolak resin and / or a triazine skeleton-containing cresol novolak resin.
- a representative multilayer printed wiring board obtained by the production method of the present invention has a conductor layer formed on the surface of an insulating layer having an arithmetic average roughness (Ra) of 200 nm or less, and an X-ray photoelectron spectrometer.
- Ra arithmetic average roughness
- X-ray photoelectron spectrometer an X-ray photoelectron spectrometer.
- the nitrogen atom concentration on the surface of the insulating layer is higher than the concentration of other portions (for example, the lower portion of the insulating layer).
- part means “part by weight”.
- PET polyethylene terephthalate
- HP-55 methyl ethyl ketone manufactured by Shin-Etsu Chemical Co., Ltd.
- a 1: 1 solution of N, N-dimethylformamide (that is, a solution using a mixed solvent having a mass ratio of MEK and DMF of 1: 1) is The solvent was removed by heating from room temperature to 140 ° C.
- a hydroxypropyl methylcellulose phthalate layer having a thickness of about 1 ⁇ m was formed on the PET film.
- about 500 nm of copper layers were formed by vapor deposition on the hydroxypropyl cellulose phthalate layer, and the film with a metal film was produced.
- ⁇ Preparation of adhesive film having curable resin composition layer 28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and 28 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP 4700” manufactured by DIC Corporation) 20 parts of phenoxy resin ("YX6954BH30" manufactured by Japan Epoxy Resin Co., Ltd.) was dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring.
- liquid bisphenol A type epoxy resin epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.
- naphthalene type tetrafunctional epoxy resin epoxy equivalent 163, “HP 4700” manufactured by DIC Corporation
- the above varnish is coated on a polyethylene terephthalate film (Lintec Co., Ltd.) with a alkyd mold release agent (AL-5, Lintec Co., Ltd.) with a thickness of 38 ⁇ m using a die coater, and the solvent is removed using a hot air drying furnace. Then, an adhesive film having a thickness of the curable resin composition layer of 40 ⁇ m was prepared. The nitrogen content with respect to the solid content at this time was about 1.2% by weight.
- the adhesive film with a metal film was obtained by laminating at 90 ° C. so that the curable resin composition surface of the adhesive film and the metal film surface of the film with the metal film were in contact with each other.
- ⁇ Blind via formation> Blind with a top opening diameter of about 65 ⁇ m on the above substrate using a carbon dioxide laser manufactured by Hitachi Via Mechanics Co., Ltd. under the conditions of an output of 0.6 W, a pulse width of 3 ⁇ s, and two shots. A via was formed.
- Electroless copper plating (using an electroless copper plating process using Atotech Japan Co., Ltd. pharmaceutical solution described in detail below) was performed on the insulating layer obtained by etching the copper film layer.
- the film thickness of the electroless copper plating was about 1 ⁇ m.
- electrolytic copper plating was performed to form a conductor layer (copper layer) having a total thickness of about 30 ⁇ m, thereby obtaining a multilayer printed wiring board.
- Example 1 A multilayer printed wiring board was obtained in the same manner as in Example 1 except that the content of spherical silica in the adhesive film having the curable resin composition layer described in Example 1 was changed to 150.
- the etching solution for the copper layer on the insulating resin layer and the base copper layer used in Example 1 was changed to a mixture of sodium peroxodisulfate (100 g), sulfuric acid (20 ml), and ion-exchanged water (938.4 ml). Except for the above, the same operation as in Example 1 was performed to obtain a multilayer printed wiring board.
- a via was formed using an ESi UV-YAG laser 5300, and the same operation as in Example 1 was performed except that desmear treatment was not performed, to obtain a multilayer printed wiring board.
- Example 2 The same operation as in Example 1 was carried out except that an adhesive film with a metal film using a film with a metal film obtained by sputtering the metal layer of the film with a metal film used in Example 1 was used. Got.
- a multilayer printed wiring board was produced in the same manner as in Example 1 except that the adhesive film having the curable resin composition layer described in Example 1 was changed as follows.
- ⁇ Preparation of adhesive film having curable resin composition layer 30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and 30 parts biphenyl type epoxy resin (epoxy equivalent 291; "NC3000H” manufactured by Nippon Kayaku Co., Ltd.) The mixture was heated and dissolved in 15 parts of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 15 parts of cyclohexanone with stirring.
- MEK methyl ethyl ketone
- active ester compound (“EXB 9460-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solids toluene solution), curing accelerator (manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethyl) Aminopyridine ”) 0.5 parts, Spherical silica (average particle size 0.5 ⁇ m," SO-C2 with aminosilane treatment “manufactured by Admatechs) 120 parts, Phenoxy resin (Japan Epoxy Resin” YL7213BH30 ”) ) 40 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
- active ester compound (“EXB 9460-65T” manufactured by DIC Corporation, active ester equivalent 223, 65% solids toluene solution)
- curing accelerator manufactured by Guangei Chemical Industry Co., Ltd., “4-dimethyl) Aminopyridine ”
- Spherical silica average particle size 0.5 ⁇ m
- the physical property evaluation in the examples described above and the following comparative examples was performed by the following methods. ⁇ Measurement of peel strength of conductor layer> The peel strength of the conductor layer was measured according to JIS C6481. The conductor thickness was about 30 ⁇ m.
- ⁇ Insulation layer surface roughness measurement> The measurement of the insulating layer surface roughness was performed by removing the copper plating layer and the metal film layer on the produced multilayer printed wiring board with a copper etching solution, and using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Beeco Instruments). Ra value (arithmetic mean roughness) of the surface of the insulating layer was determined by setting the measurement range to 121 ⁇ m ⁇ 92 ⁇ m using a VSI contact mode and a 50 ⁇ lens.
- Example 1 In place of the film with a metal film used in Example 1, the surface treatment surface (smooth surface) of ultra-flat electrolytic copper foil (“NA-DFF” manufactured by Mitsui Metal Mining Co., Ltd., 9 ⁇ m) was the same as in Example 1. A curable resin composition layer was formed to obtain an adhesive film with copper foil. Except using this adhesive film with copper foil, operation similar to Example 1 was performed and the multilayer printed wiring board was obtained. After electroless copper plating and electrolytic copper plating, no problems such as swelling occurred, but the peel strength was a low value of about 0.1 kgf / cm.
- NA-DFF ultra-flat electrolytic copper foil
- ⁇ Comparative example 2> instead of the film with a metal film used in Example 1, a curable resin composition layer similar to that in Example 1 was applied to the mat-treated surface of electrolytic copper foil ("JTC foil" manufactured by Nikko Materials Co., Ltd., 18 ⁇ m). It formed and the adhesive film with a copper foil was obtained. Except using this adhesive film with copper foil, operation similar to Example 1 was performed and the multilayer printed wiring board was obtained. After electroless copper plating and electrolytic copper plating, defects such as swelling did not occur, and the peel strength was as high as about 0.9 kgf / cm, but Ra was as large as 1000 nm or more.
- Example 3 instead of the film with a metal film used in Example 1, a curable resin composition layer similar to Example 1 is formed on the glossy surface of electrolytic copper foil ("JTC foil" manufactured by Nikko Materials Co., Ltd., 18 ⁇ m). Then, an adhesive film with copper foil was obtained. Except for using the adhesive film with copper foil, the same operation as in Example 1 was performed. However, since many blisters occurred after electroless copper plating, no subsequent evaluation was performed.
- Example 4 On the copper layer of a glass epoxy substrate on which a circuit is formed with a copper layer of 18 ⁇ m thickness roughened by CZ8100 (a copper complex of azoles, a surface treatment agent containing an organic acid (manufactured by MEC))
- CZ8100 a copper complex of azoles, a surface treatment agent containing an organic acid (manufactured by MEC)
- the adhesive film prepared in Example 1 was made so that the curable resin composition layer was in contact with the surface of the copper circuit, and the batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd.) was used.
- the lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the pressure for 30 seconds at a pressure of 7.54 kgf / cm 2 .
- the curable resin composition layer was heat-cured for 30 minutes at 160 ° C.
- via formation was performed using a UV-YAG laser in the same manner as in Example 4, and desmear treatment was not performed.
- Me Were subjected to plating is not deposited in the majority, a number of blisters in a heat treatment of 30 minutes at 0.99 ° C. after occur. For this reason, not evaluated for peel strength.
- Example 6 An adhesive film (no metal film layer) having the same curable resin composition layer as in Example 1 was produced. Roughening is performed on the copper layer of the glass epoxy substrate on which the circuit is formed with an 18 ⁇ m-thick copper layer by a CZ8100 (a surface treatment agent containing an azoles copper complex and organic acid (MEC Co., Ltd.)). did. Next, the adhesive film was laminated on both surfaces of the substrate using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho) so that the curable resin composition layer was in contact with the copper circuit surface. Lamination was performed at a pressure of 13 hPa or less by reducing the pressure for 30 seconds.
- MVLP-500 manufactured by Meiki Seisakusho
- the PET film with a release agent was peeled off and electroless copper plating was performed in the same manner as in Example 1. However, after removing from the electroless plating bath, the conductor layer easily peeled off in the process of washing with water, and adhesion A highly conductive layer could not be obtained.
- ⁇ Comparative Example 7> ⁇ Preparation of adhesive film having curable resin composition layer> 28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.) and nitrogen-containing epoxy resin (epoxy equivalent 140, “TEPIC-PAS B26” manufactured by Nissan Chemical Industries, Ltd.) 28 parts of nitrogen content (about 12% by weight) and 25 parts of phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resins Co., Ltd.) were dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring.
- liquid bisphenol A type epoxy resin epoxy equivalent 180, “Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.
- nitrogen-containing epoxy resin epoxy equivalent 140, “TEPIC-PAS B26” manufactured by Nissan Chemical Industries, Ltd.
- the above varnish is coated on a polyethylene terephthalate film (Lintec Co., Ltd.) with a alkyd mold release agent (AL-5, Lintec Co., Ltd.) with a thickness of 38 ⁇ m using a die coater, and the solvent is removed using a hot air drying furnace. Then, an adhesive film having a thickness of the curable resin composition layer of 40 ⁇ m was prepared. The nitrogen content with respect to the solid content at this time was about 5.1% by weight.
- the PET film with a release agent was peeled off and electroless copper plating was performed in the same manner as in Example 1. However, the electroless copper plating did not precipitate.
- the nitrogen atom concentration on the surface of the insulating layer was about 1.9 atomic% (about 2.0% by weight).
- Example 1 A T60 (Toray Industries, Inc., polyethylene terephthalate film) is formed in the same manner as in Example 1 to form a hydroxypropylmethylcellulose phthalate layer of about 1 ⁇ m, and then a copper layer of about 1000 nm is formed by vapor deposition. A film was prepared. The arithmetic average roughness of the metal film was 13 nm.
- a plating seed layer (electroless plating layer) can be formed by electroless plating on the surface of a very smooth insulating layer, it is possible to easily remove the unnecessary plating seed layer by etching after circuit formation by the semi-additive method. It is.
- X-ray photoelectron spectroscopy (XPS) measurement of the insulating layer surface after etching of the metal film layer of Example 1 was performed.
- the curable resin composition layer was cured with a polyethylene terephthalate film with an alkyd mold release agent (AL-5, manufactured by Lintec Co., Ltd.) of Comparative Example 6 (that is, with the polyethylene terephthalate film still attached).
- the curable resin composition layer was cured), and XPS measurement was performed on the surface of the insulating layer after peeling the PET film with a release agent.
- the curable resin composition having a higher nitrogen content in Comparative Example 7 was used, and a curable resin composition with a polyethylene terephthalate film with an alkyd mold release agent (AL-5, manufactured by Lintec Corporation) was used.
- the material layer was cured, and XPS measurement was performed on the surface of the insulating layer after peeling off the PET film with a release agent. Measuring equipment and measuring conditions are as follows.
- the results are shown in Table 3.
- the nitrogen atom concentration on the surface of the cured product (insulating layer) cured with the polyethylene terephthalate film with the alkyd mold release agent (AL-5, manufactured by Lintec Corporation) in Comparative Example 6 was about 0.9 atomic% (about 1.%). 0% by weight).
- the nitrogen atom concentration of the cured product cured with the metal film layer in Example 1 was about 7.6 atomic% (about 8.0% by weight), and despite using the same curable resin composition, As a result, the nitrogen atom concentration on the surface of the insulating layer increased significantly.
- Comparative Example 7 the nitrogen component content of the entire curable resin composition was increased, but no improvement in peel strength was observed.
- ⁇ Measurement device> Device model: QUANTERA SXM (Fully automatic scanning X-ray photoelectron spectrometer) Ultimate vacuum: 7.0 ⁇ 10 ⁇ 10 Torr X-ray source: monochromatic Al K ⁇ (1486.6 eV) Spectrometer: Electrostatic concentric hemispherical analyzer Detector: Multi-channel type (32 Multi-Channel Detector) Neutralizing gun setting Electron: 1.0 V (20 ⁇ A), ion: 10.0 V (7 mA)
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Abstract
Description
(1)以下の工程(A)~(E)を含む多層プリント配線板の製造方法;
(A)支持体層上に金属膜層が形成された金属膜付きフィルムを、内層回路基板上に硬化性樹脂組成物層を介して積層するか、又は該金属膜付きフィルムの金属膜層上に硬化性樹脂組成物層が形成された金属膜付き接着フィルムを内層回路基板に積層する工程、
(B)硬化性樹脂組成物層を硬化し絶縁層を形成する工程、
(C)支持体層を除去する工程、
(D)金属膜層を除去する工程、及び
(E)無電解めっきにより絶縁層表面に金属膜層を形成する工程。
(2)金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層が、蒸着法、スパッタリング法及びイオンプレーティング法から選ばれる1種以上の方法により形成されたものである、上記(1)記載の方法。
(3)金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層が銅により形成された、上記(1)又は(2)記載の方法。
(4)(E)無電解めっきにより絶縁層表面に金属膜層を形成する工程での金属膜層が銅により形成される、上記(1)~(3)のいずれかに記載の方法。
(5)(D)金属膜層を除去する工程後の絶縁層表面の算術平均粗さ(Ra)が200nm以下である、上記(1)~(4)のいずれかに記載の方法
(6)(D)金属膜層を除去する工程後の絶縁層表面の算術平均粗さ(Ra)が90nm以下である、上記(1)~(4)のいずれかに記載の方法。
(7)(B)硬化性樹脂組成物層を硬化し絶縁層を形成する工程の後か、又は(C)支持体層を除去する工程の後に、(F)ブラインドビアを形成する工程をさらに含む、上記(1)~(6)のいずれかに記載の方法。
(8)(F)ブラインドビアを形成する工程の後に、(G)デスミア工程をさらに含む、上記(7)記載の方法。
(9)(E)無電解めっきにより絶縁層表面に金属膜層を形成する工程の後に、(H)電解めっきにより導体層を形成する工程をさらに含む、上記(1)~(8)のいずれかに記載の方法。
(10)金属膜付きフィルム又は金属膜付き接着フィルムにおける支持体層と金属膜層間に離型層が存在する、上記(1)~(9)のいずれかに記載の方法。
(11)離型層が水溶性セルロース樹脂、水溶性ポリエステル樹脂及び水溶性アクリル樹脂から選択される1種以上の水溶性高分子から形成されている、上記(10)記載の方法。
(12)水溶性ポリエステル樹脂がスルホ基もしくはその塩及び/又はカルボキシル基もしくはその塩を有する水溶性ポリエステルであり、水溶性アクリル樹脂が、カルボキシル基又はその塩を有する水溶性アクリル樹脂である、上記(11)記載の方法。
(13)(C)支持体層を除去する工程の後に、(I)離型層を除去する工程をさらに含む、上記(10)~(12)のいずれかに記載の方法。
(14)離型層の層厚が0.01μm~20μmである、上記(10)~(13)のいずれかに記載の方法。
(15)金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層の層厚が25nm~5000nmである、上記(1)~(14)のいずれかに記載の方法。
(16)支持体層の層厚が10μm~70μmである、上記(1)~(15)のいずれかに記載の方法。
(17)支持体層の算術平均粗さ(Ra)が50nm以下である、上記(1)~(16)のいずれかに記載の方法。
(18)支持体層がプラスチックフィルムである、上記(1)~(17)のいずれかに記載の方法。
(19)支持体層がポリエチレンテレフタレートフィルムである、上記(1)~(17)のいずれかに記載の方法。
(20)硬化性樹脂組成物が分子中にヘテロ原子を含む成分を含有する、上記(1)~(19)のいずれかに記載の方法。
(21)硬化性樹脂組成物が分子中に窒素原子を含む成分を含有する、上記(1)~(19)のいずれかに記載の方法。
(22)硬化性樹脂組成物がエポキシ樹脂及び硬化剤を含有する、上記(1)~(19)のいずれかに記載の方法。
(23)硬化剤が分子中に窒素原子を含む硬化剤である、上記(22)記載の方法。
(24)硬化剤がトリアジン骨格含有フェノールノボラック樹脂及び/又はトリアジン骨格含有クレゾールノボラック樹脂である、上記(22)記載の方法。
(25)硬化性樹脂組成物が熱可塑性樹脂をさらに含有する、上記(20)~(24)のいずれかに記載の方法。
(26)硬化性樹脂組成物が無機充填材をさらに含有する、上記(20)~(25)のいずれかに記載の方法。
(27)硬化性樹脂組成物層が硬化性樹脂組成物を繊維からなるシート状補強基材中に含浸したプリプレグである、上記(1)~(26)のいずれかに記載の方法。
(28)絶縁層と導体層を有する多層プリント配線板において、算術平均粗さ(Ra)が200nm以下の絶縁層表面に導体層が形成されており、X線光電子分光分析装置で測定した場合の窒素原子濃度において、導体層が形成された該絶縁層表面の窒素原子濃度が、絶縁層下部の窒素原子濃度よりも高いことを特徴とする、多層プリント配線板。
本発明の多層プリント配線板の製法おいては、支持体層上に金属膜層が形成された金属膜付きフィルム(金属膜転写用フィルム)、又は、支持体層上に金属膜層が形成され、さらに該金属膜層上に硬化性樹脂組成物層が形成された金属膜付き接着フィルムを使用する。
支持体層は自己支持性を有するフィルム乃至シート状物であり、金属箔、プラスチックフィルム等を用いることができ、特にプラスチックフィルムが好適に用いられる。金属箔としては、アルミニウム箔、銅箔等が挙げられる。支持体層として金属箔を用いる場合で金属膜付きフィルムが離型層を有しない場合は、形成される金属膜層とは別の金属からなる金属箔が採用される。プラスチックフィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレート、ポリイミド、ポリアミドイミド、ポリアミド、ポリテトラフルオロエチレン、ポリカーボネート等が挙げられ、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルムが好ましく、中でも、安価なポリエチレンテレフタレートが特に好ましい。また支持体層表面は、コロナ処理等の表面処理が施してあってもよい。また金属膜層や離型層が存在しない側の支持体層フィルム表面にも、マット処理、コロナ処理等の表面処理が施してあってもよい。離型層が形成される側の支持体層表面は、金属膜付きフィルムを製造する際のクラック防止の観点から、算術平均粗さ(Ra)を50nm以下(0以上50nm以下)、さらには40nm以下、さらには35nm以下、さらには30nm以下とするのが好ましい。また離型層が形成されない側の支持体層表面の算術平均粗さも、上記と同じ範囲内とするのが好ましい。算術平均粗さ(Ra値)の測定は、公知の方法を用いることができ、例えば、非接触型表面粗さ計(例えば、ビーコインスツルメンツ社製WYKO NT3300等)などの装置を用いて測定することができる。支持体は市販のものを用いることもでき、例えば、T60(東レ(株)製、ポリエチレンテレフタレートフィルム)、A4100(東洋紡績(株)製、ポリエチレンテレフタレートフィルム)、Q83(帝人デュポンフィルム(株)製、ポリエチレンナフタレートフィルム)、ダイアホイルOB100(三菱化学ポリエステルフィルム(株)製、ポリエチレンテレフタレートフィルム)、リンテック(株)製の市販品であるアルキッド型離型剤(AL-5、リンテック(株)製)付きポリエチレンテレフタレートフィルム等が挙げられる。
本発明における金属膜付きフィルム及び金属膜付き接着フィルムは、金属膜を被着体表面に効率的に転写するため、支持体層と金属膜層間に離型層を有するのが好ましい。
本発明でいう「水溶性セルロース樹脂」とは、セルロースに水溶性を付与するための処理を施したセルロース誘導体のことであり、好適には、セルロースエーテル、セルロースエーテルエステル等が挙げられる。
本発明でいう「水溶性ポリエステル樹脂」とは、多価カルボン酸またはそのエステル形成性誘導体と多価アルコールまたはそのエステル形成性誘導体を主たる原料とする通常の重縮合反応によって合成されるような、実質的に線状のポリマーからなるポリエステル樹脂であって、分子中または分子末端に親水基が導入されたものである。ここで、親水基としては、スルホ基、カルボキシル基、燐酸基等の有機酸基またはその塩等が挙げられ、好ましくは、スルホン酸基またはその塩、カルボン酸基またはその塩である。水溶性ポリエステル樹脂としては、特にスルホ基もしくはその塩及び/又はカルボキシル基もしくはその塩を有するものが好ましい。
本発明でいう「水溶性アクリル樹脂」とは、カルボキシル基含有単量体を必須成分として含有することで、水に分散乃至溶解するアクリル樹脂である。
金属膜層に使用する金属としては、金、白金、銀、銅、アルミニウム、コバルト、クロム、ニッケル、チタン、タングステン、鉄、スズ、インジウム等の金属単体やニッケル・クロムアロイ等の2種類以上の金属の固溶体(アロイ)を使用することができるが、金属膜形成の汎用性、コスト、エッチングによる除去の容易性等の観点から、銅が特に好ましい。また、通常、その必要はないが、金属膜層は単層であっても異なる金属が2層以上の積層した複層構造であってもよい。
本発明における金属膜付き接着フィルムは、上述した金属膜層転写用フィルムの金属膜層上に硬化性樹脂組成物層が形成された構造を有する。すなわち、本発明における金属膜付き接着フィルムは、支持体層、金属膜層に加え、さらに硬化物樹脂組成物層を有する。また金属膜付きフィルムと同様、支持体層と金属膜層間に離型層を有するのが好ましい。金属膜付き接着フィルムにおいて、硬化性樹脂組成物層に使用する硬化性樹脂組成物は、その硬化物が、十分な硬度と絶縁性を有するものであれば、特に限定なく使用でき、例えば、エポキシ樹脂、シアネートエステル樹脂、フェノール樹脂、ビスマレイミド-トリアジン樹脂、ポリイミド樹脂、アクリル樹脂、ビニルベンジル樹脂等の硬化性樹脂にその硬化剤を少なくとも配合した組成物が使用される。中でも、硬化性樹脂としてエポキシ樹脂を含有する組成物が好ましく、例えば(a)エポキシ樹脂、(b)熱可塑性樹脂及び(c)硬化剤を少なくとも含有する組成物が好ましい。
本発明における金属膜付きフィルムを使用した多層プリント配線板の製造方法は少なくとも以下の(A)~(E)の工程を経る方法である。
(B)硬化性樹脂組成物層を硬化し絶縁層を形成する工程、
(C)支持体層を除去する工程、
(D)金属膜層を除去する工程、及び
(E)無電解めっきにより絶縁層表面に金属膜層を形成する工程。
厚み38μmのポリエチレンテレフタレート(以下、「PET」とも略する。)フィルム上に、ヒドロキシプロピルメチルセルロースフタレート(信越化学工業(株)製「HP-55」)の固形分10重量%のメチルエチルケトン(以下、「MEK」と略す)とN,N-ジメチルホルムアミド(以下、「DMF」と略す)の1:1溶液(すなわち、MEKとDMFの質量比が1:1の混合溶媒を使用した溶液)をバーコータにより塗布し、熱風乾燥炉を用いて室温から140℃まで昇温速度3℃/秒で昇温することで溶剤を除去し、PETフィルム上に約1μmのヒドロキシプロピルメチルセルロースフタレート層を形成させた。次いで、ヒドロキシプロピルセルロースフタレート層上に蒸着により、銅層約500nmを形成して、金属膜付きフィルムを作製した。
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、ジャパンエポキシレジン(株)製「エピコート828EL」)28部と、ナフタレン型4官能エポキシ樹脂(エポキシ当量163、DIC(株)製「HP4700」)28部、フェノキシ樹脂(ジャパンエポキシレジン(株)製「YX6954BH30」)20部とをMEK15部、シクロヘキサノン15部に撹拌しながら加熱溶解させた。そこへ、トリアジン含有フェノールノボラック樹脂(水酸基当量125、DIC(株)製「LA7054」、窒素含有量約12重量%)27部、ナフトール系硬化剤(水酸基当量215、東都化成(株)製「SN-485」)の固形分50重量%のMEK溶液27部、硬化触媒(四国化成工業(株)製、「2E4MZ」)0.1部、球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」)70部、ポリビニルブチラール樹脂(積水化学工業(株)製「KS-1」)の固形分15重量%のエタノールとトルエンの1:1溶液30部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。厚み38μmのアルキッド型離型剤(AL-5、リンテック(株)製)付きポリエチレンテレフタレートフィルム(リンテック(株)製)上に上記ワニスをダイコータにより塗布し、熱風乾燥炉を用いて溶剤を除去し、硬化性樹脂組成物層の厚みが40μmである接着フィルムを作製した。このときの固形分に対する窒素含有量は約1.2重量%であった。
上記接着フィルムの硬化性樹脂組成物面と金属膜付きフィルムの金属膜面が接触するように、90℃で貼り合わせて巻取り、金属膜付き接着フィルムを得た。
18μm厚の銅層で回路が形成されているガラスエポキシ基板の銅層上をCZ8100(アゾール類の銅錯体、有機酸を含む表面処理剤(メック(株)製))処理にて粗化を施した。次に、上記金属膜付き接着フィルムの離型PETを剥離し、硬化性樹脂組成物層が銅回路表面と接するようにし、バッチ式真空加圧ラミネーターMVLP-500((株)名機製作所製商品名)を用いて、基板の両面に積層した。積層は30秒間減圧して気圧を13hPa以下で行った。その後、160℃で30分間熱硬化し絶縁層を形成した。
上記基板に対し、支持体層上から、日立ビアメカニックス(株)製の炭酸ガスレーザーにより、出力0.6W、パルス幅3μs、ショット数2回の条件でトップの開口径が約65μmのブラインドビアを形成した。
ブラインドビアが形成された基板から、支持体層であるPETフィルムを剥離した後、ヒドロキシプロピルメチルセルロースフタレート層を1重量%炭酸ナトリウム水溶液で溶解除去した。次いで、デスミア工程として、膨潤液であるアトテックジャパン(株)のスエリングディップ・セキュリガントPに80℃で10分間浸漬し、次に、粗化液として、アトテックジャパン(株)のコンセントレート・コンパクトP(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で20分間浸漬し、最後に中和液として、アトテックジャパン(株)のリダクションソリューシン・セキュリガントPに40℃で5分間浸漬した。その後、水洗、乾燥させ、SEMでビア底を観察したところ残渣は確認されなかった。
上記残渣除去処理後の基板を、塩化第二鉄水溶液に25℃で2分間浸漬させ、絶縁層上の銅膜層をエッチング除去とビア底銅層表面のエッチングを行い、その後、水洗し、乾燥させた。目視で絶縁層上の銅膜層が存在しないことを確認した。
上記銅膜層をエッチングした絶縁層上に無電解銅めっき(下記に詳述のアトテックジャパン(株)製薬液を使用した無電解銅めっきプロセスを使用)を行った。無電解銅めっきの膜厚は約1μmとなった。その後、電解銅めっきを行い、合計約30μm厚の導体層(銅層)を形成し、多層プリント配線板を得た。
1.アルカリクリーニング(樹脂表面の洗浄と電荷調整)
商品名:Cleaning cleaner Securiganth 902
条件:60℃で5分
2.ソフトエッチング(ビア底、導体の銅の洗浄)
硫酸酸性ペルオキソ二硫酸ナトリウム水溶液
条件:30℃で1分
3.プレディップ(次工程のPd付与のための表面の電荷の調整が目的)
商品名:Pre. Dip Neoganth B
条件:室温で1分
4.アクティヴェーター(樹脂表面へのPdの付与)
商品名:Activator Neoganth 834
条件:35℃で5分
5.還元(樹脂に付いたPdを還元する)
商品名:Reducer Neoganth WA
:Reducer Acceralator 810 mod.の混合液
条件:30℃で5分
6.無電解銅めっき(Cuを樹脂表面(Pd表面)に析出させる)
商品名:Basic Solution Printganth MSK-DK
:Copper solution Printganth MSK
:Stabilizer Printganth MSK-DK
:Reducer Cu の混合液
条件:35℃で20分
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、ジャパンエポキシレジン(株)製「jER828EL」)30部と、ビフェニル型エポキシ樹脂(エポキシ当量291、日本化薬(株)製「NC3000H」)30部とをメチルエチルケトン(以下「MEK」と略称する。)15部、シクロヘキサノン15部に撹拌しながら加熱溶解させた。そこへ、活性エステル化合物(DIC(株)製「EXB9460-65T」、活性エステル当量223、固形分65%のトルエン溶液)80部、硬化促進剤(広栄化学工業(株)製、「4-ジメチルアミノピリジン」)0.5部、球形シリカ(平均粒径0.5μm、アミノシラン処理付「SO-C2」(株)アドマテックス製)120部、フェノキシ樹脂(ジャパンエポキシレジン(株)製「YL7213BH30」)40部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。
<導体層の剥離強度測定>
導体層の剥離強度をJIS C6481に準拠して行った。導体厚は約30μmとした。
絶縁層表面粗さの測定は、作製した多層プリント配線板上の銅めっき層及び金属膜層を銅エッチング液で除去し、非接触型表面粗さ計(ビーコインスツルメンツ製WYKO NT3300)を用いて、VSIコンタクトモード、50倍レンズにより測定範囲を121μm×92μmとして、絶縁層表面のRa値(算術平均粗さ)を求めた。
実施例1で使用した金属膜付きフィルムの代わりに、超平坦電解銅箔(三井金属鉱業(株)製「NA-DFF」、9μm)の表面処理面(平滑面)に実施例1と同様の硬化性樹脂組成物層を形成し、銅箔付き接着フィルムを得た。該銅箔付き接着フィルムを用いる以外は、実施例1と同様な操作を行い、多層プリント配線板を得た。無電解銅めっき、電解銅めっき後では、膨れ等の不具合は生じなかったが、剥離強度は約0.1kgf/cmと低い値であった。
実施例1で使用した金属膜付きフィルムの代わりに、電解銅箔((株)日鉱マテリアルズ製「JTC箔」、18μm) のマット処理面に実施例1と同様の硬化性樹脂組成物層を形成し、銅箔付き接着フィルムを得た。該銅箔付き接着フィルムを用いる以外は、実施例1と同様な操作を行い、多層プリント配線板を得た。無電解銅めっき、電解銅めっき後では、膨れ等の不具合は生じなく、剥離強度は約0.9kgf/cmと高い値であったが、Raが1000nm以上と大きな値となった。
実施例1で使用した金属膜付きフィルムの代わりに、電解銅箔((株)日鉱マテリアルズ製「JTC箔」、18μm)の光沢面に実施例1と同様の硬化性樹脂組成物層を形成し、銅箔付き接着フィルムを得た。該銅箔付き接着フィルムを用いる以外は、実施例1と同様な操作を行ったが、無電解銅めっき後に多数の膨れが発生したため、後の評価を行わなかった。
CZ8100(アゾール類の銅錯体、有機酸を含む表面処理剤(メック(株)製)処理にて粗化を施された18μm厚の銅層で回路が形成されているガラスエポキシ基板の銅層上に、実施例1で作製した接着フィルム(金属膜層なし)を、硬化性樹脂組成物層が銅回路表面と接するようにし、バッチ式真空加圧ラミネーターMVLP-500((株)名機製作所製商品名)を用いて、積層した。積層は、30秒間減圧して気圧を13hPa以下とし、その後30秒間、圧力7.54kgf/cm2でプレスすることにより行った。その後、離型PETを剥離し、硬化性樹脂組成物層を160℃で30分間熱硬化させた。その後、実施例4と同様の操作によりビアの形成をUV-YAGレーザーを用いて行い、デスミア処理を行わず、無電解めっきを行ったが、めっきは大部分で付着せず、後の150℃で30分間の熱処理で多数の膨れが発生した。そのため、剥離強度の評価を行わなかった。
比較例4と同様の操作により、接着フィルム(金属膜層なし)を、ガラスエポキシ基板上に積層し、熱硬化した。その後、実施例1と同様の操作により、ビア形成、PET剥離、デスミア処理を行った。ここでデスミア処理と同時に絶縁層表面の粗化処理を行った。その後、実施例1と同様の操作により、多層プリント配線板を得た。無電解銅めっき、電解銅めっき後では、膨れ等の不具合は生じなく、剥離強度は約0.7kgf/cmと高い値であったが、Raが500nm以上と大きな値となった。
実施例1と同じ硬化性樹脂組成物層を有する接着フィルム(金属膜層なし)を作製した。18μm厚の銅層で回路が形成されているガラスエポキシ基板の銅層上をCZ8100(アゾール類の銅錯体、有機酸を含む表面処理剤(メック(株)製))処理にて粗化を施した。次に、接着フィルムを硬化性樹脂組成物層が銅回路表面と接するようにし、バッチ式真空加圧ラミネーターMVLP-500((株)名機製作所製)を用いて、基板の両面に積層した。積層は30秒間減圧して気圧を13hPa以下で行った。その後、160℃で30分間熱硬化し絶縁層を形成した。離型剤付きPETフィルムを剥離し、実施例1と同様の操作により無電解銅めっきを行ったが、無電解めっき浴から出した後、水洗を行う過程で容易に導体層が剥がれ落ち、密着性の高い導体層が得られなかった。
<硬化性樹脂組成物層を有する接着フィルムの作製>
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、ジャパンエポキシレジン(株)製「エピコート828EL」)28部と、窒素含有エポキシ樹脂(エポキシ当量140、日産化学工業(株)製「TEPIC-PAS B26」、窒素含有量約12重量%)28部、フェノキシ樹脂(ジャパンエポキシレジン(株)製「YX6954BH30」)25部とをMEK15部、シクロヘキサノン15部に撹拌しながら加熱溶解させた。そこへ、トリアジン含有フェノールノボラック樹脂(水酸基当量146、DIC(株)製「LA1356」、窒素含有量約19重量%)44部、球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」)70部、ポリビニルブチラール樹脂(積水化学工業(株)製「KS-1」)の固形分15重量%のエタノールとトルエンの1:1溶液30部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。厚み38μmのアルキッド型離型剤(AL-5、リンテック(株)製)付きポリエチレンテレフタレートフィルム(リンテック(株)製)上に上記ワニスをダイコータにより塗布し、熱風乾燥炉を用いて溶剤を除去し、硬化性樹脂組成物層の厚みが40μmである接着フィルムを作製した。このときの固形分に対する窒素含有量は約5.1重量%であった。
18μm厚の銅層で回路が形成されているガラスエポキシ基板の銅層上をCZ8100(アゾール類の銅錯体、有機酸を含む表面処理剤(メック(株)製))で処理して粗化を施した。次に、上記接着フィルムを硬化性樹脂組成物層が銅回路表面と接するようにし、バッチ式真空加圧ラミネーターMVLP-500((株)名機製作所製)を用いて、基板の両面に積層した。積層は30秒間減圧して気圧を13hPa以下で行った。その後、160℃で30分間熱硬化し絶縁層を形成した。離型剤付きPETフィルムを剥離し、実施例1と同様の操作により無電解銅めっきを行ったが、無電解銅めっきは析出しなかった。絶縁層表面の窒素原子濃度は約1.9atomic %(約2.0重量%)であった。
T60(東レ(株)製、ポリエチレンテレフタレートフィルム)に実施例1と同様にして、約1μmのヒドロキシプロピルメチルセルロースフタレート層を形成させ、次いで、蒸着により、銅層約1000nmを形成して、金属膜付きフィルムを作製した。金属膜の算術平均粗さは13nmであった。
実施例1の金属膜層のエッチング後の絶縁層表面のX線光電子分光分析(XPS)測定を行った。また、比較として、比較例6のアルキッド型離型剤(AL-5、リンテック(株)製)付きポリエチレンテレフタレートフィルム付で硬化性樹脂組成物層を硬化し(すなわち、ポリエチレンテレフタレートフィルムを付けたままで硬化性樹脂組成物層を硬化し)、該離型剤付きPETフィルムを剥離後の絶縁層表面のXPS測定を行った。また同じく比較として、比較例7の窒素成分含有量を高めた硬化性樹脂組成物を用い、アルキッド型離型剤(AL-5、リンテック(株)製)付きポリエチレンテレフタレートフィルム付で硬化性樹脂組成物層を硬化し、該離型剤付きPETフィルムを剥離後の絶縁層表面のXPS測定を行った。測定装置、測定条件は下記のとおりである。
装置型式:QUANTERA SXM( 全自動走査型X線光電子分光分析装置 )
到達真空度:7.0×10-10Torr
X線源:単色化 Al Kα(1486.6eV)
分光器:静電同心半球型分析器
検出器:多チャンネル式(32 Multi-Channel Detector)
中和銃設定 電子:1.0 V (20μA)、イオン:10.0V(7mA)
<サーベイスペクトル>
X線ビーム径: 100μmΦ (HPモード、100.6W、20kV)
測定領域: 1400μm×100μm
信号の取り込み角: 45.0°
パスエネルギー:280.0eV
Claims (28)
- 以下の工程(A)~(E)を含む多層プリント配線板の製造方法;
(A)支持体層上に金属膜層が形成された金属膜付きフィルムを、内層回路基板上に硬化性樹脂組成物層を介して積層するか、又は該金属膜付きフィルムの金属膜層上に硬化性樹脂組成物層が形成された金属膜付き接着フィルムを内層回路基板に積層する工程、
(B)硬化性樹脂組成物層を硬化し絶縁層を形成する工程、
(C)支持体層を除去する工程、
(D)金属膜層を除去する工程、及び
(E)無電解めっきにより絶縁層表面に金属膜層を形成する工程。 - 金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層が、蒸着法、スパッタリング法及びイオンプレーティング法から選ばれる1種以上の方法により形成されたものである、請求項1記載の方法。
- 金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層が銅により形成された、請求項1又は2記載の方法。
- (E)無電解めっきにより絶縁層表面に金属膜層を形成する工程での金属膜層が銅により形成される、請求項1~3のいずれか1項に記載の方法。
- (D)金属膜層を除去する工程後の絶縁層表面の算術平均粗さ(Ra)が200nm以下である、請求項1~4のいずれか1項に記載の方法
- (D)金属膜層を除去する工程後の絶縁層表面の算術平均粗さ(Ra)が90nm以下である、請求項1~4のいずれか1項に記載の方法。
- (B)硬化性樹脂組成物層を硬化し絶縁層を形成する工程の後か、又は(C)支持体層を除去する工程の後に、(F)ブラインドビアを形成する工程をさらに含む、請求項1~6のいずれか1項に記載の方法。
- (F)ブラインドビアを形成する工程の後に、(G)デスミア工程をさらに含む、請求項7記載の方法。
- (E)無電解めっきにより絶縁層表面に金属膜層を形成する工程の後に、(H)電解めっきにより導体層を形成する工程をさらに含む、請求項1~8のいずれか1項に記載の方法。
- 金属膜付きフィルム又は金属膜付き接着フィルムにおける支持体層と金属膜層間に離型層が存在する、請求項1~9のいずれか1項に記載の方法。
- 離型層が水溶性セルロース樹脂、水溶性ポリエステル樹脂及び水溶性アクリル樹脂から選択される1種以上の水溶性高分子から形成されている、請求項10記載の方法。
- 水溶性ポリエステル樹脂がスルホ基もしくはその塩及び/又はカルボキシル基もしくはその塩を有する水溶性ポリエステルであり、水溶性アクリル樹脂が、カルボキシル基又はその塩を有する水溶性アクリル樹脂である、請求項11記載の方法。
- (C)支持体層を除去する工程の後に、(I)離型層を除去する工程をさらに含む、請求項10~12のいずれか1項に記載の方法。
- 離型層の層厚が0.01μm~20μmである、請求項10~13のいずれか1項に記載の方法。
- 金属膜付きフィルム又は金属膜付き接着フィルムにおける金属膜層の層厚が25nm~5000nmである、請求項1~14のいずれか1項に記載の方法。
- 支持体層の層厚が10μm~70μmである、請求項1~15のいずれか1項に記載の方法。
- 支持体層の算術平均粗さ(Ra)が50nm以下である、請求項1~16のいずれか1項に記載の方法。
- 支持体層がプラスチックフィルムである、請求項1~17のいずれか1項に記載の方法。
- 支持体層がポリエチレンテレフタレートフィルムである、請求項1~17のいずれか1項に記載の方法。
- 硬化性樹脂組成物が分子中にヘテロ原子を含む成分を含有する、請求項1~19のいずれか1項に記載の方法。
- 硬化性樹脂組成物が分子中に窒素原子を含む成分を含有する、請求項1~19のいずれか1項に記載の方法。
- 硬化性樹脂組成物がエポキシ樹脂及び硬化剤を含有する、請求項1~19のいずれか1項に記載の方法。
- 硬化剤が分子中に窒素原子を含む硬化剤である、請求項22記載の方法。
- 硬化剤がトリアジン骨格含有フェノールノボラック樹脂及び/又はトリアジン骨格含有クレゾールノボラック樹脂である、請求項22記載の方法。
- 硬化性樹脂組成物が熱可塑性樹脂をさらに含有する、請求項20~24のいずれか1項に記載の方法。
- 硬化性樹脂組成物が無機充填材をさらに含有する、請求項20~25のいずれか1項に記載の方法。
- 硬化性樹脂組成物層が硬化性樹脂組成物を繊維からなるシート状補強基材中に含浸したプリプレグである、請求項1~26のいずれか1項に記載の方法。
- 絶縁層と導体層を有する多層プリント配線板において、算術平均粗さ(Ra)が200nm以下の絶縁層表面に導体層が形成されており、X線光電子分光分析装置で測定した場合の窒素原子濃度において、導体層が形成された該絶縁層表面の窒素原子濃度が、絶縁層下部の窒素原子濃度よりも高いことを特徴とする、多層プリント配線板。
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Also Published As
Publication number | Publication date |
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JP2013153223A (ja) | 2013-08-08 |
US20110036625A1 (en) | 2011-02-17 |
KR20100122935A (ko) | 2010-11-23 |
TWI434641B (zh) | 2014-04-11 |
KR101560180B1 (ko) | 2015-10-14 |
US8584352B2 (en) | 2013-11-19 |
CN101960935B (zh) | 2014-09-17 |
JPWO2009107760A1 (ja) | 2011-07-07 |
TW200945989A (en) | 2009-11-01 |
JP2009231790A (ja) | 2009-10-08 |
CN101960935A (zh) | 2011-01-26 |
JP5263285B2 (ja) | 2013-08-14 |
JP5574009B2 (ja) | 2014-08-20 |
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