WO2013047726A1 - 絶縁性接着フィルム、プリプレグ、積層体、硬化物、及び複合体 - Google Patents
絶縁性接着フィルム、プリプレグ、積層体、硬化物、及び複合体 Download PDFInfo
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- WO2013047726A1 WO2013047726A1 PCT/JP2012/075033 JP2012075033W WO2013047726A1 WO 2013047726 A1 WO2013047726 A1 WO 2013047726A1 JP 2012075033 W JP2012075033 W JP 2012075033W WO 2013047726 A1 WO2013047726 A1 WO 2013047726A1
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- layer
- olefin polymer
- resin composition
- plated
- alicyclic olefin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- 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
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
- H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to an insulating adhesive film, a prepreg, a laminate, a cured product, and a composite.
- circuit boards are being made multilayered.
- an electrical insulation layer is laminated on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electrical insulation layer. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer.
- the electrical insulating layer and the conductor layer can be laminated in several stages as required.
- a circuit breakage may occur due to a difference in linear expansion between the conductor layer and the electrical insulating layer, particularly when the conductor layer has a high-density pattern.
- the problem of disconnection was significant. Therefore, in the multilayer circuit board, it is required to reduce the linear expansion of the electrical insulating layer.
- it is effective to add an inorganic filler to lower the linear expansion of the electrical insulating layer.
- the addition of the inorganic filler increases the surface roughness of the electrical insulating layer, resulting in electrical insulation.
- the electrical insulating layer has a two-layer configuration of a layer containing an inorganic filler and a layer not containing an inorganic filler. Technology is disclosed.
- the electrical insulating layer is formed of a resin component such as polyimide or polyamide, a layer containing an inorganic filler having a specific surface area of 20 m 2 / g to 600 m 2 / g, and a resin such as thermoplastic polyimide.
- the obtained electrical insulating layer has a large coefficient of linear expansion, resulting in a large difference in linear expansion from the conductor layer. There was a risk of circuit breakage.
- the technique described in Patent Document 2 when a via hole is formed, the problem is that roughness occurs at the periphery of the via hole opening, and the dispersibility of the filler in the electrical insulating layer is poor. There was a problem that became large.
- An object of the present invention is to provide an insulating adhesive film having a low surface roughness, low linear expansion, excellent via-hole formability, and capable of forming an electrically insulating layer having high peel strength, and a prepreg obtained using the same. It is providing a laminated body, hardened
- an insulating adhesive film comprises a plated layer containing 50 to 90% by weight of a polar group-containing alicyclic olefin polymer and a curing agent.
- a two-layer structure comprising an adhesive layer containing 1 to 30% by weight of a polar group-containing alicyclic olefin polymer, a curing agent, and 50 to 90% by weight of an inorganic filler, the insulating adhesive according to the film, it has been found that an electrical insulating layer having a low surface roughness, low linear expansion, excellent via-hole formability and high peel strength can be formed, and the present invention has been completed.
- a plated layer comprising a resin composition for a plated layer containing a polar group-containing alicyclic olefin polymer (A1) and a curing agent (A2), and a polar group-containing alicyclic olefin polymer (B1) ),
- An adhesive layer made of a resin composition for an adhesive layer containing a curing agent (B2) and an inorganic filler (B3), and contained in the plated layer, the polar group-containing alicyclic olefin weight
- the content ratio of the coalescence (A1) is 50 to 90% by weight
- the content ratio of the polar group-containing alicyclic olefin polymer (B1) contained in the adhesive layer is 1 to 30% by weight
- the inorganic An insulating adhesive film wherein the content ratio of the filler (B3) is 50 to 90% by weight
- a to-be-plated layer comprising a resin composition for a to-be-plated layer containing a
- Adhesive film [3]
- the resin composition for a layer to be plated that constitutes the layer to be plated further contains an inorganic filler (A3), and the inorganic filler (A3) with respect to the entire solid content contained in the layer to be plated.
- a prepreg comprising the insulating adhesive film according to any one of [1] to [7] and a fiber base material, [9] Laminated body formed by laminating the insulating adhesive film according to any one of [1] to [7] above or the prepreg according to [8] above on a substrate [10] [1] to [1] 7], the cured product obtained by curing the prepreg according to [8], or the laminate according to [9], [11] A composite formed by forming a conductor layer on the surface of the cured product according to [10] by electroless plating, and [12] The substrate for electronic material comprising the cured product according to [10] or the composite according to [11] as a constituent material, Is provided.
- the insulating adhesive film of the present invention includes a plated layer comprising a resin composition for a plated layer containing a polar group-containing alicyclic olefin polymer (A1) and a curing agent (A2), and a polar group-containing alicyclic ring.
- an adhesive layer made of a resin composition for an adhesive layer containing an olefin polymer (B1), a curing agent (B2), and an inorganic filler (B3), with respect to the entire solid content contained in the plated layer
- the content ratio of the polar group-containing alicyclic olefin polymer (A1) is 50 to 90% by weight, and the polar group-containing alicyclic olefin polymer (to the entire solid content contained in the adhesive layer)
- the content ratio of B1) is 1 to 30% by weight, and the content ratio of the inorganic filler (B3) is 50 to 90% by weight.
- the alicyclic olefin polymer means an olefin (alicyclic olefin) monomer unit having an alicyclic structure, or a monomer unit (hereinafter referred to as the monomer unit) that can be regarded as the monomer unit. For convenience, both are collectively referred to as an alicyclic olefin monomer unit).
- the resin composition for a plated layer used in the present invention contains a polar group-containing alicyclic olefin polymer (A1) and a curing agent (A2).
- the resin composition for to-be-plated layer used by this invention contains a polar group containing alicyclic olefin polymer (A1) as a resin component.
- a polar group containing alicyclic olefin polymer (A1) as a resin component.
- alicyclic structure constituting the polar group-containing alicyclic olefin polymer (A1) hereinafter abbreviated as “alicyclic olefin polymer (A1)” as appropriate
- cycloalkane is used as the present invention. Examples include a structure and a cycloalkene structure, but a cycloalkane structure is preferable from the viewpoint of mechanical strength and heat resistance.
- Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles formed by combining these.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and the carbon atoms constituting the cyclic structure. When the number is in this range, the mechanical strength, heat resistance, and moldability are highly balanced and suitable.
- the alicyclic olefin polymer (A1) is usually thermoplastic.
- the alicyclic structure of the alicyclic olefin polymer (A1) is composed of an olefin monomer unit having an alicyclic structure formed of carbon atoms, that is, an alicyclic olefin monomer unit.
- the alicyclic olefin polymer (A1) may contain other monomer units in addition to the alicyclic olefin monomer units.
- the ratio of the alicyclic olefin monomer unit in the alicyclic olefin polymer (A1) is not particularly limited, but is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight. %. When the ratio of the alicyclic olefin monomer unit is too small, the heat resistance is inferior.
- the monomer unit other than the alicyclic olefin monomer unit is not particularly limited and is appropriately selected depending on the purpose.
- the polar group possessed by the alicyclic olefin polymer (A1) is not particularly limited, but alcoholic hydroxyl group, phenolic hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group. , Ester groups, carboxylic acid anhydride groups, sulfonic acid groups, phosphoric acid groups, etc., among these, carboxyl groups, carboxylic acid anhydride groups, and phenolic hydroxyl groups are preferred, and carboxylic acid anhydride groups are preferred. More preferred.
- the alicyclic olefin polymer (A1) may have two or more polar groups.
- the polar group of the alicyclic olefin polymer (A1) may be directly bonded to an atom constituting the main chain of the polymer, but may be a methylene group, an oxy group, an oxycarbonyloxyalkylene group, a phenylene group, or the like. And may be bonded via a divalent group.
- the content of the monomer unit having a polar group in the alicyclic olefin polymer (A1) is not particularly limited, but in 100 mol% of all monomer units constituting the alicyclic olefin polymer (A1). The amount is usually 4 to 60 mol%, preferably 8 to 50 mol%.
- the alicyclic olefin polymer (A1) used in the present invention can be obtained, for example, by the following method. That is, (1) a method of polymerizing an alicyclic olefin having a polar group by adding another monomer as necessary, (2) an alicyclic olefin having no polar group having a polar group (3) Aromatic olefin having a polar group is polymerized by adding another monomer if necessary, and the aromatic ring portion of the polymer obtained by this is hydrogenated.
- Group of alicyclic olefin polymer having Sex group can be obtained by a method of converting into other polar groups (e.g., carboxyl group) by, for example, hydrolysis.
- a polymer obtained by the method (1) described above is preferable.
- ring-opening polymerization As the polymerization method for obtaining the alicyclic olefin polymer (A1) used in the present invention, ring-opening polymerization or addition polymerization is used. In the case of ring-opening polymerization, it is preferable to hydrogenate the obtained ring-opened polymer. .
- alicyclic olefin having a polar group examples include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 .
- alicyclic olefin having no polar group examples include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1] hept-2. -Ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] ] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8-diene (common name: di- Cyclopentadiene), tetracyclo [6.2.1.1 3,6 .
- dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 3,6 .
- dodec-4-ene 9-vinyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-phenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7] dodeca-4-ene, tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene, cyclopentene, cyclopentadiene and the like. These may be used alone or in combination of two or more.
- aromatic olefin having no polar group examples include styrene, ⁇ -methylstyrene, divinylbenzene and the like. When these specific examples have the said polar group, it is mentioned as an example of the aromatic olefin which has a polar group. These may be used alone or in combination of two or more.
- Examples of the monomer having a polar group other than the alicyclic olefin having a polar group that can be copolymerized with an alicyclic olefin or an aromatic olefin include ethylenically unsaturated compounds having a polar group, Specific examples thereof include unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid; maleic anhydride, butenyl anhydride And unsaturated carboxylic acid anhydrides such as succinic acid, tetrahydrophthalic anhydride and citraconic anhydride. These may be used alone or in combination of two or more.
- Examples of the monomer having no polar group other than the alicyclic olefin that can be copolymerized with the alicyclic olefin or the aromatic olefin include ethylenically unsaturated compounds having no polar group.
- Examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1- Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, Ethylene or ⁇ -olefin having 2 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexa And the like; ene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene nonconjugated dienes such. These may be used
- the molecular weight of the alicyclic olefin polymer (A1) used in the present invention is not particularly limited, but is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrohydrofuran as a solvent. It is preferably in the range of 1,000,000, more preferably in the range of 1,000 to 500,000, and particularly preferably in the range of 3,000 to 300,000. If the weight average molecular weight is too small, the mechanical strength of the cured product obtained by curing the resin composition is lowered, and if it is too large, workability tends to deteriorate when forming into a sheet or film to form a molded body. There is.
- a conventionally known metathesis polymerization catalyst can be used as a polymerization catalyst when the alicyclic olefin polymer (A1) used in the present invention is obtained by a ring-opening polymerization method.
- the metathesis polymerization catalyst include transition metal compounds containing atoms such as Mo, W, Nb, Ta, and Ru. Among them, compounds containing Mo, W, or Ru are preferable because of high polymerization activity.
- Specific examples of particularly preferred metathesis polymerization catalysts include: (1) Molybdenum or tungsten compounds having a halogen group, an imide group, an alkoxy group, an allyloxy group or a carbonyl group as a ligand as a main catalyst, and an organometallic compound. Examples thereof include a catalyst as a second component and (2) a metal carbene complex catalyst having Ru as a central metal.
- Examples of compounds used as the main catalyst in the catalyst of (1) above are halogenated molybdenum compounds such as MoCl 5 and MoBr 5, and halogenated compounds such as WCl 6 , WOCl 4 , tungsten (phenylimide) tetrachloride / diethyl ether, etc. A tungsten compound is mentioned.
- Examples of the organometallic compound used as the second component in the catalyst of (1) above include organometallic compounds of Group 1, Group 2, Group 12, Group 13 or Group 14 of the periodic table.
- organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferred, and organolithium compounds, organoaluminum compounds, and organotin compounds are particularly preferred.
- organolithium compounds, organoaluminum compounds, and organotin compounds are particularly preferred.
- the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophyllithium, and the like.
- organic magnesium examples include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride and the like.
- organic zinc compound examples include dimethyl zinc, diethyl zinc, and diphenyl zinc.
- organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, ethylaluminum diethoxide, and the like.
- An aluminoxane compound obtained by a reaction between an organoaluminum compound and water can also be used.
- the organic tin compound include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
- the amount of these organometallic compounds varies depending on the organometallic compound used, but is preferably 0.1 to 10,000 times, preferably 0.2 to 5,000 times in terms of molar ratio with respect to the central metal of the main catalyst. More preferred is 0.5 to 2,000 times.
- the use ratio of the metathesis polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000 in terms of the molar ratio of (transition metal in the metathesis polymerization catalyst: monomer) to the monomer used for the polymerization. Preferably, it is in the range of 1: 200 to 1: 1,000,000. If the amount of catalyst is too large, it is difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.
- the polymerization reaction is usually performed in an organic solvent.
- the organic solvent to be used is not particularly limited as long as the polymer is dissolved or dispersed under predetermined conditions and does not affect the polymerization, but industrially used solvents are preferable.
- Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane.
- Alicyclic hydrocarbons such as hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogenated aromatic hydrocarbons such as: Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; Diethyl ether, tetrahydrofuran, etc. Et - ether solvents; and the like; anisole, aromatic ether solvents such as phenetole.
- an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an ether solvent, and an aromatic ether solvent that are widely used industrially are preferable.
- the amount of the organic solvent used is preferably such that the concentration of the monomer in the polymerization solution is 1 to 50% by weight, more preferably 2 to 45% by weight. It is particularly preferable that the amount be% by weight. When the concentration of the monomer is less than 1% by weight, the productivity is deteriorated, and when it exceeds 50% by weight, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.
- the polymerization reaction is started by mixing a monomer used for polymerization and a metathesis polymerization catalyst.
- the metathesis polymerization catalyst solution may be added to the monomer solution, or vice versa.
- the metathesis polymerization catalyst to be used is a mixed catalyst composed of a transition metal compound as a main catalyst and an organometallic compound as a second component
- the reaction solution of the mixed catalyst may be added to the monomer solution, The reverse is also possible.
- the transition metal compound solution may be added to the mixed solution of the monomer and the organometallic compound, or vice versa.
- the organometallic compound may be added to the mixed solution of the monomer and the transition metal compound, or vice versa.
- the polymerization temperature is not particularly limited, but is usually ⁇ 30 ° C. to 200 ° C., preferably 0 ° C. to 180 ° C.
- the polymerization time is not particularly limited, but is usually 1 minute to 100 hours.
- Examples of a method for adjusting the molecular weight of the obtained alicyclic olefin polymer (A1) include a method of adding an appropriate amount of a vinyl compound or a diene compound.
- the vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group, but ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene, vinyltoluene and the like Styrenes; ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide Can be mentioned.
- Examples of the diene compound used for adjusting the molecular weight include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1
- Non-conjugated dienes such as 1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- Mention may be made of conjugated dienes such as hexadiene.
- the addition amount of the vinyl compound or diene compound can be arbitrarily selected between 0.1 and 10 mol% based on the monomer used for the polymerization, depending on the target molecular weight.
- the polymerization catalyst for obtaining the alicyclic olefin polymer (A1) used in the present invention by an addition polymerization method for example, a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound is preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually in the range of 1: 100 to 1: 2,000,000 as the molar ratio of the metal compound in the polymerization catalyst to the monomer used for the polymerization.
- hydrogenation of the ring-opening polymer when using a hydrogenated product of the ring-opening polymer is usually performed using a hydrogenation catalyst.
- the hydrogenation catalyst is not particularly limited, and a catalyst generally used for hydrogenation of an olefin compound may be appropriately employed.
- Specific examples of the hydrogenation catalyst include cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium.
- Ziegler catalyst comprising a combination of a transition metal compound and an alkali metal compound; dichlorotris (triphenylphosphine) rhodium, JP-A-7-2929, JP-A-7-149823, JP-A-11-209460,
- dichlorotris triphenylphosphine
- JP-A-7-2929 JP-A-7-149823
- JP-A-11-209460 For example, bis (tricyclohexylphosphine) benzylidine described in JP-A-11-158256, JP-A-11-193323, JP-A-11-209460, etc.
- Noble metal complex catalyst comprising a ruthenium compound such as ruthenium (IV) dichloride; include homogeneous catalysts such as.
- heterogeneous catalysts in which metals such as nickel, palladium, platinum, rhodium, ruthenium are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide, such as nickel / silica, nickel / diatomaceous earth, nickel / Alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, and the like can also be used. Further, the above-described metathesis polymerization catalyst can be used as it is as a hydrogenation catalyst.
- the hydrogenation reaction is usually performed in an organic solvent.
- the organic solvent can be appropriately selected depending on the solubility of the generated hydrogenated product, and the same organic solvent as the organic solvent used in the polymerization reaction described above can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added and reacted as it is without replacing the organic solvent.
- Aromatic ether solvents are preferred, and aromatic ether solvents are more preferred.
- Hydrogenation reaction conditions may be appropriately selected according to the type of hydrogenation catalyst used.
- the reaction temperature is usually ⁇ 20 to 250 ° C., preferably ⁇ 10 to 220 ° C., more preferably 0 to 200 ° C. If it is less than ⁇ 20 ° C., the reaction rate becomes slow. Conversely, if it exceeds 250 ° C., side reactions tend to occur.
- the pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa. When the hydrogen pressure is less than 0.01 MPa, the hydrogen addition rate is slow, and when it exceeds 10.0 MPa, a high pressure reactor is required.
- the time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate.
- the reaction time is usually in the range of 0.1 to 50 hours, 50 mol% or more, preferably 70 mol% or more, more preferably 100 mol% or more of 100 mol% of the carbon-carbon double bond of the main chain in the polymer. 80 mol% or more, particularly preferably 90 mol% or more can be hydrogenated.
- a treatment for removing the catalyst used in the hydrogenation reaction may be performed.
- the method for removing the catalyst is not particularly limited, and examples thereof include centrifugation and filtration.
- the catalyst removal can be promoted by adding a catalyst deactivator such as water or alcohol, or by adding an adsorbent such as activated clay, alumina, or silicon earth.
- the alicyclic olefin polymer (A1) used in the present invention may be used as a polymer solution after polymerization or hydrogenation reaction, or may be used after removing the solvent. It is preferable to use it as a polymer solution since the dissolution and dispersion of the additive are improved during preparation and the process can be simplified.
- the compounding amount of the alicyclic olefin polymer (A1) in the resin composition for a plated layer used in the present invention is that of the alicyclic olefin polymer (A1) with respect to the entire solid content when the plated layer is formed.
- the content ratio is preferably in the range of 50 to 90% by weight, preferably 52 to 80% by weight, more preferably 55 to 70% by weight.
- by setting the content ratio of the alicyclic olefin polymer (A1) in the layer to be plated within the above range it is possible to improve the via hole formability of a cured product obtained by curing the insulating adhesive film. In addition, the peel strength can be improved while keeping the surface roughness low.
- curing agent (A2) used by this invention is not specifically limited, The hardening
- the curing agent (A2) it is preferable to use a compound having two or more functional groups capable of reacting with the polar group of the alicyclic olefin polymer (A1) to form a bond.
- a curing agent suitably used when using an alicyclic olefin polymer (A1) having a carboxyl group, a carboxylic acid anhydride group, or a phenolic hydroxyl group includes examples thereof include a valent epoxy compound, a polyvalent isocyanate compound, a polyvalent amine compound, a polyvalent hydrazide compound, an aziridine compound, a basic metal oxide, and an organic metal halide. These may be used alone or in combination of two or more.
- a polyvalent epoxy compound is preferable from the viewpoint that the reactivity with the polar group of the alicyclic olefin polymer (A1) is moderate and the handling of the resin composition is easy.
- Examples of the polyvalent epoxy compound include a glycidyl ether type such as a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a cresol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a hydrogenated bisphenol A type epoxy compound.
- Epoxy compounds; polycyclic epoxy compounds such as alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, fluorene epoxy compounds, polyfunctional epoxy compounds, isocyanurate type epoxy compounds, phosphorus-containing epoxy compounds;
- numerator is mentioned, These may be used individually by 1 type and may use 2 or more types together.
- the insulating adhesive film of the present invention as well as the prepreg, laminate and cured product obtained using the same can be made to have good mechanical properties
- bisphenol A type epoxy compound Polyphenol type epoxy compounds and epoxy resins having an alicyclic olefin structure or a fluorene structure are preferred.
- an epoxy resin having an alicyclic olefin structure is particularly preferable from the viewpoint of improving the resin fluidity of the resin composition.
- these may be used individually by 1 type and may use 2 or more types together.
- Examples of the bisphenol A type epoxy compound include trade names “jER827, jER828, jER828EL, jER828XA, jER834” (manufactured by Mitsubishi Chemical Corporation), trade names “Epicron 840, Epicron 840-S, Epicron 850, Epicron 850-S”. , Epicron 850-LC ”(manufactured by DIC,“ Epicron ”is a registered trademark), and the like.
- Examples of the polyphenol type epoxy compound include trade names “1032H60, XY-4000” (above, manufactured by Mitsubishi Chemical Corporation).
- an epoxy resin having an alicyclic olefin structure or a fluorene structure an epoxy resin having a dicyclopentadiene skeleton [for example, trade names “Epicron HP7200L, Epicron HP7200, Epicron HP7200H, Epicron HP7200HH, Epicron HP7200HHH” (above, manufactured by DIC Corporation) ); Trade name “Tactix 558” (manufactured by Huntsman Advanced Materials); trade names “XD-1000-1L, XD-1000-2L” (above, Nippon Kayaku Co., Ltd.)] and epoxy resins having a fluorene skeleton [For example, the product names “ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX 1050, ONCOAT EX-1051 ”(above, Nagase Sangyo Co.,
- diisocyanates and triisocyanates having 6 to 24 carbon atoms are preferable.
- diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, etc. Is mentioned.
- triisocyanates include 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, etc., and these may be used alone. You may use 2 or more types together.
- polyvalent amine compound examples include aliphatic polyvalent amine compounds having 4 to 30 carbon atoms having two or more amino groups, aromatic polyvalent amine compounds, and the like, and non-conjugated nitrogen-carbon like guanidine compounds. Those having a double bond are not included.
- examples of the aliphatic polyvalent amine compound include hexamethylene diamine and N, N′-dicinnamylidene-1,6-hexane diamine.
- Aromatic polyvalent amine compounds include 4,4′-methylenedianiline, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4 ′-(m-phenylenediisopropylidene) dianiline, 4,4 ′-( p-phenylenediisopropylidene) dianiline, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 1,3,5-benzenetriamine and the like. These may be used alone or in combination of two or more.
- polyhydric hydrazide compounds include isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide, trimellitic acid dihydrazide, 1,3,5-benzenetricarboxylic acid dihydrazide, Examples include pyromellitic acid dihydrazide. These may be used alone or in combination of two or more.
- aziridine compounds include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-methyl) aziridinyl. ] Triphosphatriazine and the like. These may be used alone or in combination of two or more.
- polyvalent epoxy compounds are preferable from the viewpoint of the low reactivity with the polar group of the alicyclic olefin polymer (A1) and easy handling of the resin composition, and glycidyl ether type.
- Epoxy compounds and alicyclic polyvalent epoxy compounds are particularly preferably used.
- the blending amount of the curing agent (A2) in the resin composition for a plating layer used in the present invention is preferably such that the content ratio of the curing agent (A2) to the entire solid content in the plating layer is 5 to
- the range is preferably 50% by weight, more preferably 10 to 40% by weight, and still more preferably 15 to 30% by weight.
- the resin composition for to-be-plated layers used by this invention further contains the inorganic filler (A3) in addition to an alicyclic olefin polymer (A1) and a hardening
- the inorganic filler (A3) By further containing the inorganic filler (A3), the linear expansion coefficient of the insulating adhesive film can be made lower.
- the inorganic filler (A3) used in the present invention is not particularly limited.
- calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, water Japanese alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, clay and the like can be mentioned.
- those which are not decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate used for the surface roughening treatment of the cured product are preferable, and silica is particularly preferable. This is because if the inorganic filler is decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate, a deep hole may be formed by the etching process.
- the inorganic filler (A3) contained in the resin composition for the layer to be plated a treatment for changing the surface state, such as a surface treatment using a coupling agent, is substantially performed.
- Untreated inorganic fillers that are not treated are preferable, and by using such untreated inorganic fillers, it is possible to easily roughen the surface of the layer to be plated when a cured product is formed. The degree and the peel strength can be highly balanced.
- the inorganic filler (A3) is preferably non-conductive that does not deteriorate the dielectric properties of the resulting electrical insulating layer.
- the shape of the inorganic filler (A3) is not particularly limited, and may be spherical, fibrous, plate-like, etc., but in order to improve dispersibility and resin fluidity of the resin composition, A fine spherical shape is preferred.
- the average particle diameter of the inorganic filler (A3) is preferably 0.1 to 0.5 ⁇ m, more preferably 0.15 to 0.4 ⁇ m.
- the surface roughness of an insulating adhesive film can be made into a more suitable range.
- the average particle diameter can be measured with a particle size distribution measuring device.
- the blending amount of the inorganic filler (A3) in the resin composition for a plated layer used in the present invention is preferably such that the content ratio of the inorganic filler (A3) to the entire solid content in the plated layer is 1 to
- the range is preferably 40% by weight, more preferably 2 to 30% by weight, and still more preferably 3 to 25% by weight.
- the resin composition for to-be-plated layer used by this invention may contain the hardening accelerator as needed.
- the curing accelerator is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, imidazole derivatives, organic acid hydrazides, dicyandiamide and derivatives thereof, and urea derivatives. Among these, imidazole derivatives are particularly preferable.
- the imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, and 1-methyl.
- -2-alkylimidazole compounds such as 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Aryl groups and aralkyl groups such as methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, etc.
- the blending amount in the case of blending the curing accelerator may be appropriately selected depending on the purpose of use, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer (A1). More preferred is 0.1 to 10 parts by weight, and still more preferred is 0.1 to 5 parts by weight.
- the resin composition for a layer to be plated used in the present invention has a general electrical insulating film such as a halogen-based flame retardant or a phosphate ester-based flame retardant for the purpose of improving the flame retardancy of the insulating adhesive film.
- the amount of the flame retardant blended is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, based on 100 parts by weight of the alicyclic olefin polymer (A1).
- the resin composition for the layer to be plated used in the present invention may further include a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), if necessary.
- a flame retardant aid such as leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, natural oils, synthetic oils, waxes, emulsions, magnetic materials, dielectric property modifiers, toughening agents, etc. Also good. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.
- the method for producing the resin composition for a layer to be plated used in the present invention is not particularly limited, and the above components may be mixed as they are, or mixed in a state dissolved or dispersed in an organic solvent.
- a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.
- the resin composition for an adhesive layer used in the present invention contains a polar group-containing alicyclic olefin polymer (B1), a curing agent (B2), and an inorganic filler (B3).
- the resin composition for adhesive layers used in the present invention contains a polar group-containing alicyclic olefin polymer (B1) as a resin component.
- the polar group-containing alicyclic olefin polymer (B1) may be any alicyclic olefin polymer having a polar group. Although it does not specifically limit, For example, the thing similar to the polar group containing alicyclic olefin polymer (A1) used for the resin composition for to-be-plated layers mentioned above can be used.
- the compounding amount of the alicyclic olefin polymer (B1) in the adhesive layer resin composition used in the present invention is such that the content ratio of the alicyclic olefin polymer (B1) in the adhesive layer is 1 to The range is preferably 30% by weight, preferably 1.5 to 20% by weight, more preferably 2 to 10% by weight.
- a cured product obtained by curing the insulating adhesive film is excellent in via hole forming property.
- the coefficient of linear expansion can be kept low, thereby making the cured product excellent in heat resistance.
- the content ratio of the alicyclic olefin polymer (B1) in the adhesive layer is less than 1% by weight, the strength of the insulating adhesive film and a cured product obtained using the insulating adhesive film is extremely reduced.
- the content ratio of the alicyclic olefin polymer (B1) in the adhesive layer exceeds 30% by weight, the via hole formability is lowered and the ratio of the top diameter / bottom diameter of the formed via hole is deteriorated. And a problem that the coefficient of linear expansion is high and the heat resistance is poor.
- the compounding amount of the alicyclic olefin polymer (B1) in the adhesive layer resin composition used in the present invention is alicyclic with respect to the amount obtained by removing the inorganic filler (B3) from the entire solid content in the adhesive layer. It is preferable that the content ratio of the olefin polymer (B1) is 20% by weight or less, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.
- a cured product obtained by curing the insulating adhesive film can be excellent in via-hole formation, In addition, the coefficient of linear expansion can be kept low, whereby the cured product can be made excellent in heat resistance.
- the content of the curing agent (B2) is preferably such that the content of the curing agent (B2) is 3 to 35% by weight with respect to the total solid content in the adhesive layer. More preferably, the content is in the range of 5 to 30% by weight, more preferably 10 to 25% by weight.
- the inorganic filler (B3) used in the present invention is not particularly limited.
- calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, water Japanese alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, clay and the like can be mentioned.
- those which are not decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate used for the surface roughening treatment of the cured product are preferable, and silica is particularly preferable. This is because if the inorganic filler is decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate, a deep hole may be formed by the etching process.
- the inorganic filler (B3) contained in the resin composition for to-be-plated layers the inorganic filler formed by processing the surface with a surface treating agent is preferable, and an insulating adhesive film is hardened.
- cured material, especially the desmear tolerance of a via hole can be improved more.
- the surface treatment agent used for the surface treatment is not particularly limited, and examples thereof include silane coupling agents and organic acids such as stearic acid.
- a silane coupling agent is preferred because it is excellent and the fluidity of the resin composition is good.
- the silane coupling agent which has a functional group which can react with the polar group with which an alicyclic olefin polymer (B1) is provided is preferable.
- a functional group for example, examples thereof include an amino group, a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
- an amino group, a carboxyl group, and an epoxy group are preferable, and an amino group is more preferable.
- the surface treatment amount of the inorganic filler (B3) is preferably 0.1 to 2 weights based on the amount (100% by weight) of the inorganic filler before the surface treatment. %, More preferably 0.5 to 1.5% by weight.
- the inorganic filler (B3) is preferably non-conductive that does not deteriorate the dielectric properties of the obtained electrical insulating layer.
- the shape of the inorganic filler (B3) is not particularly limited, and may be spherical, fibrous, plate-like, etc. In order to improve dispersibility and resin fluidity of the resin composition, A fine spherical shape is preferred.
- the average particle diameter of the inorganic filler (B3) is preferably 0.2 to 3 ⁇ m, more preferably 0.25 to 1 ⁇ m.
- the compounding amount of the inorganic filler (B3) in the resin composition for the adhesive layer used in the present invention is such that the content ratio of the inorganic filler (B3) to the entire solid content when the adhesive layer is formed is 50 to 90% by weight, preferably Is preferably in the range of 55 to 80% by weight, more preferably 60 to 70% by weight.
- a cured product obtained by curing the insulating adhesive film can be excellent in via hole forming property,
- the coefficient of linear expansion can be kept low, whereby the cured product can be made excellent in heat resistance.
- the content ratio of the inorganic filler (B3) in the adhesive layer is less than 50% by weight, the via hole formability is deteriorated, and the ratio of the top diameter / bottom diameter of the formed via hole is deteriorated, or linear expansion. The coefficient will become high and the malfunction that it will become inferior to heat resistance will generate
- the content ratio of the inorganic filler (B3) in the adhesive layer exceeds 90% by weight, the fluidity of the resin composition is lowered, and a problem that the adhesiveness is deteriorated occurs.
- the adhesive layer resin composition used in the present invention may contain, for example, a curing accelerator or a flame retardant, as in the case of the above-described resin composition for a layer to be plated.
- Flame retardant aid heat stabilizer, weather stabilizer, anti-aging agent, UV absorber (laser processability improver), leveling agent, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, You may mix
- the method for producing the resin composition for the adhesive layer used in the present invention is not particularly limited, and the above components may be mixed as they are, or mixed in a state dissolved or dispersed in an organic solvent.
- a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.
- the insulating adhesive film of this invention has a to-be-plated layer which consists of the resin composition for to-be-plated layers mentioned above, and an adhesive layer which consists of the resin composition for above-mentioned adhesive layers.
- the insulating adhesive film of the present invention can be obtained, for example, by the following two methods: (1) The above-described resin composition for a layer to be plated is applied, spread or cast on a support, and dried as necessary, and then And a method for producing the adhesive layer resin composition by further applying or casting the above-described adhesive layer resin composition and drying as necessary; (2) the above-described resin composition for a layer to be plated on a support; Coating, spraying or casting, and applying the above-mentioned resin composition for a bonding layer and the above-mentioned resin composition for an adhesive layer formed into a sheet or film obtained by drying as necessary.
- the production method (1) is preferred because it is an easier process and is excellent in productivity.
- the resin composition for a layer to be plated when the resin composition for a layer to be plated is applied, spread or cast on a support, and for the resin composition for a layer to be plated applied, spread or cast,
- the resin composition for the plating layer and the resin composition for the adhesive layer are formed into a sheet or film to be plated.
- the resin composition for the layer to be plated or the resin composition for the adhesive layer is added to an organic solvent as necessary, applied to the support, spread, or It is preferable to cast.
- a resin film, a metal foil or the like can be used as the support used in this case.
- the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film.
- a polyethylene terephthalate film or a polyethylene naphthalate film is preferable from the viewpoint of heat resistance, chemical resistance, peelability, and the like.
- the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil.
- the average surface roughness Ra of the support is usually 300 nm or less, preferably 150 nm or less, more preferably 100 nm or less.
- the thickness is not particularly limited, but when the insulating adhesive film is formed, the thickness of the layer to be plated is preferably 1 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, still more preferably 2 to 5 ⁇ m, and the thickness of the adhesive layer However, the thickness is preferably 10 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and still more preferably 15 to 60 ⁇ m.
- the formability of the conductor layer may be reduced when the conductor layer is formed by electroless plating on the cured product obtained by curing the insulating adhesive film.
- the thickness of the layer to be plated is too thick, the linear expansion of the cured product obtained by curing the insulating adhesive film may increase.
- the wiring embedding property of the insulating adhesive film may be lowered.
- Examples of the method of applying the resin composition for the plating layer and the resin composition for the adhesive layer include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.
- drying may be performed as necessary. You may go.
- the drying temperature is preferably set to a temperature at which the resin composition for the plated layer and the resin composition for the adhesive layer are not cured, and is usually 20 to 300 ° C., preferably 30 to 200 ° C.
- the drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.
- the plated layer and the adhesive layer constituting the insulating adhesive film are preferably in an uncured or semi-cured state.
- the adhesive layer constituting the insulating adhesive film of the present invention can be made highly adhesive.
- uncured means that the insulating adhesive film of the present invention was immersed in a solvent capable of dissolving the alicyclic olefin polymer (A1) and a solvent capable of dissolving the alicyclic olefin polymer (B1), respectively.
- it means a state in which substantially all of the alicyclic olefin polymer (A1) and the alicyclic olefin polymer (B1) are dissolved.
- the semi-cured is a state where it is cured halfway to the extent that it can be further cured by heating.
- each of them is a solvent capable of dissolving the alicyclic olefin polymer (A1), and alicyclic olefin heavy.
- a solvent capable of dissolving the polymer (B1) a part of the alicyclic olefin polymer (A1) and a part of the alicyclic olefin polymer (B1) (specifically, an amount of 7% by weight or more, and one
- the volume after the immersion of the molded body in a solvent for 24 hours is 200% or more of the volume before the immersion (swelling ratio). .
- the prepreg of the present invention is composed of the above-described insulating adhesive film of the present invention and a fiber base material, and one surface of the prepreg is an adhesive layer composed of the above-described adhesive resin composition, and the other surface is the above-described plated object. It is an insulating composite which consists of a to-be-plated layer which consists of a resin composition for layers.
- the fiber base material examples include organic fibers such as polyamide fibers, polyaramid fibers and polyester fibers, and inorganic fibers such as glass fibers and carbon fibers.
- organic fibers such as polyamide fibers, polyaramid fibers and polyester fibers
- inorganic fibers such as glass fibers and carbon fibers.
- the form of woven fabrics such as a plain weave or a twill weave, the form of a nonwoven fabric, etc. are mentioned.
- the thickness of the fiber substrate is preferably 5 to 100 ⁇ m, and more preferably 10 to 50 ⁇ m. If it is too thin, handling becomes difficult, and if it is too thick, the resin layer becomes relatively thin and the wiring embedding property may be insufficient.
- the production method of the prepreg of the present invention is not limited as long as it has an adhesive layer on one surface, a layer to be plated on the other surface, and a fiber base material inside.
- the following method (1) The resin composition film for the adhesive layer with the support and the resin composition film for the layer to be plated with the support are aligned with the resin layer side of each film so that the fiber substrate is sandwiched therebetween, and if necessary, pressurization, vacuum, (2) By impregnating the fiber base material with either the resin composition for the adhesive layer or the resin composition for the layer to be plated, and drying if necessary
- a method of producing a prepreg by coating, spreading or casting another resin composition on the prepreg, or by laminating another resin composition film with a support; (3) Support Adhesive layer on top Either a resin composition or a resin composition for a layer to be plated is laminated by coating, spreading, or casting, and a fiber base material is stacked thereon, and another resin composition is further coated, spread, or spread there
- It can be manufactured by laminating by casting and drying if necessary.
- an organic solvent is added to the composition as necessary, and the viscosity of the composition is adjusted, so that the fiber base material is impregnated, applied to the support, applied or spread. It is preferable to control the property.
- the thickness of the prepreg of the present invention is not particularly limited, but the thickness of the layer to be plated is preferably 1 to 10 ⁇ m, more preferably 1.5 to 8 ⁇ m, still more preferably 2 to 5 ⁇ m, and the thickness of the adhesive layer is The thickness is preferably 10 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and even more preferably 15 to 60 ⁇ m.
- Examples of the method for applying the resin composition for a plating layer and the resin composition for an adhesive layer when producing the prepreg of the present invention include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating. It is done.
- the resin composition constituting the layer to be plated and the adhesive layer is in an uncured or semi-cured state, like the above-described insulating adhesive film of the present invention.
- the laminate of the present invention is formed by laminating the above-described insulating adhesive film or prepreg of the present invention on a base material.
- the laminate of the present invention may be at least the one formed by laminating the above-described insulating adhesive film or prepreg of the present invention, but the substrate having a conductor layer on the surface and the above-described insulating adhesive of the present invention.
- cured material of a film or a prepreg is preferable.
- the insulating adhesive film or prepreg of the present invention is laminated with the substrate via an adhesive layer. That is, in the laminated body of the present invention, the surface of the electrical insulating layer is formed by the layer to be plated among the layer to be plated and the adhesive layer of the insulating adhesive film or prepreg of the present invention.
- a substrate having a conductor layer on its surface is one having a conductor layer on the surface of an electrically insulating substrate.
- the electrically insulating substrate contains a known electrically insulating material (for example, alicyclic olefin polymer, epoxy resin, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, polyphenyl ether, glass, etc.).
- the resin composition is formed by curing.
- a conductor layer is not specifically limited, Usually, it is a layer containing the wiring formed with conductors, such as an electroconductive metal, Comprising: Various circuits may be included further. The configuration and thickness of the wiring and circuit are not particularly limited.
- the substrate having a conductor layer on the surface include a printed wiring board and a silicon wafer substrate.
- the thickness of the substrate having a conductor layer on the surface is usually 10 ⁇ m to 10 mm, preferably 20 ⁇ m to 5 mm, more preferably 30 ⁇ m to 2 mm.
- the substrate having a conductor layer on the surface used in the present invention is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer.
- a pretreatment method a known technique can be used without any particular limitation.
- the conductor layer is made of copper
- an oxidation treatment method in which a strong alkali oxidizing solution is brought into contact with the surface of the conductor layer to form a copper oxide layer on the conductor surface and roughened, After oxidation with this method, reduce with sodium borohydride, formalin, etc., deposit and roughen the plating on the conductor layer, contact the organic acid with the conductor layer to elute the copper grain boundaries and roughen
- a method of forming a primer layer with a thiol compound or a silane compound on the conductor layer is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer.
- the laminate of the present invention can usually be produced by heat-pressing the above-mentioned insulating adhesive film or prepreg of the present invention on a substrate having a conductor layer on the surface.
- thermocompression bonding an insulating adhesive film or prepreg with a support is superposed so that the adhesive layer constituting the insulating adhesive film or prepreg is in contact with the conductor layer of the substrate, a pressure laminator, a press , Vacuum laminator, vacuum press, roll laminator and the like, and a method of thermocompression bonding (lamination).
- bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the insulating adhesive film.
- the temperature for the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C.
- the applied pressure is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa
- the time is usually 30 seconds to 5
- the time is preferably 1 minute to 3 hours.
- the thermocompression bonding is preferably performed under reduced pressure in order to improve the embedding property of the wiring pattern and suppress the generation of bubbles.
- the pressure under reduced pressure for thermocompression bonding is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.
- the insulating adhesive film or prepreg of the present invention can be laminated on the substrate in an uncured state, a semi-cured state, or a cured state by appropriately adjusting temperature conditions and the like. .
- cured material of this invention is obtained by performing the process which hardens
- the curing process may be performed in a stepwise manner. For example, first, the thermocompression operation may be performed under conditions that do not cause curing, that is, at a relatively low temperature and in a short time, and then cured.
- the composite of the present invention is obtained by further forming a conductor layer by electroless plating on the surface of the cured product of the present invention, specifically, the plated layer of the cured product.
- the method for producing a composite according to the present invention will be described using a multilayer circuit board as an example of the composite according to the present invention.
- the cured product of the insulating adhesive film (or prepreg) of the present invention forms an electrical insulating layer.
- via holes and through holes that penetrate the electrical insulating layer are formed in the laminate.
- the via hole is formed to connect the respective conductor layers constituting the multilayer circuit board when the multilayer circuit board is used.
- the via hole or the through hole can be formed by chemical processing such as photolithography or physical processing such as drilling, laser, or plasma etching.
- a laser method carbon dioxide laser, excimer laser, UV-YAG laser, etc. is preferable because a finer via hole can be formed without degrading the characteristics of the electrical insulating layer.
- the surface average roughness Ra of the electrical insulating layer is preferably 0.05 ⁇ m or more and less than 0.5 ⁇ m, more preferably 0.06 ⁇ m or more and 0.3 ⁇ m or less, and the surface 10-point average roughness Rzjis is preferably 0.00. 3 ⁇ m or more and less than 4 ⁇ m, more preferably 0.5 ⁇ m or more and 2 ⁇ m or less.
- Ra is the arithmetic average roughness shown in JIS B0601-2001
- the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.
- the surface roughening treatment method is not particularly limited, and examples thereof include a method in which the surface of the electrical insulating layer (that is, the surface of the layer to be plated of the cured adhesive adhesive film) and an oxidizing compound are brought into contact.
- the oxidizing compound include known compounds having oxidizing ability, such as inorganic oxidizing compounds and organic oxidizing compounds. In view of easy control of the average surface roughness of the electrical insulating layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound.
- inorganic oxidizing compounds include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, and the like.
- organic oxidizing compound examples include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, and ozone.
- the method of roughening the surface of the electrical insulating layer using an inorganic oxidizing compound or an organic oxidizing compound there is a method in which an oxidizing compound solution prepared by dissolving the oxidizing compound in a soluble solvent is brought into contact with the surface of the electrical insulating layer.
- the method for bringing the oxidizing compound solution into contact with the surface of the electrical insulating layer is not particularly limited.
- the dipping method in which the electrical insulating layer is immersed in the oxidizing compound solution, the surface tension of the oxidizing compound solution is used.
- Any method may be used, such as a liquid filling method in which the oxidizing compound solution is placed on the electric insulating layer, or a spray method in which the oxidizing compound solution is sprayed on the electric insulating layer.
- a liquid filling method in which the oxidizing compound solution is placed on the electric insulating layer
- a spray method in which the oxidizing compound solution is sprayed on the electric insulating layer.
- the temperature and time for bringing these oxidizing compound solutions into contact with the surface of the electrical insulating layer may be arbitrarily set in consideration of the concentration and type of the oxidizing compound, the contact method, and the like.
- the temperature is 150 ° C., preferably 20 to 100 ° C., and the time is usually 0.5 to 60 minutes, preferably 1 to 40 minutes.
- the surface of the electrical insulating layer after the surface roughening treatment is washed with water.
- the substance can be further washed with a dissolvable cleaning solution or brought into contact with other compounds to make it soluble in water. Wash with water.
- a dissolvable cleaning solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution
- a mixed solution of hydroxyamine sulfate and sulfuric acid is used to remove the generated manganese dioxide film. It can wash
- a conductor layer is formed.
- the conductive layer is formed by electroless plating from the viewpoint that a conductive layer having excellent adhesion can be formed.
- the electrical insulation layer ie, the plated layer of the cured product of the insulating adhesive film
- catalyst nuclei such as silver, palladium, zinc, cobalt
- the method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited.
- a metal compound such as silver, palladium, zinc, or cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform to 0.001.
- Examples include a method of reducing a metal after dipping in a solution dissolved at a concentration of ⁇ 10% by weight (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary).
- electroless plating solution used in the electroless plating method a known autocatalytic electroless plating solution may be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration is not particularly limited.
- electroless nickel-phosphorous plating solution using sodium hypophosphite as reducing agent Electroless nickel-boron plating solution using dimethylamine borane as reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as reducing agent; electroless gold plating solution; electroless silver Plating solution: An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used.
- the surface of the substrate can be brought into contact with a rust preventive agent to carry out a rust prevention treatment.
- a metal thin film can also be heated in order to improve adhesiveness.
- the heating temperature is usually 50 to 350 ° C., preferably 80 to 250 ° C. In this case, heating may be performed under a pressurized condition.
- a pressurizing method at this time for example, a method using a physical pressurizing means such as a hot press machine or a pressurizing and heating roll machine can be cited.
- the applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.
- a resist pattern for plating is formed on the metal thin film thus formed, and further, plating is grown thereon by wet plating such as electrolytic plating (thick plating), then the resist is removed, and further etched.
- the metal thin film is etched into a pattern to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal thin film and plating grown thereon.
- the multilayer circuit board obtained as described above is used as a board for manufacturing the above-described laminate.
- the insulating adhesive film (or prepreg) of the present invention is heat-pressed and cured to be electrically insulated.
- a layer is formed, and a conductive layer is formed thereon according to the above-described method.
- further multilayering can be performed, whereby a desired multilayer circuit board can be obtained. .
- the composite of the present invention thus obtained (and the multilayer circuit board as an example of the composite of the present invention) has an electrical insulating layer comprising the insulating adhesive film (or prepreg) of the present invention, Since the electrical insulating layer has a low surface roughness, low linear expansion, excellent via-hole formation, and high peel strength, a conductive layer is formed on the electrical insulating layer, and the formed conductive layer is When patterning is performed and fine wiring is formed, the conductor layer can be satisfactorily patterned.
- the composite of the present invention (and the multilayer circuit board as an example of the composite of the present invention) is excellent in via hole formation, it can form good via holes and has low surface roughness. Regardless, since it has a high peel strength, a high-density wiring can be formed by this, and furthermore, the coefficient of linear expansion is small, so that it has excellent heat resistance.
- substrate for electronic materials of this invention contains the hardened
- a substrate for electronic materials of the present invention includes a mobile phone, PHS, notebook computer, PDA (personal digital assistant), mobile video phone, personal computer, supercomputer, server, router, liquid crystal projector, engineering workstation (EWS). , Pagers, word processors, televisions, viewfinder type or monitor direct view type video tape recorders, electronic notebooks, electronic desk calculators, car navigation devices, POS terminals, devices equipped with touch panels, etc. .
- desmear treatment swelling treatment, oxidation treatment, neutralization reduction treatment
- desmear treatment is performed on the laminate having via holes, and the via holes of the laminate subjected to desmear treatment are observed with an electron microscope, and evaluation of the hole state after desmear treatment is performed. Went.
- the hole state after drilling and the hole state after desmear treatment were evaluated according to the following criteria. The results are shown in Table 1.
- ⁇ Ratio of bottom diameter / top diameter is 70% or more.
- X Ratio of bottom diameter / top diameter is less than 70%.
- the state of via holes after desmear treatment was evaluated according to the following criteria. The results are shown in Table 1.
- ⁇ Ratio of top diameter after desmear / top diameter before desmear is less than 105%.
- X Ratio of top diameter after desmear / top diameter before desmear is 105% or more. The evaluation was based on the following criteria. The results are shown in Table 1. ⁇ : No abnormality ⁇ : Abnormalities such as cracks, resin scattering, and roughness
- peel strength Adhesion between the insulating layer and the metal layer (peel strength)
- the peel strength between the insulating layer and the copper plating layer in the multilayer printed wiring board was measured according to JIS C6481-1996.
- ⁇ Peel strength is 5 N / cm or more
- ⁇ Peel strength is less than 5 N / cm
- Synthesis example 1 As the first stage of polymerization, 35 mol parts of 5-ethylidene-bicyclo [2.2.1] hept-2-ene (EdNB), 0.9 mol parts of 1-hexene, 340 mol parts of anisole and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) 0.005 mol part of nitrogen-substituted pressure glass reactor And a polymerization reaction was carried out at 80 ° C.
- the resulting polymer (P-1) had a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution of 2.
- the hydrogenation rate was 95%, and the content of monomer units having a carboxylic anhydride group was 30 mol%.
- the solid content concentration of the polymer (P-1) solution was 22%.
- Synthesis example 2 Tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene (MTF) 70 mol part, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride (NDCA) 30 mol Part, 1-hexene 0.9 mol part, anisole 590 mol part and C1063 0.015 mol part were charged into a nitrogen-substituted pressure-resistant glass reactor, and the polymerization reaction was carried out at 80 ° C. for 1 hour with stirring to produce a norbornene series. A solution of the ring-opening polymer was obtained.
- the solution of the obtained ring-opening polymer was charged into an autoclave equipped with a stirrer substituted with nitrogen and stirred for 5 hours at 150 ° C. and a hydrogen pressure of 7 MPa to carry out a hydrogenation reaction, whereby hydrogen of the norbornene-based ring-opening polymer was obtained.
- a solution of the alicyclic olefin polymer (P-2) as an additive was obtained.
- the obtained polymer (P-2) had a weight average molecular weight of 50,000, a number average molecular weight of 26,000, and a molecular weight distribution of 1.9.
- the hydrogenation rate was 97%, and the content of monomer units having a carboxylic anhydride group was 30 mol%.
- the solid content concentration of the polymer (P-2) solution was 22%.
- the obtained ring-opened polymer solution was charged into an autoclave equipped with a stirrer purged with nitrogen, and a hydrogenation reaction was performed by stirring at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours.
- the obtained hydrogenation reaction solution was concentrated to obtain a solution of an alicyclic olefin polymer (P-3).
- the resulting alicyclic olefin polymer (P-3) had a weight average molecular weight of 10,000, a number average molecular weight of 5,000, and a molecular weight distribution of 2.
- the hydrogenation rate was 97%, and the content of monomer units having a carboxylic anhydride group was 30 mol%.
- the solid content concentration of the alicyclic olefin polymer (P-3) solution was 55%.
- Example 1 (Resin composition for plated layer) 45 parts of the solution of the alicyclic olefin polymer (P-1) obtained in Synthesis Example 1 and untreated spherical silica as an inorganic filler (A3) (Admafine (registered trademark) SO-C1, manufactured by Admatechs) , Volume average particle size 0.25 ⁇ m) 98% and alicyclic olefin polymer (P-2) 2% obtained in Synthesis Example 2 were mixed with anisole so that the solid content would be 75%, and then mixed with a high-pressure homogenizer. 6 parts of the dispersed silica slurry was mixed and stirred with a planetary stirrer for 3 minutes.
- the varnish of the resin composition for an adhesive layer obtained as described above is applied to the formation surface of the layer to be plated of the resin composition for a layer to be plated of a film with a support, and a doctor blade (manufactured by Tester Sangyo Co., Ltd.) Application using an auto film applicator (manufactured by Tester Sangyo Co., Ltd.), followed by drying at 80 ° C. for 10 minutes in a nitrogen atmosphere, and adhesion with a support on which a layer to be plated and an adhesive layer having a total thickness of 40 ⁇ m are formed A film was obtained.
- the said adhesive film with a support body was formed in order of the support body, the to-be-plated layer which consists of a resin composition for to-be-plated layers, and the adhesive layer which consists of the resin composition for adhesive layers.
- Table 1 shows the content ratios of main components constituting the plated layer and the adhesive layer of the obtained adhesive film.
- the primary press Went After bonding the adhesive film with the support obtained above to 150 mm square on both surfaces of this inner layer substrate so that the surface on the resin composition side for the adhesive layer is inside, the primary press Went.
- the primary press is thermocompression bonding at a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom. Furthermore, using a hydraulic press device provided with metal press plates at the top and bottom, thermocompression bonding was performed at a pressure bonding temperature of 110 ° C. and 1 MPa for 90 seconds.
- the support body was peeled off to obtain a laminate of the resin layer and the inner layer substrate made of the plated layer resin composition and the adhesive layer resin composition. Further, the laminate was left in an air atmosphere at 180 ° C. for 60 minutes to cure the resin layer and form an electrical insulating layer on the inner layer substrate. And the via-hole formation property was evaluated according to the said method using the obtained laminated body. The results are shown in Table 1.
- the obtained laminate was prepared to have a swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech, “Securigant” is a registered trademark) of 500 mL / L, sodium hydroxide 3 g / L. After dipping in the aqueous solution for 15 minutes, it was washed with water.
- a swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech, “Securigant” is a registered trademark) of 500 mL / L, sodium hydroxide 3 g / L.
- an aqueous solution of hydroxyamine sulfate (“Reduction Securigant P 500”, manufactured by Atotech Co., Ltd., “Securigant” is a registered trademark) is 100 mL / L, and an aqueous solution at 40 ° C. prepared to have 35 mL / L of sulfuric acid is added to the laminate. Was immersed for 5 minutes, neutralized and reduced, and then washed with water.
- the laminate was dipped in an aqueous solution prepared so as to have a sulfuric acid concentration of 100 g / L for 1 minute to perform pickling treatment, and then washed with water.
- Alcup Activator MAT-1-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 200 mL / L
- Alcup Activator MAT-1-B (top product name, manufactured by Mura Kogyo Co., Ltd., “Alcup”) was immersed in a 60 ° C.
- Pd salt-containing plating catalyst aqueous solution prepared so that the registered trademark was 30 mL / L and sodium hydroxide was 0.35 g / L, and then washed with water.
- Alcup Redeusa MAB-4-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 20 mL / L
- Alcup Redeusa MAB-4-B (trade name, manufactured by Uemura Kogyo Co., Ltd., “ Alcup "is a registered trademark) in an aqueous solution adjusted to 200 mL / L.
- the laminate was immersed at 35 ° C. for 3 minutes to reduce the plating catalyst, and then washed with water.
- sulcup PEA-6-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Sulcup” is a registered trademark) 100 mL / L
- sulcup PEA-6-B-2X (trade name, Uemura Industrial Co., Ltd.) 50 mL / L
- Sulcup PEA-6-C (trade name, manufactured by Uemura Kogyo Co., Ltd.) 14 mL / L
- Sulcup PEA-6-D (trade name, manufactured by Uemura Industrial Co., Ltd.) 15 mL / L
- Sulcup PEA-6 -E (trade name, manufactured by Uemura Kogyo Co., Ltd.) 50 mL / L, 37% Formalin aqueous solution 5 mL / L prepared by immersion in electroless copper plating solution at a temperature of 36 ° C.
- Electroless copper plating treatment was performed to form an electroless plating film on the surface of the laminate (the surface of the layer to be plated made of the resin composition for the layer to be plated).
- annealing was performed at 150 ° C. for 30 minutes in an air atmosphere.
- the laminate subjected to the annealing treatment was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 30 ⁇ m.
- the laminate was heat-treated at 180 ° C. for 60 minutes to obtain a double-sided, two-layer multilayer printed wiring board A in which a circuit was formed on the laminate with a conductor layer composed of the metal thin film layer and the electrolytic copper plating film. .
- the peel strength of the obtained circuit board was measured according to the said method. The results are shown in Table 1.
- a dry film of a commercially available photosensitive resist is attached to the laminated body subjected to the annealing treatment by thermocompression bonding, and then a mask for an evaluation pattern is brought into close contact with the dry film, exposed, and then developed.
- a resist pattern was obtained.
- it was immersed in an aqueous solution of 50 mL / L sulfuric acid for 1 minute at 25 ° C. to remove the rust inhibitor, and electrolytic copper plating was applied to the resist non-formed portion to form an electrolytic copper plating film having a thickness of 18 ⁇ m.
- the resist pattern on the laminate was removed using a stripping solution, and an etching process was performed with a mixed solution of ferric chloride and hydrochloric acid.
- the laminated body is heat-treated at 180 ° C. for 60 minutes, whereby a multilayer printed wiring board B having a wiring pattern having two layers on both sides, in which a circuit is formed on the laminated body with a conductor layer composed of the metal thin film layer and the electrolytic copper plating film.
- a multilayer printed wiring board B having a wiring pattern having two layers on both sides in which a circuit is formed on the laminated body with a conductor layer composed of the metal thin film layer and the electrolytic copper plating film.
- the surface average roughness Ra of the electrical insulating layer in the portion where the conductor circuit was not formed was measured according to the above method. The results are shown in Table 1.
- Example 2 When obtaining the resin composition for the layer to be plated, 45.2 parts of the solution of the alicyclic olefin polymer (P-1) obtained in Synthesis Example 1 and untreated spherical silica as the inorganic filler (A3) ( Admafine SO-C1, manufactured by Admatechs Corporation, volume average particle size 0.25 ⁇ m) 98% and alicyclic olefin polymer (P-2) 2% obtained in Synthesis Example 2 to a solid content of 75%
- A3 Admafine SO-C1, manufactured by Admatechs Corporation, volume average particle size 0.25 ⁇ m
- P-2 alicyclic olefin polymer
- a varnish was obtained, and an adhesive film, a laminate, and multilayer printed wiring boards A and B were obtained in the same manner as in Example 1 except that the varnish of the obtained resin composition for a layer to be plated was used. Evaluation was performed. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- Example 3 When obtaining the resin composition for the layer to be plated, 45.4 parts of the solution of the alicyclic olefin polymer (P-1) obtained in Synthesis Example 1 and untreated spherical silica as the inorganic filler (A3) ( Admafine SO-C1, manufactured by Admatechs, volume average particle size 0.25 ⁇ m) 98% and alicyclic olefin polymer (P-2) 2% obtained in Synthesis Example 2 to a solid content of 78% In the same manner as in Example 1, except that the silica slurry mixed with anisole, treated with a high-pressure homogenizer for 15 minutes and dispersed was changed to 0.9 part and the anisole was changed to 53.3 parts.
- A3 Admafine SO-C1, manufactured by Admatechs, volume average particle size 0.25 ⁇ m
- Example 1 In the same manner as in Example 1 except that the product varnish was obtained and the varnish of the obtained resin composition for a plated layer was used, an adhesive film, a laminate, and multilayer printed wiring boards A and B were obtained. Evaluation was performed in the same manner. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- Example 4 In obtaining the adhesive resin composition, 9.1 parts of the alicyclic olefin polymer (P-2) solution was added to 2.1 parts, and surface spherical silica as an inorganic filler (B3) (Admafine SC- 2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0.5 ⁇ m), and alicyclic olefin polymer (P-3) obtained in Synthesis Example 3 and anisole.
- B3 Admafine SC- 2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0.5 ⁇ m
- silica slurry 63 parts of surface spherical silica (Admafine SC-2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0.5 ⁇ m) is added to dicyclopentadiene type novolac resin. (GDP-6140, Gunei Chemical Industry Co., Ltd.) Same as Example 1 except that 15 parts were changed to 16 parts and anisole was changed to 28 parts Thus, an adhesive film, a laminate, and multilayer printed wiring boards A and B were obtained in the same manner as in Example 1 except that the adhesive resin composition varnish was obtained and the obtained adhesive resin composition was used. The same evaluation was performed. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- Example 5 In obtaining an adhesive resin composition, 9.1 parts of the alicyclic olefin polymer (P-2) solution was added to 24.6 parts, and surface spherical silica as an inorganic filler (B3) (Admafine SC- 2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0.5 ⁇ m), and alicyclic olefin polymer (P-3) obtained in Synthesis Example 3 and anisole.
- B3 surface spherical silica as an inorganic filler
- the adhesive film, the laminate, and the multilayer printed wiring boards A and B were obtained in the same manner as in Example 1 except that the resin composition for varnish was obtained and the obtained adhesive resin composition was used. To evaluate Was Tsu. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- Comparative Example 1 When obtaining the resin composition for the adhesive layer, instead of the solution of the alicyclic olefin polymer (P-2) obtained in Synthesis Example 2, the alicyclic olefin polymer (P -3), 1.4 parts of surface treated spherical silica as an inorganic filler (B3) (Admafine SC-2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0 0.5 ⁇ m) 98.5% and 1.5% of the alicyclic olefin polymer (P-3) obtained in Synthesis Example 3 were mixed with anisole so that the solid content was 78%, and then treated with a high-pressure homogenizer.
- B3 surface treated spherical silica as an inorganic filler
- Example 1 In the same manner as in Example 1 except that the product varnish was obtained and the varnish of the obtained resin composition for a plated layer was used, an adhesive film, a laminate, and multilayer printed wiring boards A and B were obtained. Evaluation was performed in the same manner. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- Comparative Example 3 In obtaining the resin composition for the adhesive layer, 40.9 parts of the solution of the alicyclic olefin polymer (P-2) obtained in Synthesis Example 2 and the alicyclic olefin polymer obtained in Synthesis Example 3 ( 1.4 parts of a solution of P-3), surface-treated spherical silica as an inorganic filler (B3) (Admafine SC-2500-SXJ, manufactured by Admatechs, treated with aminosilane type silane coupling agent, volume average particle size 0 0.5 ⁇ m) 98.5% and 1.5% of the alicyclic olefin polymer (P-3) obtained in Synthesis Example 3 were mixed with anisole so that the solid content was 78%, and the mixture was mixed with a high-pressure homogenizer.
- B3 surface-treated spherical silica as an inorganic filler
- the mixture was mixed with 20.8 parts of the silica slurry that had been treated for 5 minutes and dispersed, and stirred with a planetary stirrer for 3 minutes.
- bisphenol A type epoxy resin [Epicoat (registered trademark) 828EL, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194] 0.8 parts as a curing agent (B2), polyfunctional epoxy resin (1032H60, manufactured by Mitsubishi Chemical Corporation), 2 parts of epoxy equivalents 163 to 175) and 0.1 part of tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate as an antioxidant were mixed and stirred for 3 minutes with a planetary stirrer.
- Example 1 0.3 part of a solution in which 50% 1-benzyl-2-phenylimidazole was dissolved in anisole as a curing accelerator was mixed, and the mixture was stirred for 5 minutes with a planetary stirrer to give a varnish of a resin composition for an adhesive layer.
- the varnish of the resin composition for the adhesive layer was obtained in the same manner as Example 1, except that the varnish of the obtained resin composition for the adhesive layer was used.
- An adhesive film, a laminate, and multilayer printed wiring boards A and B were obtained and evaluated in the same manner. Table 1 shows these evaluation results and the content ratios of the main components constituting the plated layer and the adhesive layer of the adhesive film.
- the content ratio of each component is a ratio to the entire solid content constituting the layer to be plated or the entire solid content constituting the adhesive layer.
- a layer comprising a resin composition for a plating layer containing 50 to 90% by weight of a polar group-containing alicyclic olefin polymer and a curing agent is included as a plating layer
- 1 Use of an insulating adhesive film having, as an adhesive layer, a layer comprising a resin composition for an adhesive layer containing -30% by weight of a polar group-containing alicyclic olefin polymer, a curing agent, and 50 to 90% by weight of an inorganic filler As a result, it was possible to form an electrical insulating layer having a low coefficient of linear expansion, a low surface roughness, and excellent via hole formation and peel strength (Examples 1 to 3).
Abstract
Description
また、特許文献2に記載の技術では、ビアホールを形成した際に、ビアホール開口周縁に粗れが発生してしまうという問題や、電気絶縁層中におけるフィラーの分散性が悪く、そのため、表面粗度が大きくなってしまうという問題などがあった。
本発明の目的は、表面粗度が低く、低線膨張であり、ビアホール形成性に優れ、高いピール強度を有する電気絶縁層を形成可能な絶縁性接着フィルム、ならびに、これを用いて得られるプリプレグ、積層体、硬化物、及び複合体を提供することにある。
〔1〕極性基含有脂環式オレフィン重合体(A1)、及び硬化剤(A2)を含有する被めっき層用樹脂組成物からなる被めっき層と、極性基含有脂環式オレフィン重合体(B1)、硬化剤(B2)及び無機フィラー(B3)を含有する接着層用樹脂組成物からなる接着層とを有し、前記被めっき層中に含有される、前記極性基含有脂環式オレフィン重合体(A1)の含有比率が50~90重量%であり、前記接着層中に含有される、前記極性基含有脂環式オレフィン重合体(B1)の含有比率が1~30重量%、前記無機フィラー(B3)の含有比率が50~90重量%であることを特徴とする絶縁性接着フィルム、
〔2〕極性基含有脂環式オレフィン重合体(A1)、及び硬化剤(A2)を含有する被めっき層用樹脂組成物からなる被めっき層と、極性基含有脂環式オレフィン重合体(B1)、硬化剤(B2)及び無機フィラー(B3)を含有する接着層用樹脂組成物からなる接着層とを有し、前記被めっき層中に含有される固形分全体に対する、前記極性基含有脂環式オレフィン重合体(A1)の含有比率が50~90重量%であり、前記接着層中に含有される固形分全体から無機フィラー(B3)を除いた量に対する、前記極性基含有脂環式オレフィン重合体(B1)の含有比率が20重量%以下、前記接着層中に含有される固形分全体に対する前記無機フィラー(B3)の含有比率が50~90重量%であることを特徴とする絶縁性接着フィルム、
〔3〕前記被めっき層を構成する被めっき層用樹脂組成物が、無機フィラー(A3)をさらに含有し、前記被めっき層中に含有される固形分全体に対する、前記無機フィラー(A3)の含有比率が1~40重量%であることを特徴とする前記〔1〕または〔2〕に記載の絶縁性接着フィルム、
〔4〕前記無機フィラー(B3)が、平均粒径0.2~3μmの球状シリカであることを特徴とする前記〔1〕~〔3〕のいずれかに記載の絶縁性接着フィルム、
〔5〕前記無機フィラー(B3)が、表面処理された表面処理球状シリカであることを特徴とする前記〔1〕~〔4〕のいずれかに記載の絶縁性接着フィルム、
〔6〕前記無機フィラー(A3)が、平均粒径0.1~0.5μmの球状シリカであることを特徴とする前記〔3〕~〔5〕のいずれかに記載の絶縁性接着フィルム、
〔7〕前記無機フィラー(A3)が、表面処理をしていない未処理球状シリカであることを特徴とする前記〔3〕~〔6〕のいずれかに記載の絶縁性接着フィルム、
〔8〕前記〔1〕~〔7〕のいずれかに記載の絶縁性接着フィルムと繊維基材からなるプリプレグ、
〔9〕前記〔1〕~〔7〕のいずれかに記載の絶縁性接着フィルム、又は前記〔8〕に記載のプリプレグを基材に積層してなる積層体
〔10〕前記〔1〕~〔7〕のいずれかに記載の絶縁性接着フィルム、前記〔8〕に記載のプリプレグ、又は前記〔9〕に記載の積層体を硬化してなる硬化物、
〔11〕前記〔10〕に記載の硬化物の表面に、無電解めっきにより、導体層を形成してなる複合体、ならびに、
〔12〕前記〔10〕に記載の硬化物、又は前記〔11〕に記載の複合体を構成材料として含む電子材料用基板、
が提供される。
なお、本明細書において脂環式オレフィン重合体とは、脂環式構造を有するオレフィン(脂環式オレフィン)単量体単位、又は当該単量体単位と同視しうる単量体単位(以下、便宜的に、両者をまとめて脂環式オレフィン単量体単位という。)を含んでなる重合体をいう。
まず、被めっき層を形成するための被めっき層用樹脂組成物について説明する。本発明で用いる被めっき層用樹脂組成物は、極性基含有脂環式オレフィン重合体(A1)、及び硬化剤(A2)を含有する。
本発明で用いる被めっき層用樹脂組成物は、樹脂成分として、極性基含有脂環式オレフィン重合体(A1)を含有する。本発明で用いる、極性基含有脂環式オレフィン重合体(A1)(以下、適宜、「脂環式オレフィン重合体(A1)」と略記する。)を構成する脂環式構造としては、シクロアルカン構造やシクロアルケン構造などが挙げられるが、機械的強度や耐熱性などの観点から、シクロアルカン構造が好ましい。また、脂環式構造としては、単環、多環、縮合多環、橋架け環や、これらを組み合わせてなる多環などが挙げられる。脂環式構造を構成する炭素原子数は、特に限定されないが、通常4~30個、好ましくは5~20個、より好ましくは5~15個の範囲であり、環式構造を構成する炭素原子数がこの範囲にある場合に、機械的強度、耐熱性、及び成形性の諸特性が高度にバランスされ好適である。また、脂環式オレフィン重合体(A1)は、通常、熱可塑性のものである。
本発明で用いる脂環式オレフィン重合体(A1)を得る重合法は開環重合や付加重合が用いられるが、開環重合の場合には得られた開環重合体を水素添加することが好ましい。
本発明で用いられる脂環式オレフィン重合体(A1)は、重合や水素添加反応後の重合体溶液として使用しても、溶媒を除去した後に使用してもどちらでもよいが、樹脂組成物を調製する際に添加剤の溶解や分散が良好になるとともに、工程が簡素化できるため、重合体溶液として使用するのが好ましい。
本発明で用いられる硬化剤(A2)は、特に限定されず、一般の電気絶縁膜形成用の樹脂組成物に配合される硬化剤を用いることができる。硬化剤(A2)としては、脂環式オレフィン重合体(A1)の備える極性基と反応して結合を形成することができる官能基を2個以上有する化合物を用いることが好ましい。
また、本発明で用いる被めっき層用樹脂組成物は、脂環式オレフィン重合体(A1)、及び硬化剤(A2)に加えて、無機フィラー(A3)をさらに含有していることが好ましい。無機フィラー(A3)をさらに含有させることにより、絶縁性接着フィルムの線膨張係数をより低いものとすることができる。
また、本発明で用いる被めっき層用樹脂組成物には、必要に応じて、硬化促進剤を含有していてもよい。硬化促進剤としては特に限定されないが、たとえば、脂肪族ポリアミン、芳香族ポリアミン、第2級アミン、第3級アミン、イミダゾール誘導体、有機酸ヒドラジド、ジシアンジアミド及びその誘導体、尿素誘導体などが挙げられるが、これらのなかでも、イミダゾール誘導体が特に好ましい。
次いで、接着層を形成するための接着層用樹脂組成物について説明する。本発明で用いる接着層用樹脂組成物は、極性基含有脂環式オレフィン重合体(B1)、硬化剤(B2)及び無機フィラー(B3)を含有する。
本発明で用いる接着層用樹脂組成物は、樹脂成分として、極性基含有脂環式オレフィン重合体(B1)を含有する。
硬化剤(B2)としては、特に限定されないが、上述した脂環式オレフィン重合体(B1)の備える極性基と反応して結合を形成することができる官能基を有する化合物であればよいが、たとえば、上述した被めっき層用樹脂組成物に用いる硬化剤(A2)と同様のものを用いることができる。
本発明で用いる無機フィラー(B3)としては、特に限定されないが、たとえば、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、酸化亜鉛、酸化チタン、酸化マグネシウム、ケイ酸マグネシウム、ケイ酸カルシウム、ケイ酸ジルコニウム、水和アルミナ、水酸化マグネシウム、水酸化アルミニウム、硫酸バリウム、シリカ、タルク、クレーなどが挙げられる。これらのなかでも、硬化物の表面粗化処理に使用される過マンガン酸塩の水溶液などの酸化性化合物により、分解もしくは溶解しないものが好ましく、特にシリカが好ましい。過マンガン酸塩の水溶液などの酸化性化合物により、無機フィラーが分解もしくは溶解してしまうと、エッチング処理によって深い穴ができることがあるためである。
また、本発明で用いる接着層用樹脂組成物には、上述した被めっき層用樹脂組成物と同様に、例えば、硬化促進剤や、難燃剤を配合してもよし、さらに必要に応じて、難燃助剤、耐熱安定剤、耐候安定剤、老化防止剤、紫外線吸収剤(レーザー加工性向上剤)、レベリング剤、帯電防止剤、スリップ剤、アンチブロッキング剤、防曇剤、滑剤、染料、天然油、合成油、ワックス、乳剤、磁性体、誘電特性調整剤、靭性剤などの任意成分を配合してもよい。これらの任意成分の配合割合は、本発明の目的を損なわない範囲で適宜選択すればよい。
本発明の絶縁性接着フィルムは、上述した被めっき層用樹脂組成物からなる被めっき層と、上述した接着層用樹脂組成物からなる接着層とを有するものである。
本発明のプリプレグは、上述した本発明の絶縁性接着フィルムと繊維基材とからなり、プリプレグの一方の面が上述した接着用樹脂組成物からなる接着層で、他方の面が上述した被めっき層用樹脂組成物からなる被めっき層からなる絶縁性複合体である。
本発明の積層体は、上述した本発明の絶縁性接着フィルム又はプリプレグを基材に積層してなるものである。本発明の積層体としては、少なくとも、上述した本発明の絶縁性接着フィルム又はプリプレグを積層してなるものであればよいが、表面に導体層を有する基板と、上述した本発明の絶縁性接着フィルム又はプリプレグの硬化物からなる電気絶縁層とを積層してなるものが好ましい。なお、この際においては、本発明の絶縁性接着フィルム又はプリプレグが、接着層を介して基板と積層されるような構成とする。すなわち、本発明の積層体においては、電気絶縁層の表面は、本発明の絶縁性接着フィルム又はプリプレグの被めっき層及び接着層のうち、被めっき層により形成されることとなる。
本発明の硬化物は、上述した方法により得られる本発明の、絶縁性接着フィルム、プリプレグ、又は積層体について硬化する処理を行なうことで得られるものである。硬化は、例えば、前記積層体の製造方法における加熱圧着操作の温度に示す温度範囲にて前記フィルム等を加熱することにより行うことができる。硬化対象が、例えば、本発明の積層体であれば、通常、導体層上に、本発明の絶縁性接着フィルム又はプリプレグが積層された基板全体を加熱することにより行う。また、当該硬化は、上述した加熱圧着操作と同時に行うことができる。なお、硬化する処理は段階的に行っても良く、例えば、先ず加熱圧着操作を硬化の起こらない条件、すなわち比較的低温、短時間で行った後、硬化を行ってもよい。
本発明の複合体は、本発明の硬化物の表面、具体的には当該硬化物の被めっき層上に、無電解めっきにより、さらに導体層を形成してなるものである。以下、本発明の複合体の製造方法を、本発明の複合体の一例としての多層回路基板を例示して、説明する。当該多層回路基板において、本発明の絶縁性接着フィルム(又はプリプレグ)の硬化物は電気絶縁層を形成する。
電気絶縁層の表面平均粗さRaは、好ましくは0.05μm以上0.5μm未満、より好ましくは0.06μm以上0.3μm以下であり、かつ表面十点平均粗さRzjisは、好ましくは0.3μm以上4μm未満、より好ましくは0.5μm以上2μm以下である。なお、本明細書において、RaはJIS B0601-2001に示される算術平均粗さであり、表面十点平均粗さRzjisは、JIS B0601-2001付属書1に示される十点平均粗さである。
酸化性化合物溶液を、電気絶縁層の表面に接触させる方法としては、特に限定されないが、たとえば、電気絶縁層を酸化性化合物溶液に浸漬するディップ法、酸化性化合物溶液の表面張力を利用して、酸化性化合物溶液を、電気絶縁層に載せる液盛り法、酸化性化合物溶液を、電気絶縁層に噴霧するスプレー法、などいかなる方法であってもよい。表面粗化処理を行うことにより、電気絶縁層の、導体層など他の層との間の密着性を向上させることができる。
導体層の形成方法は、密着性に優れる導体層を形成できるという観点より、無電解めっき法により行なう。
本発明の電子材料用基板は、上述した本発明の硬化物又は複合体を構成材料として含むものである。かかる本発明の電子材料用基板は、携帯電話機、PHS、ノート型パソコン、PDA(携帯情報端末)、携帯テレビ電話機、パーソナルコンピューター、スーパーコンピューター、サーバー、ルーター、液晶プロジェクタ、エンジニアリング・ワークステーション(EWS)、ページャ、ワードプロセッサ、テレビ、ビューファインダ型又はモニタ直視型のビデオテープレコーダ、電子手帳、電子卓上計算機、カーナビゲーション装置、POS端末、タッチパネルを備えた装置などの各種電子機器に好適に用いることができる。
脂環式オレフィン重合体の数平均分子量(Mn)、及び重量平均分子量(Mw)は、テトラヒドロフランを展開溶媒として、ゲル・パーミエーション・クロマトグラフィー(GPC)により測定し、ポリスチレン換算値として求めた。
水素添加前における重合体中の不飽和結合のモル数に対する水素添加された不飽和結合のモル数の比率を、400MHzの1H-NMRスペクトル測定により求め、これを水素添加率とした。
重合体中の総単量体単位モル数に対するカルボン酸無水物基を有する単量体単位のモル数の割合を、400MHzの1H-NMRスペクトル測定により求め、これを重合体のカルボン酸無水物基を有する単量体単位の含有率とした。
フィルム状硬化物から幅6mm、長さ15.4mmの小片を切り出し、支点間距離10mm、昇温速度10℃/分の条件で、熱機械分析装置(TMA/SDTA840:メトラー・トレド社製)により、30℃~150℃の線膨張係数の測定を行った。
○:線膨張係数の値が30ppm/℃未満
×:線膨張係数の値が30ppm/℃以上
積層体の電気絶縁層に、炭酸ガスレーザー加工機(日立ビアメカニクス社製:LC-2K212/2C)を使用して、パルス幅17μs、周波数1000Hz、2ショットで穴あけを行い、ビアホール(トップ径60μm)を形成し、ビアホールを有する積層体を得た。そして、得られたビアホールを有する積層体のビアホール及びビアホール開口周縁を電子顕微鏡(倍率:1100倍、以下、同じ。)で観察し、穴あけ後のホール状態及びビアホール開口周縁の粗れの評価を行った。また、ビアホールを有する積層体に、デスミア処理(膨潤処理、酸化処理、中和還元処理)を行い、デスミア処理を行なった積層体のビアホールを電子顕微鏡で観察し、デスミア処理後のホール状態の評価を行った。なお、穴あけ後のホール状態及びデスミア処理後のホール状態は、以下の基準で評価した。結果を表1に示す。
○:ボトム径/トップ径の比が、70%以上
×:ボトム径/トップ径の比が、70%未満
また、デスミア処理後のビアホールの状態については、以下の基準で評価した。結果を表1に示す。
○:デスミア後のトップ径/デスミア前のトップ径の比が、105%未満
×:デスミア後のトップ径/デスミア前のトップ径の比が、105%以上
また、ビアホール開口周縁の粗れについては、以下の基準で評価した。結果を表1に示す。
○:異常なし
×:クラック、樹脂飛び散り、粗れ等の異常あり
多層プリント配線板における絶縁層と銅めっき層との引き剥がし強さをJIS C6481-1996に準拠して測定した。
○:ピール強度が5N/cm以上
×:ピール強度が5N/cm未満
配線パターン付き多層プリント配線板の導体回路が形成されていない部分における電気絶縁層の表面を、表面形状測定装置(ビーコインスツルメンツ社製、WYKO NT1100)を用いて、測定範囲91μm×120μmで表面粗度(算術平均粗さRa)を測定した。
○:表面粗度Raが0.2μm未満
△:表面粗度Raが0.2μm以上、0.5μm未満
×:表面粗度Raが0.5μm以上
重合1段目として5-エチリデン-ビシクロ[2.2.1]ヘプト-2-エン(EdNB)35モル部、1-ヘキセン0.9モル部、アニソール340モル部及び4-アセトキシベンジリデン(ジクロロ)(4,5-ジブロモ-1,3-ジメシチル-4-イミダゾリン-2-イリデン)(トリシクロヘキシルホスフィン)ルテニウム(C1063、和光純薬社製)0.005モル部を、窒素置換した耐圧ガラス反応器に仕込み、攪拌下に80℃で30分間の重合反応を行ってノルボルネン系開環重合体の溶液を得た。
次いで、重合2段目として重合1段目に得た溶液中にテトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(MTF)35モル部、ビシクロ[2.2.1]ヘプト-2-エン-5,6-ジカルボン酸無水物(NDCA)30モル部、アニソール250モル部及びC1063 0.01モル部を追加し、攪拌下に80℃で1.5時間の重合反応を行ってノルボルネン系開環重合体の溶液を得た。この溶液について、ガスクロマトグラフィーを測定したところ、実質的に単量体が残留していないことが確認され、重合転化率は99%以上であった。
次いで、窒素置換した攪拌機付きオートクレーブに、得られた開環重合体の溶液を仕込み、C1063 0.03モル部を追加し、150℃、水素圧7MPaで、5時間攪拌させて水素添加反応を行って、ノルボルネン系開環重合体の水素添加物である脂環式オレフィン重合体(P-1)の溶液を得た。得られた重合体(P-1)の重量平均分子量は60,000、数平均分子量は30,000、分子量分布は2であった。また、水素添加率は95%であり、カルボン酸無水物基を有する単量体単位の含有率は30モル%であった。重合体(P-1)の溶液の固形分濃度は22%であった。
テトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(MTF)70モル部、ビシクロ[2.2.1]ヘプト-2-エン-5,6-ジカルボン酸無水物(NDCA)30モル部、1-ヘキセン0.9モル部、アニソール590モル部及びC1063 0.015モル部を、窒素置換した耐圧ガラス反応器に仕込み、攪拌下に80℃で1時間の重合反応を行ってノルボルネン系開環重合体の溶液を得た。この溶液について、ガスクロマトグラフィーを測定したところ、実質的に単量体が残留していないことが確認され、重合転化率は99%以上であった。
次いで、窒素置換した攪拌機付きオートクレーブに、得られた開環重合体の溶液を仕込み、150℃、水素圧7MPaで、5時間攪拌させて水素添加反応を行って、ノルボルネン系開環重合体の水素添加物である脂環式オレフィン重合体(P-2)の溶液を得た。得られた重合体(P-2)の重量平均分子量は50,000、数平均分子量は26,000、分子量分布は1.9であった。また、水素添加率は97%であり、カルボン酸無水物基を有する単量体単位の含有率は30モル%であった。重合体(P-2)の溶液の固形分濃度は22%であった。
テトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(MTF)70モル部、ビシクロ[2.2.1]ヘプト-2-エン-5,6-ジカルボン酸無水物(NDCA)30モル部、1-ヘキセン6モル部、アニソール590モル部及びC1063 0.015モル部を、窒素置換した耐圧ガラス反応器に仕込み、攪拌下に80℃で1時間の重合反応を行って開環重合体の溶液を得た。この溶液について、ガスクロマトグラフィーを測定したところ、実質的に単量体が残留していないことが確認され、重合転化率は99%以上であった。
次いで、窒素置換した攪拌機付きオートクレーブに、得られた開環重合体の溶液を仕込み、150℃、水素圧7MPaで、5時間攪拌させて水素添加反応を行った。次いで、得られた水素化反応溶液を濃縮して、脂環式オレフィン重合体(P-3)の溶液を得た。得られた脂環式オレフィン重合体(P-3)の重量平均分子量は10,000、数平均分子量は5,000、分子量分布は2であった。また、水素添加率は97%であり、カルボン酸無水物基を有する単量体単位の含有率は30モル%であった。脂環式オレフィン重合体(P-3)の溶液の固形分濃度は55%であった。
(被めっき層用樹脂組成物)
合成例1で得られた脂環式オレフィン重合体(P-1)の溶液45部、及び無機フィラー(A3)としての未処理球状シリカ(アドマファイン(登録商標)SO-C1、アドマテックス社製、体積平均粒径0.25μm)98%と合成例2で得られた脂環式オレフィン重合体(P-2)2%とを固形分が75%になるようにアニソールに混合し高圧ホモジナイザーで分散したシリカスラリー6部を混合し、遊星式攪拌機で3分間攪拌した。
これに、硬化剤(A2)としてジシクロペンタジエン型多官能エポキシ樹脂(EPICLON HP-7200L、DIC社製、エポキシ当量242~252)3.5部、レーザー加工性向上剤として2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール0.1部、老化防止剤としてトリス-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレート(IRGANOX(登録商標)3114、BASF社製)0.1部、老化防止剤としてテトラキス(1,2,2,6,6-ペンタメチル-4-ピペリジル)1,2,3,4-ブタンテトラカルボキシラート(アデカスタブ(登録商標)LA52、ADEKA社製)0.05部、及びアニソール75.2部を混合し、遊星式攪拌機で3分間攪拌した。
さらにこれに、硬化促進剤として1-べンジル-2-フェニルイミダゾールをアニソールに50%溶解した溶液0.1部を混合し、遊星式攪拌機で5分間攪拌して被めっき層用樹脂組成物のワニスを得た。
合成例2で得られた脂環式オレフィン重合体(P-2)の溶液9.1部、無機フィラー(B3)としての表面処理球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)98.5%と合成例3で得られた脂環式オレフィン重合体(P-3)1.5%とを固形分が78%になるようにアニソールに混合し、高圧ホモジナイザーで処理し、分散させたシリカスラリー84.6部を混合し、遊星式攪拌機で3分間攪拌した。
これに、硬化剤(B2)としてビスフェノールA型エポキシ樹脂〔エピコート(登録商標)828EL、三菱化学社製、エポキシ当量184~194〕3部、多官能エポキシ樹脂(1032H60、三菱化学社製、エポキシ当量163~175)3部、ジシクロペンタジエン型多官能エポキシ樹脂(EPICLON HP-7200L)11部、老化防止剤としてトリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレート0.1部、ジシクロペンタジエン型ノボラック樹脂(GDP-6140、群栄化学工業社製)15部、およびアニソール2.4部を混合し、遊星式攪拌機で3分間攪拌した。さらにこれに、硬化促進剤として1-べンジル-2-フェニルイミダゾールをアニソールに50%溶解した溶液0.3部を混合し、遊星式攪拌機で5分間攪拌して接着層用樹脂組成物のワニスを得た。
上記にて得られた被めっき層用樹脂組成物のワニスを、厚さ100μmのポリエチレンテレフタレートフィルム(支持体)上にワイヤーバーを用いて塗布し、次いで、窒素雰囲気下、85℃で5分間乾燥させて、未硬化の被めっき層用樹脂組成物からなる、厚み3μmの被めっき層が形成された支持体付きフィルムを得た。
次いで、銅張り積層基板の上に厚さ10μmの銅箔をのせ、その上から、上記にて得られた支持体付き接着フィルムを、支持体が付いた状態で、接着層が内側になるようにして、耐熱性ゴム製プレス板を上下に備えた真空ラミネータを用い、200Paに減圧して、温度110℃、圧力0.1MPaで60秒間加熱圧着積層し、その後180℃で120分間空気中で加熱硬化した。硬化後、銅箔付き硬化樹脂を切り出し、銅箔を1mol/Lの過硫酸アンモニウム水溶液にて溶解し、乾燥させて、フィルム状硬化物を得た。そして、得られたフィルム状硬化物について、上記方法に従い、線膨張係数の測定を行った。結果を表1に示す。
次いで、上記とは別に、ガラスフィラー及びハロゲン不含エポキシ樹脂を含有するワニスをガラス繊維に含浸させて得られたコア材の表面に、厚さ35μmの銅が貼られた、厚さ0.8mm×縦150mm×横150mmの両面銅張り積層基板の銅表面を有機酸との接触によってマイクロエッチング処理した両面銅張り積層基板(内層基板)を得た。
得られた積層体を、膨潤液(「スウェリング ディップ セキュリガント P」、アトテック社製、「セキュリガント」は登録商標)500mL/L、水酸化ナトリウム3g/Lになるように調製した60℃の水溶液に15分間揺動浸漬した後、水洗した。
次いで、過マンガン酸塩の水溶液(「コンセントレート コンパクト CP」、アトテック社製)500mL/L、水酸化ナトリウム濃度40g/Lになるように調製した80℃の水溶液に20分間揺動浸漬をした後、水洗した。
続いて、硫酸ヒドロキシアミン水溶液(「リダクション セキュリガント P 500」、アトテック社製、「セキュリガント」は登録商標)100mL/L、硫酸35mL/Lになるように調製した40℃ の水溶液に、積層体を5分間浸漬し、中和還元処理をした後、水洗した。
次いで、クリーナー・コンディショナー水溶液(「アルカップ MCC-6-A」、上村工業社製、「アルカップ」は登録商標)を濃度50ml/Lとなるよう調整した50℃の水溶液に積層体を5分間浸漬し、クリーナー・コンディショナー処理を行った。次いで40℃の水洗水に積層体を1分間浸漬した後、水洗した。
次いで、硫酸濃度100g/L、過硫酸ナトリウム100g/Lとなるように調製した水溶液に積層体を2分間浸漬しソフトエッチング処理を行った後、水洗した。
次いで、硫酸濃度100g/Lなるよう調製した水溶液に積層体を1分間浸漬し酸洗処理を行った後、水洗した。
次いで、アルカップ アクチベータ MAT-1-A(商品名、上村工業社製、「アルカップ」は登録商標)が200mL/L、アルカップ アクチベータ MAT-1-B(上商品名、村工業社製、「アルカップ」は登録商標)が30mL/L、水酸化ナトリウムが0.35g/Lになるように調製した60℃のPd塩含有めっき触媒水溶液に積層体を5分間浸漬した後、水洗した。
続いて、アルカップ レデユーサ- MAB-4-A(商品名、上村工業社製、「アルカップ」は登録商標)が20mL/L、アルカップ レデユーサ- MAB-4-B(商品名、上村工業社製、「アルカップ」は登録商標)が200mL/Lになるように調整した水溶液に積層体を35℃で、3分間浸漬し、めっき触媒を還元処理した後、水洗した。
次いで、アルカップ アクセレレーター MEL-3-A(商品名、上村工業社製、「アルカップ」は登録商標)が50mL/Lになるように調製した水溶液に積層体を25℃で、1分間浸漬した。
このようにして得られた積層体を、スルカップ PEA-6-A(商品名、上村工業社製、「スルカップ」は登録商標)100mL/L、スルカップ PEA-6-B-2X(商品名、上村工業社製)50mL/L、スルカップ PEA-6-C(商品名、上村工業社製)14mL/L、スルカップ PEA-6-D(商品名、上村工業社製)15mL/L、スルカップ PEA-6-E(商品名、上村工業社製)50mL/L、37%ホルマリン水溶液5mL/Lとなるように調製した無電解銅めっき液に空気を吹き込みながら、温度36℃で、20分間浸漬して無電解銅めっき処理して積層体表面(被めっき層用樹脂組成物からなる被めっき層の表面)に無電解めっき膜を形成した。次いで、空気雰囲気下において150℃で30分間アニール処理を行った。
被めっき層用樹脂組成物を得る際に、合成例1で得られた脂環式オレフィン重合体(P-1)の溶液を45.2部、無機フィラー(A3)としての未処理球状シリカ(アドマファインSO-C1、アドマテックス社製、体積平均粒径0.25μm)98%と合成例2で得られた脂環式オレフィン重合体(P-2)2%とを固形分が75%になるようにアニソールに混合し高圧ホモジナイザーで処理し分散したシリカスラリーを3.3部、アニソールを63.7部に変更した以外は、実施例1と同様にして、被めっき層用樹脂組成物のワニスを得て、得られた被めっき層用樹脂組成物のワニスを用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
被めっき層用樹脂組成物を得る際に、合成例1で得られた脂環式オレフィン重合体(P-1)の溶液を45.4部、無機フィラー(A3)としての未処理球状シリカ(アドマファインSO-C1、アドマテックス社製、体積平均粒径0.25μm)98%と合成例2で得られた脂環式オレフィン重合体(P-2)2%とを固形分が78%になるようにアニソールに混合し高圧ホモジナイザーで15分間処理し分散したシリカスラリーを0.9部、アニソールを53.3部に変更した以外は、実施例1と同様にして、被めっき層用樹脂組成物のワニスを得て、得られた被めっき層用樹脂組成物のワニスを用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
接着用樹脂組成物を得る際に、脂環式オレフィン重合体(P-2)の溶液9.1部を2.1部に、及び無機フィラー(B3)としての表面球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)と合成例3で得られた脂環式オレフィン重合体(P-3)とアニソールとからなるシリカスラリーの代わりに、表面球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)63部に、ジシクロペンタジエン型ノボラック樹脂(GDP-6140、群栄化学工業社製)15部を16部に変更し、アニソールを28部に変更した以外は、実施例1と同様にして接着用樹脂組成物のワニスを得て、得られた接着用樹脂組成物を用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
接着用樹脂組成物を得る際に、脂環式オレフィン重合体(P-2)の溶液9.1部を24.6部に、及び無機フィラー(B3)としての表面球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)と合成例3で得られた脂環式オレフィン重合体(P-3)とアニソールとからなるシリカスラリー84.6部を91.2部に、ジシクロペンタジエン型ノボラック樹脂(GDP-6140、群栄化学工業社製)15部を14部に変更した以外は、実施例1と同様にして接着用樹脂組成物のワニスを得て、得られた接着用樹脂組成物を用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
接着層用樹脂組成物を得る際に、合成例2で得られた脂環式オレフィン重合体(P-2)の溶液の代わりに、合成例3で得られた脂環式オレフィン重合体(P-3)の溶液を1.4部、無機フィラー(B3)としての表面処理球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)98.5%と合成例3で得られた脂環式オレフィン重合体(P-3)1.5%とを固形分が78%になるようにアニソールに混合し、高圧ホモジナイザーで処理し、分散させたシリカスラリーを19.2部に、アニソールを2.5部に変更した以外は、実施例1と同様にして、接着層用樹脂組成物のワニスを得て、得られた接着層用樹脂組成物のワニスを用いた以外は、実施例2と同様にして接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
被めっき層用樹脂組成物を得る際に、合成例1で得られた脂環式オレフィン重合体(P-1)の溶液を44.5部、無機フィラー(A3)としての未処理球状シリカ(アドマファインSO-C1、アドマテックス社製、体積平均粒径0.25μm)98%と合成例2で得られた脂環式オレフィン重合体(P-2)2%とを固形分が78%になるようにアニソールを添加し高圧ホモジナイザーで15分間処理し分散したシリカスラリーを13.3部、アニソールを106.8部に変更した以外は、実施例1と同様にして、被めっき層用樹脂組成物のワニスを得て、得られた被めっき層用樹脂組成物のワニスを用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
接着層用樹脂組成物を得る際に、合成例2で得られた脂環式オレフィン重合体(P-2)の溶液40.9部、合成例3で得られた脂環式オレフィン重合体(P-3)の溶液1.4部、無機フィラー(B3)としての表面処理球状シリカ(アドマファインSC-2500-SXJ、アドマテックス社製、アミノシランタイプシランカップリング剤処理品、体積平均粒径0.5μm)98.5%と合成例3で得られた脂環式オレフィン重合体(P-3)1.5%とを固形分が78%になるようにアニソールに混合し、高圧ホモジナイザーで15分間処理し、分散させたシリカスラリー20.8部を混合し、遊星式攪拌機で3分間攪拌した。
これに、硬化剤(B2)としてビスフェノールA型エポキシ樹脂〔エピコート(登録商標)828EL、三菱化学社製、エポキシ当量184~194〕0.8部、多官能エポキシ樹脂(1032H60、三菱化学社製、エポキシ当量163~175)2部、老化防止剤としてトリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレート0.1部を混合し、遊星式攪拌機で3分間攪拌した。さらにこれに、硬化促進剤として1-べンジル-2-フェニルイミダゾールをアニソールに50%溶解した溶液0.3部を混合し、遊星式攪拌機で5分間攪拌して接着層用樹脂組成物のワニスを得た以外は、実施例1と同様にして、接着層用樹脂組成物のワニスを得て、得られた接着層用樹脂組成物のワニスを用いた以外は、実施例2と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
被めっき層用樹脂組成物を得る際に、脂環式オレフィン重合体(P-1)の溶液、及び無機フィラー(A3)としての未処理球状シリカ(アドマファインSO-C1、アドマテックス社製、体積平均粒径0.25μm)と合成例2で得られた脂環式オレフィン重合体(P-2)脂環式オレフィン重合体(P-2)とアニソールからなるシリカスラリーの代わりに、3or4-メチル-ヘキサヒドロ無水フタル酸(HN-5500、日立化成社製)2.2部、未処理球状シリカ(アドマファインSO-C1)1.5部に変更し、アニソールを6.7部に変更した以外は、実施例1と同様にして、被めっき層用樹脂組成物のワニスを得て、得られた被めっき層用樹脂組成物のワニスを用いた以外は、実施例1と同様にして、接着フィルム、積層体、多層プリント配線板A、Bを得て、同様に評価を行った。これらの評価結果、ならびに、接着フィルムの被めっき層及び接着層を構成する主な成分の含有割合を表1に示す。
被めっき層を形成する被めっき層用樹脂組成物中における、極性基含有脂環式オレフィン重合体の含有割合が50重量%未満である場合には、ビアホール形成性、特に、ビアホール開口周縁の粗れが発生するとともに、ピール強度が低下し、めっき密着性に劣り、さらには、表面粗度にも劣る結果となった(比較例2)。
また、接着層を形成する接着層用樹脂組成物中における、極性基含有脂環式オレフィン重合体の含有割合が30重量%超である場合には、ビアホール形成性、特に、穴あけ後のホール状態が悪化するとともに、線膨張係数が高く、耐熱性に劣る結果となった(比較例3)。
さらに、被めっき層を形成する被めっき層用樹脂組成物の樹脂成分として、フェノール樹脂を用いた場合には、ビアホール形成性、特に、デスミア後のホール状態が悪化するとともに、ビアホール開口周縁の粗れが発生し、さらには、ピール強度及び表面粗度にも劣る結果となった(比較例4)。
Claims (12)
- 極性基含有脂環式オレフィン重合体(A1)、及び硬化剤(A2)を含有する被めっき層用樹脂組成物からなる被めっき層と、
極性基含有脂環式オレフィン重合体(B1)、硬化剤(B2)及び無機フィラー(B3)を含有する接着層用樹脂組成物からなる接着層とを有し、
前記被めっき層中に含有される固形分全体に対する、前記極性基含有脂環式オレフィン重合体(A1)の含有比率が50~90重量%であり、
前記接着層中に含有される固形分全体に対する、前記極性基含有脂環式オレフィン重合体(B1)の含有比率が1~30重量%、前記無機フィラー(B3)の含有比率が50~90重量%であることを特徴とする絶縁性接着フィルム。 - 極性基含有脂環式オレフィン重合体(A1)、及び硬化剤(A2)を含有する被めっき層用樹脂組成物からなる被めっき層と、
極性基含有脂環式オレフィン重合体(B1)、硬化剤(B2)及び無機フィラー(B3)を含有する接着層用樹脂組成物からなる接着層とを有し、
前記被めっき層中に含有される固形分全体に対する、前記極性基含有脂環式オレフィン重合体(A1)の含有比率が50~90重量%であり、
前記接着層中に含有される固形分全体から無機フィラー(B3)を除いた量に対する、前記極性基含有脂環式オレフィン重合体(B1)の含有比率が20重量%以下、前記接着層中に含有される固形分全体に対する前記無機フィラー(B3)の含有比率が50~90重量%であることを特徴とする絶縁性接着フィルム。 - 前記被めっき層を構成する被めっき層用樹脂組成物が、無機フィラー(A3)をさらに含有し、
前記被めっき層中に含有される固形分全体に対する、前記無機フィラー(A3)の含有比率が1~40重量%であることを特徴とする請求項1または2に記載の絶縁性接着フィルム。 - 前記無機フィラー(B3)が、平均粒径0.2~3μmの球状シリカであることを特徴とする請求項1~3のいずれかに記載の絶縁性接着フィルム。
- 前記無機フィラー(B3)が、表面処理された表面処理球状シリカであることを特徴とする請求項1~4のいずれかに記載の絶縁性接着フィルム。
- 前記無機フィラー(A3)が、平均粒径0.1~0.5μmの球状シリカであることを特徴とする請求項3~5のいずれかに記載の絶縁性接着フィルム。
- 前記無機フィラー(A3)が、表面処理をしていない未処理球状シリカであることを特徴とする請求項3~6のいずれかに記載の絶縁性接着フィルム。
- 請求項1~7のいずれかに記載の絶縁性接着フィルムと繊維基材からなるプリプレグ。
- 請求項1~7のいずれかに記載の絶縁性接着フィルム、又は請求項8に記載のプリプレグを基材に積層してなる積層体。
- 請求項1~7のいずれかに記載の絶縁性接着フィルム、請求項8に記載のプリプレグ、又は請求項9に記載の積層体を硬化してなる硬化物。
- 請求項10に記載の硬化物の表面に、無電解めっきにより、導体層を形成してなる複合体。
- 請求項10に記載の硬化物、又は請求項11に記載の複合体を構成材料として含む電子材料用基板。
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