JPWO2009038177A1 - Curable resin composition and use thereof - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition capable of forming an electrical insulation layer having a low relative dielectric constant when an electrical insulation layer of a multilayer circuit board used in a high frequency region is formed. The curable resin composition of the present invention is a curable resin composition containing an alicyclic olefin polymer, a curing agent, and porous silica aggregated particles, and the porous silica aggregated particles have a lattice spacing of 1 nm or more. Porous silica spherical primary particles exhibiting an X-ray diffraction pattern having one or more diffraction lines in the range of the diffraction angle (2θ / °) corresponding to (d), and a void layer between these porous silica spherical primary particles It is characterized by being porous silica aggregated particles aggregated so as to form.

Description

  The present invention relates to a curable resin composition and a multilayer circuit board having an electrically insulating layer formed from the composition.

  With the recent miniaturization of semiconductor circuits and the increase in the number of layers, through via holes, blind via holes, etc., and the increased density of circuit boards due to the surface mounting of small chip components, electronic devices have become smaller and lighter and higher in size. Performance and multifunction are progressing. A multilayer circuit board, which is one of such high-density mounting boards, is a laminated body in which conductor circuits and electrical insulating layers are alternately stacked. As a method of stacking an electrical insulation layer on a conductor circuit (wiring layer), a film or sheet-like molding of an electrically insulating resin is performed on a substrate having a conductor circuit on the surface (hereinafter sometimes referred to as “substrate”). The method of laminating | stacking by stacking | stacking an object and heating and pressurizing is common.

 However, as the density of electronic components has increased, the speed has increased to the point where electrical performance cannot be ensured due to delays in the electrical signal. It has become. The deterioration of the electric signal is the sum of the loss of the electric signal from the conductor and the loss of the electric signal from the dielectric. For example, in a multilayer circuit board, the loss of an electric signal from a dielectric that constitutes an electric insulating layer increases remarkably with an increase in the frequency of the electric signal, and the electric signal deteriorates at a frequency in the GHz band. It is the main factor. For this reason, generally used epoxy resin, polyimide resin, etc. as materials for the electrical insulation layer of electronic devices such as multilayer circuit boards have insufficient electrical properties such as dielectric constant and dielectric loss tangent, and high-speed transmission of electrical signals. In some cases, it may be difficult to cope with the process.

 Therefore, polynorbornene-based resin is used as a material for a wiring board for mounting a semiconductor element and other mounting parts in an electronic device with excellent dielectric characteristics (see, for example, Patent Document 1). However, polynorbornene-based resins have a large coefficient of thermal expansion, and there remains a problem from the viewpoint of dimensional stability with respect to narrow pitches associated with downsizing and high performance. In order to improve such a problem, the thermal expansion coefficient was suppressed by filling nonporous inorganic silica (for example, refer to Patent Document 2). However, filling non-porous inorganic silica still has a problem that the dielectric properties as an insulating material deteriorate.

  In order to solve such a problem, Patent Document 3 discloses that “(A) a cyclic olefin-based resin, (B) a porous inorganic filler, an inorganic hollow filler, or a polytetrafluoroethylene (PTFE) particle” A resin composition characterized by comprising a combination of a plurality of types is disclosed. According to the resin composition of Patent Document 3, since both dielectric characteristics and dimensional stability are excellent, by using this as an interlayer insulating material for electronic devices such as multilayer circuit boards, high-speed transmission of electrical signals and small size are achieved. It is described that it is possible to cope with a narrow pitch accompanying high performance.

  However, as the frequency of electrical signals increases, it is desired to provide a material that can form an electrical insulating layer with further improved dielectric characteristics.

JP 2002-232138 A WO94 / 20575 pamphlet JP 2006-104318 A

 An object of the present invention is to provide a curable resin composition capable of forming an electrical insulation layer having a low relative dielectric constant, particularly when an electrical insulation layer of a multilayer circuit board used in a high frequency region is formed. .

  The inventors of the present invention have added a specific porous silica aggregated particle to the curable resin composition as described above, thereby reducing the dielectric constant without deteriorating other electrical and mechanical properties. It was found that a layer was formed, and the present invention was completed.

That is, the gist of the present invention to solve the above problems is as follows.
(1) An alicyclic olefin polymer, a curing agent, and porous silica aggregated particles, wherein the porous silica aggregated particles have a diffraction angle (2θ / °) corresponding to a lattice spacing (d) of 1 nm or more. Porous silica aggregated particles obtained by aggregating porous silica spherical primary particles having an X-ray diffraction pattern having one or more diffraction lines in a range so as to form a void layer between these porous silica spherical primary particles A curable resin composition characterized by the above.
(2) The curable resin composition according to (1), wherein the alicyclic olefin polymer has a carboxyl group or an acid anhydride group.
(3) A molded product obtained by molding the curable resin composition according to (1) or (2) into a film or a sheet.
(4) A composite containing the curable resin composition according to (1) or (2) above and a fiber substrate.
(5) Hardened | cured material formed by hardening | curing the molded object as described in said (3).
(6) Hardened | cured material formed by hardening | curing the composite_body | complex as described in said (4).
(7) A laminate in which a substrate having a conductor layer on the surface and an electrical insulating layer made of the cured product according to (5) or (6) are laminated.
(8) On the substrate having a conductor layer on the surface, the molded body according to (3) or the composite body according to (4) is thermocompression bonded, and the molded body or the composite body is cured to form an electrical insulating layer. The manufacturing method of the laminated body including a process.
(9) A multilayer circuit board obtained by further forming a conductor layer on the electrical insulating layer of the laminate according to (7).
(10) An electronic device including the multilayer circuit board according to (9).
(11) Porous silica spherical primary particles exhibiting an X-ray diffraction pattern having one or more diffraction lines in a diffraction angle (2θ / °) range corresponding to a lattice plane spacing (d) of 1 nm or more are formed by using these porous materials. Formed from a curable resin composition containing an alicyclic olefin polymer and a curing agent, characterized by adding porous silica aggregated particles assembled so as to form a void layer between spherical silica spherical primary particles For reducing the relative dielectric constant of a cured product.

  According to the curable resin composition of the present invention, it is possible to easily obtain an electrical insulating layer having a decreased dielectric constant without impairing other electrical and mechanical properties. Therefore, the curable resin composition of the present invention is preferably used for forming an electrical insulating layer of a multilayer circuit board used particularly in a high frequency region.

It is a FE-SEM image of the porous silica aggregation particle used in the Example. Fig. 2 is an enlarged FE-SEM image of a part of Fig. 1. It is a FE-SEM image which shows a porous silica spherical primary particle.

 Hereinafter, the curable resin composition of the present invention and the multilayer circuit board having an electrical insulating layer formed from the composition will be described more specifically.

(A) Curable resin composition The curable resin composition of the present invention includes an alicyclic olefin polymer, a curing agent, and porous silica aggregated particles, and further includes a curing accelerator, a flame retardant, and laser processing as necessary. Includes property improvers, other fillers, and additives.

(1) Alicyclic olefin polymer In the present invention, the alicyclic olefin polymer is a homopolymer or copolymer of an alicyclic compound (referred to as alicyclic olefin) having a carbon-carbon unsaturated bond, In addition, these are generic names for these derivatives (hydrogenated products and the like). The polymerization mode may be addition polymerization or ring-opening polymerization.

  Specific examples of alicyclic olefin polymers include ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition weights of norbornene monomers and vinyl compounds. Polymers, monocyclic cycloalkene addition polymers, alicyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers and hydrogenated products thereof, aromatic olefin polymer aromatic ring hydrogenated products, and the like after polymerization Examples thereof include a polymer in which an alicyclic structure is formed by hydrogenation and has a structure equivalent to that of an alicyclic olefin polymer. Among these, ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition polymers of norbornene monomers and vinyl compounds, aromatic olefin polymers Aromatic ring hydrogenated products are preferred, and hydrogenated products of ring-opening polymers of norbornene monomers are particularly preferred.

  The alicyclic olefin polymer used in the present invention has a weight average molecular weight (Mw) of usually 10,000 to 250,000, preferably 15,000 to 150,000, more preferably 20,000 to 100. , 000. The alicyclic olefin polymer has a number average molecular weight (Mn) of usually 1,000 to 500,000, preferably 3,000 to 300,000, and more preferably 5,000 to 250,000. belongs to.

  If the molecular weight of the alicyclic olefin polymer is too small, the strength of the obtained electrical insulation layer becomes insufficient, and the electrical insulation properties may be lowered. On the other hand, if the molecular weight is too large, the compatibility between the alicyclic olefin polymer and the curing agent decreases, the surface roughness of the electrical insulating layer increases, and the accuracy of the wiring pattern may decrease.

  Mw and Mn of the alicyclic olefin polymer can be measured by gel permeation chromatography (GPC) and determined as a polystyrene equivalent value.

  The method for adjusting the Mw and Mn of the alicyclic olefin polymer to the above ranges may be in accordance with a conventional method. For example, when performing ring-opening polymerization of an alicyclic olefin using a titanium-based or tungsten-based catalyst, a vinyl compound And a method of adding about 0.1 to 10 mol% of a molecular weight modifier such as a diene compound with respect to the total amount of the monomers. Specific examples of such molecular weight regulators include, as vinyl compounds, α-olefin compounds such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene compounds such as styrene and vinyltoluene; ethyl vinyl ether and isobutyl vinyl ether. And ether compounds such as allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; other vinyl compounds such as allyl acetate, allyl alcohol, glycidyl methacrylate, and acrylamide; Further, as the diene compound, non-conjugated such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, etc. Diene compounds; conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene; Can be mentioned.

  In addition, the alicyclic olefin polymer preferably has a carboxyl group or an acid anhydride group in the structure (hereinafter, both may be collectively referred to as “carboxyl group and the like”). Even if the carboxyl group or the like is directly bonded to the carbon atom forming the alicyclic structure of the alicyclic olefin polymer, other divalent groups such as a methylene group, an oxy group, an oxycarbonyloxyalkylene group, and a phenylene group can be used. It may be bonded via.

  In the alicyclic olefin polymer preferably used in the present invention, Mw and Mn are within the above ranges, and the content of carboxyl groups and the like is preferably 5 to 60 mol%, more preferably 10 to 50 mol%. Particularly preferably, it is 15 to 40 mol%. Here, the content of carboxyl groups and the like refers to the ratio of the number of moles of carboxyl groups and the like to the total number of monomer units in the polymer.

If the content of carboxyl group or the like of the alicyclic olefin polymer is too small, the plating adhesion and heat resistance may be lowered, and if the content is too large, the electrical insulation may be lowered.
The content of carboxyl groups and the like of the alicyclic olefin polymer can be determined by ¹ H-NMR spectrum measurement of the alicyclic olefin polymer.

  The method of setting the content of the alicyclic olefin polymer such as carboxyl group in the above range is not particularly limited. For example, (i) an alicyclic olefin monomer containing a carboxyl group or the like is homopolymerized, or a monomer copolymerizable therewith (an alicyclic olefin monomer having no carboxyl group or the like, A method of copolymerizing with ethylene, 1-hexene, 1,4-hexadiene, etc.); (ii) a carbon-carbon unsaturated bond-containing compound having a carboxyl group or the like to an alicyclic olefin polymer not containing a carboxyl group or the like. For example, a method of introducing a carboxyl group or the like by graft bonding in the presence of a radical initiator; (iii) a norbornene monomer having a group that becomes a precursor of a carboxyl group, such as a carboxylic acid ester group, is polymerized Thereafter, there is a method of converting a precursor group into a carboxyl group by hydrolysis or the like.

As the carboxyl group-containing alicyclic olefin monomer used in the method (i), 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 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, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxymethyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the acid anhydride group-containing alicyclic olefin monomer used in the method (i) include bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid anhydride, tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-ene-11,12-dicarboxylic acid anhydride and the like.

  Moreover, as an alicyclic olefin monomer which does not have a carboxyl group etc. which are used as needed in the method of (i), the alicyclic olefin weight which does not have a carboxyl group etc. which are used for the method of the following (ii) The thing similar to the monomer for obtaining a coalescence is mention | raise | lifted.

Specific examples of the monomer for obtaining an alicyclic olefin polymer having no carboxyl group and the like used in the method (ii) 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 [4.3.0] .1 ^2,5] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^2,8 ] tetradeca-3,5,7,12,11-tetraene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  Examples of the carbon-carbon unsaturated bond-containing compound having a carboxyl group used in the method (ii) include acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethylacrylic acid, 2-hydroxyethylmethacrylic acid. , Maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] hept-5-ene Unsaturated carboxylic acid compounds such as -2,3-dicarboxylic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, and citraconic anhydride; .

As the norbornene-based monomer containing a carboxyl group precursor used in the method (iii), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2 -Ene etc. are mentioned.

  The alicyclic olefin polymer may further have a functional group other than a carboxyl group or the like (hereinafter sometimes referred to as “other functional group”). Examples of other functional groups include an alkoxycarbonyl group, a cyano group, a hydroxyl group, an epoxy group, an alkoxyl group, an amino group, an amide group, and an imide group. The amount of these other functional groups is preferably 30 mol% or less, more preferably 10 mol% or less, and particularly preferably 1 mol% or less with respect to the carboxyl group or the like.

  Although the glass transition temperature (Tg) of the alicyclic olefin polymer used for this invention is not specifically limited, It is preferable that it is 120-300 degreeC. If the Tg is too low, the resulting electrical insulation layer cannot maintain sufficient electrical insulation at high temperatures, and if the Tg is too high, the multilayer circuit board will crack when subjected to a strong impact, causing damage to the conductor layer. there's a possibility that.

The alicyclic olefin polymer used in the present invention is electrically insulating.
The volume resistivity according to ASTM D257 of the alicyclic olefin polymer is preferably 1 × 10 ¹² Ω · cm or more, more preferably 1 × 10 ¹³ Ω · cm or more, and 1 × 10 ¹⁴ Ω · cm. It is especially preferable that it is cm or more.

(2) Curing Agent The curing agent used in the present invention is not limited as long as it can crosslink the alicyclic olefin polymer by heating. Especially, when an alicyclic olefin polymer contains a carboxyl group etc., the compound which can react with a carboxyl group etc. and can form a crosslinked structure is preferable.

  Examples of such curing agents include polyvalent epoxy compounds, polyvalent isocyanate compounds, polyvalent amine compounds, polyvalent hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides. These curing agents can be used alone or in combination of two or more. Peroxides can also be used as curing agents.

  Examples of the polyvalent epoxy compound include 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, a brominated bisphenol A type epoxy compound, and a brominated bisphenol F. Type epoxy compounds, glycidyl ether type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds; polycyclic epoxy compounds such as alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds; etc. And compounds having two or more epoxy groups in the molecule.

  As the polyvalent isocyanate compound, diisocyanates and triisocyanates having 6 to 24 carbon atoms are preferable. Examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, etc. Is mentioned. Examples of triisocyanates include 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, and the like.

  Examples of the polyvalent amine compound include aliphatic polyvalent amine compounds having 4 to 30 carbon atoms having two or more amino groups, aromatic polyvalent amine compounds, etc., 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, N, N′-dicinnamylidene-1,6-hexanediamine, and the like.
Examples of 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.

  Examples of 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.

  Examples of the aziridine compound include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) aziridinyl] phosphinoxide, hexa [1- (2-methyl) aziridinyl. And triphosphatriazine.

  Examples of the peroxide include known organic peroxides such as ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide, diacyl peroxide, peroxyester, and peroxydicarbonate.

  Among these curing agents, a polyhydric epoxy compound is preferred because of its mild reactivity with the alicyclic olefin polymer and easy processing and lamination of the resulting molded product or composite. Bisphenol A bis (Propylene glycol glycidyl ether) Bisphenol A type epoxy compounds such as ether and glycidyl ether type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds are more preferred.

  The usage-amount of a hardening | curing agent is 1-100 weight part normally with respect to 100 weight part of alicyclic olefin polymers, Preferably it is 5-80 weight part, More preferably, it is the range of 10-50 weight part.

(3) Porous silica agglomerated particles The porous silica agglomerated particles used in the present invention have one or more diffraction lines in a diffraction angle range (2θ / °) corresponding to a lattice spacing (d) of 1 nm or more. The porous silica aggregated particles are formed by aggregating porous silica spherical primary particles exhibiting a line diffraction pattern so as to form a void layer between these porous silica spherical primary particles.

The X-ray diffraction pattern of the porous spherical silica primary particles has one or more diffraction lines in a diffraction angle range (2θ / °) corresponding to a lattice spacing (d) of 1 nm or more.
The diffraction lines appearing on the X-ray diffraction pattern mean that the porous silica spherical primary particles have a periodic structure having a d value (lattice spacing) corresponding to the diffraction angle (2θ / °) of the diffraction lines. Therefore, “having one or more diffraction lines in the range of the diffraction angle (2θ / °) corresponding to the lattice spacing (d) of 1 nm or more” means that the pores are regular or oriented at intervals of 1 nm or more. Will have.

FIG. 1 is a field emission scanning electron microscope (FE-SEM) image showing porous silica aggregated particles, and FIG. 2 is a field emission scanning electron microscope (FE-SEM) obtained by enlarging a rectangular region in FIG. FIG. 3 is a field emission scanning electron microscope (FE-SEM) image showing the porous silica spherical primary particles constituting the porous silica aggregated particles of the present invention.
1 and 2, it can be seen that void layers (dotted black portions in FIG. 2) are formed between the porous silica spherical primary particles.
Moreover, according to FIG. 3, it turns out that many pores (dotted black part in FIG. 3) are formed in the porous silica spherical primary particles.

Porous silica agglomerated particles are prepared by preparing silica spherical primary particles and agglomerating the silica spherical primary particles without going through the pulverization and pulverization steps, and then making the particles porous. Is done.
The method for preparing the silica spherical primary particles is not particularly limited. For example, using a basic catalyst and a surfactant, a colloidal silica fine particle slurry filled with the surfactant in an oriented state is prepared, and this is fired. Alternatively, spherical primary particles having pores having regularity or orientation can be obtained by extracting and removing the surfactant using a solvent. Details of this method are described in JP-A-2005-213122.

The colloidal silica fine particle slurry is preferably in a state in which the colloidal silica fine particles are dispersed. When the primary particles settle over time, an appropriate dispersant or the like is added to maintain dispersibility. Alternatively, the dispersion may be stabilized by substituting the solvent.
As a method of agglomerating the prepared silica spherical primary particles, the silica spherical primary particles are aggregated and settled by adding a polymer flocculant or the like to the dispersion containing the silica spherical primary particles, and the obtained precipitate is In addition to the method of drying after filtration and recovery, freeze drying, spray drying, and the like are applicable, and although not particularly limited, spraying is possible in that the silica spherical primary particles can be dried, aggregated and granulated simultaneously. A dry method is preferred.

  The spray drying method is a method in which a slurry containing silica spherical primary particles is made into fine mist-like droplets, and the fine droplets are blown into hot air to instantaneously dry the slurry. In order to obtain porous silica aggregated particles by agglomerating silica spherical primary particles, there are centrifugal spraying by a disk (rotary disk) in which a large number of ejection holes are formed and pressure spraying by a pressure nozzle. Pressure spraying with a pressure nozzle is preferred.

  By applying this spray drying method, it becomes possible to simultaneously dry, agglomerate and granulate the silica spherical primary particles. Therefore, silica agglomerated particles in which silica spherical primary particles are aggregated can be easily obtained without going through a pulverization step such as pulverization and pulverization, which is a conventional powder technology.

Since the silica agglomerated particles thus obtained contain a surfactant, the silica agglomerated particles are regularly baked or extracted with a solvent to remove the contained surfactant. In addition, porous silica agglomerated particles obtained by aggregating porous silica spherical primary particles having pores having orientation or orientation can be formed, and a void layer can be formed between these porous silica spherical primary particles.
As described above, the particle size, pore size and shape of the silica primary particles are controlled, and the pore volume, pore size and shape are controlled without going through conventional powder technology such as pulverization and pulverization. Silica agglomerated particles can be obtained.

The porous silica aggregated particles are characterized in that the pore volume and the pore diameter are controlled. The pore volume and pore diameter can be determined by a nitrogen adsorption method.
More specifically, it is preferable that the pore volume by a nitrogen adsorption method when the pore diameter is 50 nm or less is 1.5 mL / g or more and the pore volume fraction having a pore diameter of 5 nm or less is 0.4 or more. .

The pore volume and pore diameter can be determined by calculating the pore diameter distribution by the DH (Dollimore-Heal) method from the isothermal adsorption curve measured by the BET method by nitrogen adsorption.
Here, when the pore volume is less than 1.5 mL / g, or when the pore volume fraction with a pore diameter of 5 nm or less is less than 0.4 with respect to the pore volume with a pore diameter of 50 nm or less, This is not preferable because the ratio of the pores occupied in the porous silica aggregated particles becomes small and it becomes difficult to hold the void layer in the pores of the porous particles.

In the porous silica aggregated particles, the average pore diameter peak calculated by the DH (Dollimore-Heal) method from the isothermal adsorption curve measured by the BET method is preferably 5 nm or less.
If this average pore diameter peak exceeds 5 nm, the mechanical strength of the primary particles of silica tends to decrease, and the mechanical strength of the curable resin composition tends to decrease.

  By controlling these pore volume, pore volume fraction and average pore diameter peak, it is possible to retain a void layer in the pores in the silica primary particles and in the gaps between the primary particles in various applications. Become.

In the porous silica aggregated particles, the average particle size is preferably 5 μm or less, more preferably in the range of 0.5 μm to 5 μm.
Here, when the average particle diameter exceeds 5 μm, it tends to be unevenly distributed in the curable resin composition, and as a result, various characteristics are likely to be deteriorated.

  If the average particle size is smaller than 0.5 μm, the contact points between the porous silica spherical primary particles constituting the porous silica agglomerated particles are reduced, and there is a possibility that the particle gap may be reduced. More preferred.

In the porous silica agglomerated particles, when the sphericity is represented by the ratio between the average value of the short axis and the average value of the long axis, this ratio is preferably 0.7 or more.
If this ratio is less than 0.7, the shrinkage stress applied during the production of molded articles and composites made of the curable resin composition is not dispersed and cracks are likely to occur. Become.

  In the porous silica aggregated particles, the particle diameter, pore volume, pore diameter and shape of the porous silica primary particles are controlled, and the particle diameter and pores of the porous silica aggregated particles constituted by the porous silica primary particles are controlled. Since the volume, the pore diameter, and the shape are controlled, it is suitable for use in holding a void layer in the pores.

  In the porous silica aggregated particles, a surface treatment layer or a coating layer is formed on the surface of the porous silica aggregated particles, or on the surface of the porous silica spherical primary particles constituting the porous silica aggregated particles. Is preferred.

  Thus, there are two main purposes for forming the surface treatment layer or the coating layer on the surface. The first point is the affinity control in a paint in which a binder component such as an organic polymer is dissolved in water or an organic solvent. The second point is that the void layer is more easily held in the pores in the porous silica aggregated particles. It is to be.

  The material for forming this surface treatment layer or coating layer is not particularly limited, for example, coupling agents such as silane, aluminum, titanate, silicone oil, silicone resin, anionic, cationic, nonionic, Surfactants such as fluorine-based compounds, esterification with hydroxyl groups in various solvents including alcohol, various organic polymers, and the like can be used, and silane coupling agents and silicone oils / resins are particularly preferable.

  For example, as the silane coupling agent, vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-N-phenyl -Amino silane coupling agent such as γ-aminopropyltrimethoxysilane; Epoxy silane coupling agent such as γ-glycidoxypropyltrimethoxysilane; Acryloxy silane coupling agent such as acryloxypropyltrimethoxysilane; Methacryloxy silane coupling agents such as 3-methacryloxypropyltrimethoxysilane; Mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane; Methyltrimethoxysilane, Trimethylmethoxysilane, Decyltriethoxy Examples include alkyl silane coupling agents such as silane and hydroxyethyltrimethoxysilane; silicon compounds having fluorine-containing organic groups such as (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, and the like. it can.

  Examples of the silicone oil include polydimethylsiloxane, and at least one methyl group at the side chain or terminal of the polydimethylsiloxane is hydrogen, alkyl group, cyclohexyl group, phenyl group, benzyl group, amino group, epoxy group, poly group. Modified with one or more groups selected from the group of ether group, carboxyl group, mercapto group, chloroalkyl group, alkyl higher alcohol ester group, alcohol group, aralkyl group, vinyl group and trifluoromethyl group Mention may be made of modified polysiloxanes or mixtures thereof.

Examples of the silicone resin include resins having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent.

The surfactant is not limited to any of anionic, cationic, nonionic, and fluorine, but a cationic surfactant is preferable.
Among the cationic surfactants, ammonium compounds are preferable, and quaternary ammonium salts are particularly preferable.

  Examples of the quaternary ammonium salt include octyltrimethylammonium salt, decyltrimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, hexadecyltrimethylammonium salt, octadecyltrimethylammonium salt, and the like.

In particular, when a surfactant having a catalytic action is used as the surfactant, porous fine particles can be produced without adding a catalyst.
As the surfactant having a catalytic action, an ammonium compound, particularly a quaternary ammonium hydroxide is preferable.

  Examples of the quaternary ammonium hydroxide include octyltrimethylammonium hydroxide, octyltrimethylammonium hydroxide, decyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethyl Ammonium hydroxide or the like is used.

  According to the porous silica agglomerated particles used in the present embodiment, pores are formed in the porous silica spherical primary particles, and a void layer is formed between these porous silica spherical primary particles. The pore diameter, pore volume, shape and particle diameter of the aggregated particles can be controlled to the optimum state.

(4) Curing accelerator It is preferable that the curable resin composition used for this invention further contains a curing accelerator from a viewpoint which can obtain hardened | cured material with high heat resistance easily. For example, when a polyvalent epoxy compound is used as the curing agent, a curing accelerator such as a tertiary amine compound or a boron trifluoride complex compound is preferably used. Among these, the use of a tertiary amine compound is preferable because the lamination property, insulation resistance, heat resistance, chemical resistance and the like for fine wiring are improved.

  As tertiary amine compounds, chain tertiary amine compounds such as benzylmethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide; pyrazoles, pyridines, pyrazines, pyrimidines, indazoles , Nitrogen-containing heterocyclic compounds such as quinolines, isoquinolines, imidazoles, and triazoles; Among these, imidazoles, particularly substituted imidazole compounds having a substituent are preferable.

  Examples of substituted imidazole compounds include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, and 2,4-dimethyl. Alkyl-substituted imidazole compounds such as imidazole and 2-heptadecylimidazole; 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 ′-(3 ″, 5 ″ -diaminotriazinyl) ethyl] imidazole, 1-benzyl-2-phenylimidazole, etc. Carbonization with a ring structure such as aryl or aralkyl groups Imidazole compounds substituted with a containing group; and the like. These curing accelerators can be used singly or in combination of two or more. Among these, an imidazole compound substituted with a hydrocarbon group having a ring structure is preferable, and 1-benzyl-2-phenylimidazole is particularly preferable.

  Although the compounding quantity of a hardening accelerator is suitably set according to a use purpose, Preferably it is 0.001-30 weight part with respect to 100 weight part of alicyclic olefin polymers, More preferably, it is 0.01-10 weight. Parts, more preferably 0.03 to 5 parts by weight.

(5) Flame retardant For the purpose of improving the flame retardancy of a cured product obtained by curing the curable resin composition of the present invention, the curable resin composition may further contain a flame retardant.

  As the flame retardant to be used, a halogen-free flame retardant that generates little harmful substances during incineration is preferable. Specific examples of the halogen-free flame retardant include antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate; aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine sulfamate, zirconium compound, molybdenum compound, aluminum borate Inorganic flame retardants such as tin compounds; organometallic compounds such as ferrocene; phosphate esters, aromatic condensed phosphate esters, phosphazene compounds, phosphorus-containing epoxy compounds, reactive phosphorus compounds, ammonium polyphosphate, melamine phosphate, polyphosphorus And phosphorous flame retardants such as melamine salt of polyphosphate, melam salt of polyphosphate, melem salt of polyphosphate, double salt of melamine, melam, and melem polyphosphate, red phosphorus, and phosphazene compound. Of these, magnesium hydroxide, aluminum hydroxide, phosphazene compounds, melamine phosphate, melamine polyphosphate, melam salt polyphosphate, and melem salt polyphosphate are preferred, especially for improving heat resistance, moisture resistance and flame retardancy. From the viewpoint of superiority, magnesium hydroxide and melamine / melam / melem double salt polyphosphate are preferable.

(6) Laser processability improver The curable resin composition of the present invention may further contain a laser processability improver for the purpose of further improving the laser processability of the cured product. Examples of the laser processability improver include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole.

(7) Filler, Additive The curable resin composition of the present invention further contains an amount of filler or additive in a range that does not impair the original properties for the purpose of imparting desired performance according to its use. You may do it.

  Examples of the filler used include carbon black, alumina, barium titanate, talc, mica, glass beads, and glass hollow spheres. Further, silica other than the porous silica aggregated particles, for example, commercially available silica particles may be used.

  Additives include soft polymer, heat stabilizer, weather stabilizer, anti-aging agent, leveling agent, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, natural oil, synthetic oil , Wax, emulsion, magnetic material, dielectric property adjusting agent, toughening agent and the like.

(8) Production of curable resin composition The curable resin composition of the present invention includes the alicyclic olefin polymer, a curing agent, and porous silica aggregated particles, and further includes a curing accelerator and a flame retardant as necessary. , Laser workability improver, other fillers, additives. These components may be mechanically mixed by an extruder or the like, but are usually used as a varnish (curable resin varnish) dissolved or dispersed in an organic solvent.

  As an organic solvent used for preparation of a varnish, a thing with a boiling point of 30-250 degreeC is preferable, and a 50-200 degreeC thing is more preferable. When an organic solvent having a boiling point in such a range is used, it is suitable for heating and volatilizing and drying later.

  Specific examples of such organic solvents include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and trimethylbenzene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; cyclopentane and cyclohexane And alicyclic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone;

  The amount of the organic solvent used is appropriately selected according to the thickness and surface flatness of the desired molded article, but the solid content concentration of the varnish is usually from 5 to 70% by weight, preferably from 10 to 65% by weight. Preferably it is the range which becomes 20 to 60 weight%.

  There is no special limitation in the preparation method of a varnish, For example, an alicyclic olefin polymer, a hardening | curing agent, a porous silica aggregated particle polymer, and the arbitrary component mix | blended as needed may be mixed in accordance with a conventional method.

Examples of the mixer used for mixing include a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, and a three-roller.
The mixing temperature is preferably in the range where no curing reaction is caused by the curing agent and not more than the boiling point of the organic solvent.

(B) Molded body The molded body according to the present invention is obtained by molding the curable resin composition into a film or a sheet. Specifically, the varnish is applied on a support and dried to obtain a molded body.

  Examples of the support include a resin film and a metal foil. Examples of the resin film include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, and a nylon film. Among these films, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable from the viewpoints of heat resistance, chemical resistance, peelability, and the like. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil. Among these, a copper foil, particularly an electrolytic copper foil or a rolled copper foil is preferable from the viewpoint of good conductivity.

  Although there is no restriction | limiting in the thickness of a support body, from viewpoints of workability | operativity etc., it is 1-150 micrometers normally, Preferably it is 2-100 micrometers, More preferably, it is 5-80 micrometers.

  The surface average roughness Ra of the support is usually 300 nm or less, preferably 150 nm or less, more preferably 100 nm or less. If the surface average roughness Ra of the support is too large, the surface average roughness Ra of the electrically insulating layer formed by curing the resulting molded body increases, and it becomes difficult to form a fine wiring pattern as a conductor layer. .

  The method for applying the varnish to the support is not particularly limited. For example, known coating methods such as dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating can be used.

  The drying conditions for the varnish are appropriately selected depending on the type of organic solvent. Specifically, the drying temperature is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds and the resulting molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

The thickness of the molded body is not particularly limited and is appropriately selected depending on the application of the molded body, but is usually 1 to 150 μm, preferably 3 to 100 μm, and more preferably about 5 to 80 μm. Moreover, the thickness of a coating film can be suitably set to the usage-amount of the organic solvent in a varnish. When forming a thick film, use less organic solvent and use a higher viscosity varnish. When using a thinner film, use less organic solvent and use a higher viscosity. A varnish may be used.
The molded body formed on the support may be used as it is, or may be used after being peeled from the support.

(C) Composite The composite of the present invention contains the curable resin composition and a fiber base material. Specific examples of such a composite include a prepreg obtained by filling a varnish containing a curable resin composition into a gap of a fiber base material and drying it. As the fiber substrate, inorganic and / or organic fibers can be used. For example, glass fiber, metal fiber, ceramic fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, poly Examples include known liquid crystal fibers such as arylate. These can be used alone or in combination of two or more. Examples of the shape of the fiber base material include mats, cloths, and nonwoven fabrics. Moreover, it is preferable that the above-mentioned support body is stuck on the single side | surface of a fiber base material.

  In order to impregnate a fiber base material with a varnish, for example, a predetermined amount of varnish is poured onto the fiber base material, and a protective film is stacked on the fiber base material as necessary, and pressed from above with a roller or the like. Can do. Then, it dries on the same conditions as the above-mentioned compact, and the composite of the present invention is obtained.

  The molded body and composite of the present invention are excellent in flame retardancy, electrical insulation and crack resistance, and hardly generate harmful substances during incineration. Therefore, it is particularly suitable as a material for forming an electrical insulating layer of a multilayer circuit board.

(D) Hardened | cured material The hardened | cured material of this invention is obtained by hardening | curing the molded object or composite_body | complex of this invention mentioned above (Hereafter, these may be described only as "a molded object etc."). Curing of the molded body or the like is performed by heating.

  Curing conditions are appropriately selected according to the type of curing agent. The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

  Prior to curing, it is preferable to provide a step of bringing a compound having metal coordination ability into contact with a molded body and the like, and then washing with a good solvent of these compounds such as water. By this step, the surface of the molded body and the like can be smoothed, and the adhesion with the metal thin film coated thereon in the subsequent step can be improved. Examples of the compound having metal coordination ability include imidazoles such as 1- (2-aminoethyl) -2-methylimidazole; pyrazoles; triazoles; triazines;

  The cured product of the present invention is obtained by curing the above molded body, etc., has a low relative dielectric constant, excellent flame retardancy, electrical insulation and crack resistance, and generates harmful substances during incineration. It is hard to do. Therefore, it is suitable as an electrical insulating layer of a multilayer circuit board used particularly in a high frequency region.

(E) Laminate The laminate of the present invention is formed by laminating a substrate having a conductor layer (I) on the surface and an electrically insulating layer made of the cured product of the present invention.

(1) Substrate The substrate used in the present invention has a conductor layer (I) 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, acrylic resin, methacrylic resin, diallyl phthalate resin, triazine resin, polyphenyl ether, glass, etc.). It is formed by curing a curable resin composition.

(2) Conductor layer (I)
The conductor layer (I) is not particularly limited, but is usually a layer including wiring formed of a conductor such as a conductive metal, and may further include various circuits. Further, the configuration and thickness of the wiring and circuit are not particularly limited.

  Specific examples of the substrate having the conductor layer (I) on the surface include a printed wiring board and a silicon wafer substrate. The thickness of the substrate having the conductor layer (I) on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, more preferably 30 μm to 2 mm.

  The substrate having the conductor layer (I) 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.

  As a pretreatment method, a known technique is not particularly limited and can be used. For example, if the conductor layer (I) 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 surface of the conductor layer, and then the conductor is formed. A method in which the surface of the layer is oxidized by the above method and then reduced with sodium borohydride, formalin, etc., a method in which the conductor layer (I) is plated and roughened, and an organic acid is brought into contact with the conductor layer (I). Examples include a method in which copper grain boundaries are eluted and roughened, and a method in which a primer layer is formed on the conductor layer (I) with a thiol compound, a silane compound, or the like.

  Among these, from the viewpoint of easy maintenance of the shape of a fine wiring pattern, a method of bringing an organic acid into contact with the conductor layer (I) to elute and roughen the copper grain boundaries, and a thiol compound or a silane compound A method of forming the primer layer by, for example, is preferable.

(3) Manufacture of a laminated body The laminated body of this invention can be manufactured by thermocompression-bonding the said molded object etc. on the board | substrate which has conductor layer (I) on the surface, and hardening and forming an electrically insulating layer.

  As a specific example of the thermocompression bonding method, a molded body or the like is laminated so as to be in contact with the conductor layer (I) of the substrate, and a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like is used. And a method of thermocompression bonding (lamination). By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer (I) on the surface of the substrate and the molded body. In addition, when a metal foil is used as a support such as a molded body, the adhesion between the molded body and the metal foil is improved, so that the metal foil is used as it is as a conductor layer (I) of a multilayer circuit board described later. be able to.

  The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., and the applied pressure is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa. The thermocompression bonding time is usually 30 seconds to 5 hours, 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 of the atmosphere in which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

  Curing of the molded body or the like is usually performed by heating the entire substrate on which the molded body or the like is formed on the conductor layer (I). Curing can be performed simultaneously with the thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature for a short time.

  Further, for the purpose of improving the flatness of the electrical insulating layer or increasing the thickness of the electrical insulating layer, two or more molded bodies or the like may be bonded and laminated on the conductor layer (I) of the substrate. Good.

(F) Multilayer circuit board and method for producing the same The multilayer circuit board of the present invention is formed by further forming a conductor layer (II) on the electrical insulating layer of the laminate of the present invention described above.

  In the multilayer circuit board of the present invention, when a resin film is used as a support for a molded body or the like in the production of the laminated body, after peeling the resin film, the conductor layer (II ). When a metal foil is used as a support such as a molded body, the metal foil can be produced by etching the metal foil into a pattern by a known etching method and further forming a conductor layer (II). In the present invention, the former method is preferred.

  Hereinafter, a method for producing the multilayer circuit board of the present invention by forming the conductor layer (II) on the electrical insulating layer by plating will be specifically described.

  First, in manufacturing a multilayer circuit board, normally, before forming the conductor layer (II), via holes penetrating the laminate are formed in order to connect the conductor layers in the multilayer circuit board.

  The via hole can be formed by chemical processing such as photolithography, or physical processing such as drilling, laser, or plasma etching. Among these methods, a method using a laser (a carbon dioxide gas laser, an excimer laser, a UV-YAG laser, or the like) is preferable because a finer via hole can be formed without degrading the characteristics of the electrical insulating layer.

  Next, in order to improve the adhesiveness with the conductor layer (II), the surface of the electrical insulating layer is oxidized and roughened, and adjusted to a desired average surface roughness.

In the present invention, the surface average roughness Ra of the electrical insulating layer is 0.05 μm or more and less than 0.3 μm, preferably 0.06 μm or more and 0.2 μm or less, and the surface ten-point average roughness Rzjis is 0.3 μm or more and less than 4 μm. The thickness is preferably 0.5 μm or more and 2 μm or less.
Here, Ra is the centerline average roughness shown in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.

The electrical insulating layer surface can be oxidized by bringing the electrical insulating layer surface into contact with the oxidizing compound.
Examples of the oxidizing compound to be used include known compounds having an oxidizing ability such as inorganic peroxides and organic peroxides; gas; In view of easy control of the average surface roughness of the electrical insulating layer, it is particularly preferable to use an inorganic peroxide or an organic peroxide.

Specific examples of inorganic peroxides include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, Examples include ozone.
Specific examples of the organic peroxide include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid and the like.

  There is no particular limitation on the method of oxidizing the surface of the electrical insulating layer using an inorganic peroxide or an organic peroxide. For example, 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.

  There is no particular limitation on the method of bringing the inorganic peroxide or organic peroxide or these solutions into contact with the surface of the electrical insulating layer. For example, a dipping method in which the electrical insulating layer is immersed in an oxidizing compound solution, an oxidizing compound solution Any method may be used, such as a liquid filling method in which a surface tension is applied to an electric insulating layer, or a spray method in which a solution of an oxidizing compound is sprayed onto a substrate.

  The temperature and time for bringing these inorganic peroxides and organic peroxides into contact with the surface of the electrical insulating layer may be arbitrarily set in consideration of the concentration and type of peroxide, the contact method, and the like. The said temperature is 10-250 degreeC normally, Preferably it is 20-180 degreeC, and the said time is 0.5-60 minutes normally, Preferably it is 1-30 minutes.

  Examples of the method for oxidizing using gas include plasma treatment for radical or ionization of gas such as reverse sputtering and corona discharge. Examples of the gas include air, oxygen, nitrogen, argon, water, carbon disulfide, and carbon tetrachloride.

When the gas for oxidation treatment is liquid at the treatment temperature but becomes gas under reduced pressure, the oxidation treatment is performed under reduced pressure.
When the gas for oxidation treatment is a gas at the treatment temperature and pressure, the oxidation treatment is performed after radicalizing or ionizing the gas by an appropriate means.

  The temperature and time for bringing the plasma into contact with the surface of the electrical insulating layer may be set in consideration of the type and flow rate of the gas. The contacting temperature is usually 10 to 250 ° C., preferably 20 to 180 ° C., and the contacting time is usually 0.5 to 60 minutes, preferably 1 to 30 minutes.

  Further, when the surface of the electrical insulating layer is oxidized using an oxidizing compound solution, the curable resin composition constituting the electrical insulating layer contains a polymer or an inorganic filler that is soluble in the oxidizing compound solution. It is preferable to keep it. Since the inorganic filler and the alicyclic olefin polymer are selectively dissolved after forming a fine sea-island structure, it is easy to control the surface roughness of the insulating layer within the above-described range.

  Examples of the polymer soluble in the solution of the oxidizing compound include liquid epoxy resin, polyester resin, bismaleimide-triazine resin, silicone resin, polymethylmethacrylate resin, natural rubber, styrene rubber, isoprene rubber, butadiene Examples thereof include rubber, nitrile rubber, ethylene rubber, propylene rubber, urethane rubber, butyl rubber, silicone rubber, fluorine rubber, norbornene rubber, and ether rubber.

  There is no particular restriction on the blending ratio of the polymer soluble in the solution of the oxidizing compound, usually 1 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer. Preferably it is 5-20 weight part.

  Examples of inorganic fillers soluble in oxidizing compound solutions include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina , Magnesium hydroxide, aluminum hydroxide, barium sulfate, talc, clay and the like. Further, silica other than the porous silica aggregated particles, for example, commercially available silica particles may be used. Among these, calcium carbonate and silica are easy to obtain fine particles and are easily eluted with a filler-soluble aqueous solution, and are suitable for obtaining a fine rough surface shape. These inorganic fillers may be treated with a silane coupling agent or an organic acid such as stearic acid.

The added inorganic filler is preferably non-conductive so as not to deteriorate the dielectric properties of the electrical insulating layer.
Further, the shape of the added inorganic filler is not particularly limited, and may be spherical, fibrous, plate-like, or the like, but in order to obtain a fine rough surface shape, it may be a fine powder. preferable.

  The average particle size of the inorganic filler used is usually 0.008 μm or more and less than 2 μm, preferably 0.01 μm or more and less than 1.5 μm, particularly preferably 0.02 μm or more and less than 1 μm. If the average particle size is too small, there is a possibility that uniform adhesion cannot be obtained on a large substrate, and conversely, if it is too large, a large rough surface is generated in the electrical insulating layer, and a high-density wiring pattern may not be obtained. There is sex.

  The amount of the inorganic filler soluble in the solution of the oxidizing compound is appropriately selected according to the required degree of adhesion, but is usually 1 to 100 parts by weight of the alicyclic olefin polymer. 80 parts by weight, preferably 3 to 60 parts by weight, more preferably 5 to 40 parts by weight.

  Polymers and inorganic fillers that are soluble in such an oxidizable compound solution include flame retardant aids, heat stabilizers, dielectric property modifiers, toughness that are optionally added to the curable resin composition used in the present invention. It may be part of the agent.

  After the oxidation treatment of the electrical insulating layer, the surface of the electrical insulating layer is usually washed with water in order to remove the oxidizing compound. If a substance that cannot be cleaned with water alone is attached, wash the substance further with a cleaning solution that can be dissolved, or make it a water-soluble substance by bringing it into contact with other compounds, and then wash with water. To do. For example, when an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the electrical insulating layer, a mixed solution of hydroxyamine sulfate and sulfuric acid for the purpose of removing the generated manganese dioxide film, etc. It can wash | clean with water, after neutralizing-reducing process with the acidic aqueous solution of this.

After the electrical insulating layer is oxidized to adjust the surface average roughness, the conductor layer (II) is formed on the surface of the electrical insulating layer and the inner wall surface of the via hole.
Although it does not specifically limit as a formation method of conductor layer (II), The plating method is preferable from a viewpoint of forming conductor layer (II) excellent in adhesiveness.

  Although there is no particular limitation on the method of forming the conductor layer (II) by plating, for example, a method of forming a metal thin film on the electrical insulating layer by plating or the like and then growing the metal layer by thick plating is employed.

  When forming a metal thin film by electroless plating, it is common to deposit catalyst nuclei such as silver, palladium, zinc and cobalt on the electrical insulation layer before forming the metal thin film on the surface of the electrical insulation layer. It is.

  The method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited. For example, 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 of the method include a method of reducing a metal after being immersed in a solution (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved at a concentration of 10 to 10% by weight.

  As the 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 and the like are not particularly limited.

  For example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution using dimethylamine borane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a 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.

  After forming the metal thin film, the substrate surface can be brought into contact with a rust preventive agent to carry out a rust prevention treatment. Moreover, after forming a metal thin film, a metal thin film can also be heated for the adhesive improvement etc. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C.

  Heating may be performed under pressurized conditions. As 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 the metal thin film is formed by etching. The conductor layer (II) is formed by etching in a pattern. Therefore, the conductor layer (II) formed by this method is usually composed of a patterned metal thin film and plating grown thereon.

  Using the multilayer circuit board obtained as described above as a new laminate, by repeating the steps of forming the electrical insulating layer and the conductor layer (II) described above, further multilayering can be performed. Thereby, a desired multilayer circuit board can be obtained.

  The multilayer circuit board of the present invention is excellent in adhesion between the electrical insulating layer and the conductor layer (II). The peel strength measured according to JIS C6481 between the conductor layer (II) and the electrical insulating layer in the multilayer circuit board of the present invention is usually 6 N / cm or more, preferably 8 N / cm or more.

  The multilayer circuit board of the present invention is excellent in crack resistance. When the multilayer circuit board of the present invention was tested according to JIS Z2247 Eriksen test A method, the distance (Erichsen value) that the punch tip moved from the wrinkle holding surface when the surface of the board was cracked was usually It is 4 mm or more, preferably 5 mm or more.

  Since the multilayer circuit board of the present invention has excellent electrical characteristics, as will be described later, it is suitable as a substrate for semiconductor elements such as CPU and memory and other mounting parts in electronic devices such as computers and mobile phones. Can be used.

(G) Electronic device An electronic device according to the present invention includes the multilayer circuit board according to the present invention described above.
The electronic device 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), pager. , A word processor, a television, a viewfinder type or a monitor direct-view type video tape recorder, an electronic notebook, an electronic desk calculator, a car navigation device, a POS terminal, a device equipped with a touch panel, and the like.

  Since the electronic device of the present invention includes the multilayer circuit board of the present invention, it is a high-performance and high-quality electronic device.

(Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are mass references | standards unless there is particular notice.

  In addition, the definition and evaluation method of each characteristic are as follows.

(1) Number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer
The polymer not subjected to the modification reaction was measured by gel permeation chromatography (GPC) using toluene as a developing solvent, and the polymer subjected to the modification reaction was determined as a polystyrene equivalent value using tetrahydrofuran as a developing solvent.

(2) Hydrogenation rate of polymer The hydrogenation rate refers to the ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation. ¹ H-NMR spectrum measurement Determined by

(3) Maleic anhydride residue content of polymer The ratio of the number of moles of acid anhydride groups to the total number of monomer units in the polymer was determined by ¹ H-NMR spectrum measurement.

(4) Glass transition temperature (Tg) of polymer
The temperature was measured at 10 ° C./min by a differential scanning calorimetry (DSC method).

(5) Volume resistivity of polymer Measured based on ASTM D257.

(6) Electrical characteristics of the molded product (dielectric constant)
A part of the molded body with a support produced in Examples and Comparative Examples was cut out, laminated on one side of a rolled copper foil having a thickness of 75 μm, and the polyethylene terephthalate film as a support was peeled off, and then at 60 ° C. in a nitrogen atmosphere. The molded body was cured by heating for 30 minutes and then by heating at 170 ° C. for 60 minutes. Subsequently, the rolled copper foil was all removed by etching with a cupric chloride / hydrochloric acid mixed solution to obtain a sheet-like cured product. A test piece having a width of 2.0 mm, a length of 80 mm, and a thickness of 30 μm was cut out from the obtained cured product, and the relative dielectric constant was measured at 10 GHz using a cavity resonator perturbation method dielectric constant measuring device, and judged according to the following criteria. did.

A: The relative dielectric constant is less than 2.2 B: The relative dielectric constant is 2.2 or more and less than 2.5 C: The relative dielectric constant is 2.5 or more

(7) Circuit patternability With respect to 50 wiring patterns formed on the electrical insulating layer of the evaluation board manufactured in the example and the comparative example, 50 of which all are not disturbed in shape A, and the shape is disturbed An evaluation was made with B but no defect, and C with a defect.

(8) Interlayer insulation reliability After forming an electrode on the electrical insulating layer of the evaluation board manufactured in the example and the comparative example, under the condition of 135 ° C. and 85% humidity with a DC voltage of 5.5 V applied. After standing for 200 hours, the electrical resistance value was measured. The case where there was no short circuit for 200 hours or more was evaluated as A, and the case where the short circuit occurred in less than 200 hours was evaluated as C.

The properties of the colloidal silica fine particles and the porous silica aggregated particles were evaluated as follows.
(Diffraction angle)
Using a freeze dryer, moisture contained in the colloidal silica fine particle slurry prepared below was removed, and the obtained powder was fired at 550 ° C. for 5 hours.
A diffraction angle of the calcined powder was measured using an X-ray diffractometer X'Pert PRO MPD (manufactured by PANalytical) with CuKα rays, output 45 kV, 40 mA, light source slit width 1/16 °, and detection slit width 1/8 °. .

(Measurement of pore volume and average pore diameter)
The calcined powder of colloidal silica fine particles was dried at 200 ° C. for 1 hour, and then its N ₂ gas adsorption isotherm was measured using a constant volume method gas adsorption apparatus BELSORP-mini (manufactured by Nippon Bell Co., Ltd.). From the mesopore pore distribution curve, the pore volume and average pore diameter at pore diameters of 50 nm and 5 nm or less were determined.

(Measurement of average particle size of primary particles)
Porous silica primary particles are obtained by putting 12.00 g of the above-mentioned calcined powder into a sand mill container together with 108.00 g of pure water and 0.1 mmφ glass beads, dispersing at 2500 rpm for 4 hours, and then separating the glass beads. A dispersion was obtained.
Subsequently, the particle diameter of this dispersion was measured using a Microtrac particle size distribution measuring apparatus 9340UPA (Nikkiso Co., Ltd.) to which the laser diffraction scattering method was applied, and the average value was taken as the average particle diameter of primary particles.

(Evaluation of sphericity of primary particles)
TEM image (20,000 times) of porous silica primary particles was taken using a transmission electron microscope H-800 (manufactured by Hitachi, Ltd.), and this image was analyzed using image analysis particle size distribution measurement software Mac View ver.4 (Mounttech) The ratio of the average value of the minor axis to the average value of the major axis of the obtained statistical data was defined as sphericity.

(Evaluation of average particle diameter of porous silica aggregated particles)
0.1 g of porous silica agglomerated particles was added to 10.0 g of pure water, and then dispersed using an ultrasonic disperser to obtain a slurry. Next, the particle size of this slurry was measured using a Microtrac particle size distribution analyzer 9340UPA (manufactured by Nikkiso Co., Ltd.), and the average value was taken as the average particle size of the porous silica aggregated particles.

(Evaluation of sphericity of porous silica aggregated particles)
An image (200x or 2000x) of porous silica aggregated particles was taken using a field emission scanning microscope S-4000 (manufactured by Hitachi, Ltd.), and this image was analyzed using image analysis type particle size distribution measurement software Mac View ver. .4 (manufactured by Mountec Co., Ltd.), and the ratio of the average value of the minor axis to the average value of the major axis in the obtained statistical data was defined as the sphericity.

Example 1
(Production of alicyclic olefin polymer (COP))
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter abbreviated as ETD) is added with 1-butene as a molecular weight regulator for ring-opening polymerization, and then hydrogenated to perform ETD ring-opening hydrogenation polymerization. Coalescence was obtained. The obtained ETD ring-opening hydrogenated polymer had Mn of 31,200, Mw of 55,800, and Tg of 140 ° C. The hydrogenation rate was 99% or more. Next, 100 parts of the ETD ring-opening hydrogenated polymer, 40 parts of maleic anhydride and 5 parts of dicumyl peroxide were dissolved in 250 parts of t-butylbenzene, and a graft bonding reaction was carried out at 140 ° C. for 6 hours. The reaction solution was poured into 1,000 parts of isopropyl alcohol to precipitate the reaction product, and then dried under vacuum at 100 ° C. for 20 hours and modified with maleic anhydride (hereinafter referred to as “COP”). Is sometimes described). Mn of COP was 33,200, Mw was 68,300, Tg was 170 ° C., and the maleic anhydride residue content was 25 mol%. The volume resistivity was 1 × 10 ¹⁴ Ω · cm or more.

(Preparation of porous silica spherical primary particles)
64.0 g of n-hexadecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 1 L of pure water. Next, while stirring the aqueous solution, anion exchange resin (Diaion SA10A: manufactured by Mitsubishi Chemical Corporation) was added until the pH became constant, and ion exchange was performed. Subsequently, this aqueous solution was passed through the column at a space velocity of 2 to separate the anion exchange resin, and a 0.2 mol / kg n-hexadecyltrimethylammonium hydroxide aqueous solution was obtained. The pH of this aqueous solution was 12.7, and the chlorine ion concentration was 1.0 g / L.

Further, 5.4 g of ammonium chloride (manufactured by Kanto Chemical Co., Inc.) was dissolved in 390.4 g of pure water to obtain an ammonium chloride aqueous solution.
Next, 500.0 g of the above n-hexadecyltrimethylammonium hydroxide aqueous solution was added to this aqueous ammonium chloride solution, and the mixture was stirred for 15 minutes. The pH of the obtained solution was 9.0.

  Next, while stirring this solution at 30 ° C., 104.0 g of tetraethoxysilane (manufactured by Kanto Chemical Co., Inc.) is dropped at about 5 mL / second by a tube pump, and stirred for 24 hours while maintaining the temperature at 30 ° C. after completion of the dropping. As a result, a colloidal silica fine particle slurry filled with the surfactant aligned was prepared. The silica solid content in the slurry was 3% by weight.

Next, a part of the colloidal silica fine particle slurry was taken out, water contained in the colloidal silica fine particle slurry was removed using a freeze dryer, and the obtained powder was fired at 550 ° C. for 5 hours.
This fired powder had a peak at a diffraction angle corresponding to a d value of 4.8 nm.
The pore volume when the pore diameter is 50 nm or less is 1.54 mL / g, the pore volume when the pore diameter is 5 nm or less is 0.82 mL / g, the pore volume fraction when the pore diameter is 5 nm or less is 0.53, and the average pore diameter peak is It was 3 nm.
The average particle diameter of the porous spherical silica primary particles was 82 nm.
The sphericity of the porous silica spherical primary particles was 0.95.

(Preparation of porous silica aggregated particles)
The colloidal silica fine particle slurry is spray-dried using a spray drying apparatus for producing fine powder, Micro Mist Dryer MDL-050 (manufactured by Fujisaki Electric Co., Ltd.), and the resulting dried powder is fired at 550 ° C. for 5 hours. Porous agglomerated particles were prepared.
The average particle diameter of the porous silica aggregated particles was 3.7 μm.
The sphericity of the porous silica aggregated particles was 0.92.

(Preparation of silica slurry (1))
20 parts of the above-mentioned porous silica aggregated particles and 80 parts of methyl ethyl ketone were mixed and then subjected to ultrasonic irradiation to obtain silica slurry (1).

(Production of varnish)
100 parts of the above COP as the insulating polymer component, 40 parts of bisphenol A bis (propylene glycol glycidyl ether) ether as the curing agent component, and 2- [2-hydroxy-3,5-bis (α, α) as the laser processability improver -Dimethylbenzyl) phenyl] benzotriazole 5 parts, 1 part of 1-benzyl-2-phenylimidazole as curing accelerator, tris (3,5-di-t-butyl-4-hydroxybenzyl)-as anti-aging agent 1 part of isocyanurate, 40 parts of the above silica slurry (1) in the form of porous silica aggregated particles (in terms of solids), and liquid polybutadiene (Nisseki polybutadiene B-1000 as a polymer soluble in the oxidation treatment liquid): 10 parts of Nippon Petrochemical Co., Ltd., 215 parts of xylene and 54 parts of cyclopentyl methyl ether It was dissolved in Ranaru mixed solvent to obtain a varnish of a curable resin composition.

(Creation of circuit board with wiring pattern)
The varnish obtained above is coated on a polyethylene naphthalate film (support) having a size of 300 mm in length and 300 mm in width with a thickness of 40 μm and a surface average roughness Ra of 0.08 μm using a die coater. did. Subsequently, it dried for 10 minutes at 80 degreeC in nitrogen atmosphere, and the molded object with a support body whose thickness is 40 micrometers was obtained. Table 1 shows the electrical property results of the obtained molded body.

  The core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy resin was coated with 18 μm thick copper, 0.8 mm thickness, 150 mm length × 150 mm width A substrate having a conductor layer on the surface, on which a conductor layer having a wiring width and a distance between wirings of 50 μm, a thickness of 18 μm, and a micro-etched surface by contact with an organic acid is formed on the surface of the double-sided copper-clad substrate Got. The molded body with the support obtained above is cut into a size of 150 mm in length and 150 mm in width, and the molded body with the support is on the inside and the support is on the outside. It was.

  This was depressurized to 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom, and thermocompression bonded at a temperature of 110 ° C. and a pressure of 1.0 MPa for 60 seconds (primary press). Furthermore, using a vacuum laminator provided with heat resistant rubber press plates covered with a metal press plate, the pressure was reduced to 200 Pa and thermocompression bonded at a temperature of 140 ° C. and 1.0 MPa for 60 seconds (secondary press ). Next, the support was peeled off to obtain a substrate having a molded body layer.

  The substrate having this molded body layer was immersed in a 1.0% aqueous solution of 1- (2-aminoethyl) -2-methylimidazole at 30 ° C. for 10 minutes, and then immersed in water at 25 ° C. for 1 minute. Excess solution was removed with an air knife. This was left to stand at 170 ° C. for 60 minutes in a nitrogen atmosphere, and the molded body layer was cured to form an electrical insulating layer.

  The obtained substrate on which the electrical insulation layer was formed was rock-immersed for 10 minutes in a 70 ° C. aqueous solution adjusted to a permanganate concentration of 60 g / liter and a sodium hydroxide concentration of 28 g / liter. Next, the substrate was immersed in a water tank for 1 minute and further immersed in another water tank for 1 minute for washing with water. Subsequently, the substrate was immersed in an aqueous solution at 25 ° C. adjusted to have a hydroxylamine sulfate concentration of 170 g / liter and sulfuric acid of 80 g / liter for 5 minutes, neutralized and reduced, and then washed with water.

  Subsequently, as a pretreatment for plating, the above-mentioned washed substrate is 200 ml / liter of Alcup Activator MAT-1-A (manufactured by Uemura Kogyo Co., Ltd.) and 30 ml / liter of Alcup Activator MAT-1-B (manufactured by Uemura Kogyo Co., Ltd.). Then, it was immersed in a 60 ° C. Pd salt-containing plating catalyst aqueous solution adjusted so that sodium hydroxide was 0.35 g / liter for 5 minutes. Next, the substrate was immersed in a water tank for 1 minute and further immersed in another water tank for 1 minute to be washed with water, and then Alcup Redeuser MAB-4-A (manufactured by Uemura Kogyo Co., Ltd.) was 20 ml / liter. The plating catalyst was subjected to reduction treatment by immersing it in a solution prepared so that Alcap Reducer MAB-4-B (manufactured by Uemura Kogyo Co., Ltd.) was 200 ml / liter at 35 ° C. for 3 minutes. In this manner, a plating catalyst was adsorbed to obtain a substrate subjected to pretreatment for plating.

  Next, the substrate after the plating pretreatment was adjusted so as to be sulcup PSY-1A (manufactured by Uemura Kogyo Co., Ltd.) 100 ml / liter, sulcup PSY-1B (manufactured by Uemura Kogyo Co., Ltd.) 40 ml / liter, and formalin 0.2 mol / liter. Electroless copper plating treatment was performed by dipping for 5 minutes at a temperature of 36 ° C. while blowing air into the aqueous solution.

  The substrate on which the metal thin film layer is formed by the electroless plating process is further immersed in a water tank for 1 minute, and further washed in a water tank for 1 minute by rocking, then dried and subjected to rust prevention treatment. A substrate having an electroless plating film formed on the electrical insulating layer was obtained.

  A commercially available dry film of a photosensitive resist is bonded to the surface of the substrate subjected to the rust prevention treatment by thermocompression bonding. Further, an evaluation pattern (wiring length is 30 μm, wiring length is 30 μm and wiring length is 30 μm). A mask having a pattern corresponding to (50 wiring patterns having a length of 5 cm) was closely contacted and exposed, and then developed to obtain a resist pattern. Next, it was immersed in an aqueous solution of 100 g / liter of sulfuric acid at 25 ° C. for 1 minute to remove the rust preventive, and electrolytic copper plating was applied to the resist non-formed portion to form an electrolytic copper plating film having a thickness of 18 μm. Next, the resist pattern is stripped and removed with a stripping solution, and an etching process is performed with a mixed aqueous solution of cupric chloride and hydrochloric acid to form a wiring pattern composed of the metal thin film and the electrolytic copper plating film. A substrate with a pattern was obtained. Finally, annealing was performed at 170 ° C. for 30 minutes to obtain an evaluation substrate. The obtained evaluation substrate was evaluated for circuit patterning properties and interlayer insulation reliability. The evaluation results are shown in Table 1.

(Example 2)
An experiment similar to that of Example 1 was performed except that the amount of silica slurry (1) used was changed to an amount of 107 parts in the amount of porous silica aggregated particles (in terms of solids). The evaluation results are shown in Table 1.

(Comparative Example 1)
In 85 parts of dry xylene, 15 parts of a porous inorganic filler (average particle size 1.5 μm, pore diameter 20 nm, product name: silica microbead P-500, manufactured by Catalyst Kasei Co., Ltd.) and 128 parts of zirconia beads 1 mm in diameter are zirconia. Fill in a pot, and use a medium planetary mill (P-5, manufactured by Fritsch) to remove centrifugal acceleration 5G [disk rotation speed (revolution speed) 200 rpm, pot rotation speed (rotation speed) 434 rpm], stirring time 5 minutes. Crushing was performed to obtain a silica primary particle slurry.
The same experiment as in Example 1 was performed except that the silica primary particle slurry was used instead of the silica slurry (1). The evaluation results are shown in Table 1.

(Comparative Example 2)
The same experiment as in Example 1 was performed except that the silica slurry (1) was not used. The evaluation results are shown in Table 1.

(Comparative Example 3)
Instead of COP and bisphenol A bis (propylene glycol glycidyl ether) ether in Example 1, 133 parts of epoxy resin (Epicoat 1000, manufactured by Yuka Shell Epoxy Co., Ltd., Mw is 1,300) and 7 parts of dicyandiamide were added. The same experiment as in Example 1 was performed. The evaluation results are shown in Table 1.

Claims (11)

Including an alicyclic olefin polymer, a curing agent, and porous silica aggregated particles,
The porous silica aggregated particles are
Porous silica spherical primary particles exhibiting an X-ray diffraction pattern having one or more diffraction lines in the range of the diffraction angle (2θ / °) corresponding to the lattice spacing (d) of 1 nm or more are used. A curable resin composition, which is porous silica aggregated particles aggregated so as to form a void layer between primary particles.   2. The curable resin composition according to claim 1, wherein the alicyclic olefin polymer has a carboxyl group or an acid anhydride group.   The molded object formed by shape | molding the curable resin composition of Claim 1 or 2 in the shape of a film or a sheet.   The composite_body | complex containing the curable resin composition of Claim 1 or 2, and a fiber base material.   Hardened | cured material formed by hardening | curing the molded object of Claim 3.   Hardened | cured material formed by hardening | curing the composite_body | complex of Claim 4.   The laminated body by which the board | substrate which has a conductor layer on the surface, and the electrically insulating layer which consists of hardened | cured material of Claim 5 or 6 are laminated | stacked.   The method includes a step of heat-pressing the molded body according to claim 3 or the composite body according to claim 4 on a substrate having a conductor layer on a surface, and curing the molded body or the composite body to form an electrical insulating layer. A manufacturing method of a layered product.   A multilayer circuit board obtained by further forming a conductor layer on the electrically insulating layer of the laminate according to claim 7.   An electronic device comprising the multilayer circuit board according to claim 9.   Porous silica spherical primary particles exhibiting an X-ray diffraction pattern having one or more diffraction lines in the range of the diffraction angle (2θ / °) corresponding to the lattice spacing (d) of 1 nm or more are used. Curing formed from a curable resin composition comprising an alicyclic olefin polymer and a curing agent, characterized by adding porous silica aggregated particles assembled so as to form a void layer between primary particles A method for reducing the relative dielectric constant of an object.

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