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WO2015016165A1 - Substrat pour matériau électronique - Google Patents

Substrat pour matériau électronique Download PDF

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Publication number
WO2015016165A1
WO2015016165A1 PCT/JP2014/069789 JP2014069789W WO2015016165A1 WO 2015016165 A1 WO2015016165 A1 WO 2015016165A1 JP 2014069789 W JP2014069789 W JP 2014069789W WO 2015016165 A1 WO2015016165 A1 WO 2015016165A1
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WIPO (PCT)
Prior art keywords
group
substrate
compound
resin composition
layer
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PCT/JP2014/069789
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English (en)
Japanese (ja)
Inventor
洋平 立石
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Zeon Corp
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Zeon Corp
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Priority to JP2015529559A priority Critical patent/JPWO2015016165A1/ja
Publication of WO2015016165A1 publication Critical patent/WO2015016165A1/fr
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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10159—Memory

Definitions

  • the present invention relates to an electronic material substrate, and more particularly, to an electronic material substrate including an electrical insulating layer having excellent adhesion to a glass core substrate.
  • a circuit board having a multilayer structure (hereinafter referred to as a multilayer circuit board) is used.
  • Such a multilayer circuit board is obtained by, for example, laminating an electric insulating layer on a core substrate having a conductor layer formed on the surface thereof to obtain a substrate for electronic material, and forming the conductor layer on the substrate for electronic material. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer.
  • a multi-layer laminated substrate in which a plurality of prepregs obtained by impregnating glass cloth with a resin composition containing an inorganic filler is used as the base material constituting the core substrate.
  • a base material made of such a composite material there has been an increasing demand for producing through holes at a high density and further reducing the thermal expansion coefficient.
  • glass is used as a material for a base material that constitutes a core substrate, and an electrical insulating layer is formed on the glass base material. It has been proposed to obtain a core substrate by forming a conductor layer thereon.
  • thermosetting epoxy resin composition As a material for forming the electrical insulating layer constituting the multilayer circuit board, generally, a thermosetting epoxy resin composition is frequently used, but the problem is that the resin composition is inferior in adhesion to glass. There is.
  • An object of the present invention is to provide a substrate for an electronic material that has excellent adhesion between the core substrate and the electrical insulating layer when a glass core substrate is used.
  • An electronic material substrate comprising a glass core substrate and an electrically insulating layer formed on the core substrate, wherein the core substrate is a glass substrate and at least one of the glass substrates A surface treatment layer formed on the surface, wherein the electrical insulating layer includes an adhesive layer formed of a curable resin composition, and the surface treatment layer is formed of the surface treatment layer composition.
  • the curable resin composition comprises a polar group-containing alicyclic olefin polymer containing a polar group A, and a curing agent containing a functional group X having reactivity with the polar group A.
  • the surface treatment layer composition includes a silane coupling agent containing a functional group Y having reactivity with the polar group A.
  • the substrate for electronic materials wherein the polar group A includes at least one group selected from the group consisting of a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, and an epoxy group.
  • the electronic material substrate, wherein the functional group Y includes at least one group selected from the group consisting of an epoxy group, an amino group, an isocyanate group, and an imidazole group.
  • the substrate for electronic materials, wherein the other layer is formed from a curable epoxy composition.
  • the electronic material substrate having a through hole penetrating the core substrate and the electrical insulating layer.
  • the substrate for electronic material, wherein the through hole is formed by irradiating a laser beam.
  • an electronic material substrate having excellent adhesion between the core substrate and the electrical insulating layer can be provided.
  • the substrate for electronic materials of the present invention includes a glass core substrate and an electrical insulating layer formed on the core substrate.
  • numerical ranges indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the electrical insulating layer includes an adhesive layer formed of a curable resin composition
  • the curable resin composition includes a polar group-containing alicyclic olefin polymer containing a polar group A, the polar group A, and And a curing agent containing a functional group X having the following reactivity.
  • cured material is said polarity from a viewpoint of improving the electrical property, water resistance, and heat resistance of the hardened
  • the polar group-containing alicyclic olefin polymer contains an alicyclic structure in part or all of the monomer unit, and has at least one polar group A in the polymer molecule.
  • the alicyclic structure examples include a cycloalkane structure and a cycloalkene structure, and the mechanical strength and heat resistance of a cured product obtained by curing a curable resin composition containing an alicyclic olefin polymer. From this viewpoint, a cycloalkane structure is preferable.
  • the alicyclic structure is not particularly limited, and examples thereof include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a polycyclic ring formed by combining these.
  • the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, and the number of carbon atoms constituting the cyclic structure. Is in this range, the mechanical strength, heat resistance, and moldability are highly balanced and suitable.
  • the alicyclic structure of the alicyclic olefin polymer is composed of an olefin monomer unit having an alicyclic structure formed of carbon atoms, that is, an alicyclic olefin monomer unit.
  • the alicyclic olefin polymer may contain other monomer units in addition to the alicyclic olefin monomer units.
  • the ratio of the alicyclic olefin monomer unit in the alicyclic olefin polymer is not particularly limited, but is usually 30 to 100% by mass, preferably 50 to 100% by mass, more preferably 70 to 100% by mass. .
  • the obtained cured product is excellent in heat resistance.
  • the monomer unit other than the alicyclic olefin monomer unit is not particularly limited and is appropriately selected depending on the purpose.
  • the polar group A is not particularly limited, but alcoholic hydroxyl group, phenolic hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amino group, ester group, carboxylic acid anhydride Group, sulfonic acid group, phosphoric acid group and the like.
  • the polar group A includes a carboxyl group, a carboxylic acid anhydride group, and a phenol from the viewpoint of excellent mechanical strength and heat resistance of a cured product obtained by reacting with the functional group X of the curing agent. It is preferable to include at least one group selected from the group consisting of a functional hydroxyl group and an epoxy group.
  • an alicyclic olefin polymer may contain 1 type of polar groups, and may contain 2 or more types.
  • the polar group A contained in the alicyclic olefin polymer may be directly bonded to the atoms constituting the main chain of the polymer, or may be a methylene group, an oxy group, an oxycarbonyloxyalkylene group, a phenylene group, or the like. You may couple
  • the content rate of the monomer unit which has the polar group A in an alicyclic olefin polymer is not restrict
  • the alicyclic olefin polymer may have an aromatic ring in addition to the polar group A and the alicyclic structure. If an aromatic ring-containing alicyclic olefin polymer having a polar group A is used as the alicyclic olefin polymer, the rigidity of the polymer increases, and the strength of the film formed using the resin composition increases. This is because it increases. Moreover, it is because the aromatic ring containing alicyclic olefin polymer which has polar group A is excellent in compatibility with the other compound which can be mix
  • the alicyclic olefin polymer can be obtained, for example, by the following method. That is, (1) a method of polymerizing an alicyclic olefin having a polar group A by adding another monomer as necessary, and (2) an alicyclic olefin having no polar group A is converted to a polar group A method of copolymerizing with a monomer having A, (3) an aromatic olefin having a polar group A is polymerized by adding another monomer as necessary, and the aromatic ring of the polymer obtained thereby A method of hydrogenating a part, (4) a method of copolymerizing an aromatic olefin having no polar group A with a monomer having a polar group A, and hydrogenating an aromatic ring part of a polymer obtained thereby, Or (5) a method of introducing a polar group A into a polymer by reacting a compound having a polar group A with an alicyclic olefin polymer having no polar
  • ring-opening polymerization or addition polymerization is used as a polymerization method for obtaining an alicyclic olefin polymer.
  • the aromatic ring-containing alicyclic olefin polymer having a polar group A is, for example, (7) an aromatic ring-containing alicyclic having a polar group A as the alicyclic olefin having the polar group A in the method of (1) described above.
  • Examples of alicyclic olefins having a polar group A include, but are not limited to, 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2 .1] Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-carboxymethyl-9-hydroxycarbonyltetracyclo [6.2.1.1 3,6 .
  • Alicyclic olefins having a carboxylic acid anhydride group such as 0 4,9 ] heptadeca-6-ene-13,14-dicarboxylic acid anhydride; 9-methyl-9-methoxycarbonyltetracyclo [6.2.1 .1,3,6 .
  • Examples of the alicyclic olefin having no polar group A include, but are not limited to, bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2. 1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [ 2.2.1] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8-diene (Common name: dicyclopentadiene), tetracyclo [6.2.1.1 3,6 .
  • dodec-4-ene (common name: tetracyclododecene), 9-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 3,6 .
  • dodec-4-ene 9-vinyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-phenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7] dodeca-4-ene, tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene, cyclopentene, cyclopentadiene and the like. These may be used alone or in combination of two or more.
  • aromatic olefin having no polar group A examples include, but are not limited to, styrene, ⁇ -methylstyrene, divinylbenzene and the like. When these specific examples have the polar group A, examples thereof include aromatic olefins having the polar group A. These may be used alone or in combination of two or more.
  • aromatic ring-containing alicyclic olefin having a polar group A examples include, but are not limited to, an alicyclic olefin having a phenolic hydroxyl group, 1,4-methano-1,4,4a, 9a-tetrahydrodibenzofuran.
  • aromatic ring-containing alicyclic olefin having no polar group A examples include, but are not limited to, 9-phenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7] dodeca-4 and ene, 5- (4-methylphenyl-2-norbornene, 5- (1-naphthyl) -2-norbornene, tetracyclo [9.2.1.0 2,10 .0 3,8 ] tetradeca-3,5,7,12-tetraene (MTF), 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene and the like.
  • 9-phenyl-tetracyclo [6.2.1.1 3,6 . 0 2,7] dodeca-4 and ene 5- (4-methylphenyl-2-norbornene, 5- (1-naphthyl) -2-norbornene, tetracyclo [9.2.1.0 2,
  • ethylenically unsaturated compound which has the polar group A is mentioned.
  • ethylenically unsaturated compounds having a polar group A include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. Acid compounds; unsaturated carboxylic acid anhydrides such as maleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride; and the like. These may be used alone or in combination of two or more.
  • Examples of the monomer having no polar group A include an ethylenically unsaturated compound having no polar group A.
  • Examples of ethylenically unsaturated compounds having no polar group A include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Ethylene or ⁇ -olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; , 4-hexadiene,
  • the weight average molecular weight of the alicyclic olefin polymer is not particularly limited, but in order to improve the mechanical strength of the cured product obtained by curing, it is preferably 500 or more, and 1,000 or more. More preferably 3,000 or more, and in order to improve the workability when forming a film (adhesive layer) comprising the curable resin composition, 1,000,000 Or less, more preferably 500,000 or less, and particularly preferably 300,000 or less.
  • the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the polymerization catalyst for obtaining the alicyclic olefin polymer by the ring-opening polymerization method for example, a conventionally known metathesis polymerization catalyst described in International Publication No. 2012/090980 can be used.
  • the metathesis polymerization catalyst include transition metal compounds containing atoms such as Mo, W, Nb, Ta, and Ru. Among them, compounds containing Mo, W, or Ru are preferable because of high polymerization activity.
  • particularly preferred metathesis polymerization catalysts include ⁇ 1> a molybdenum or tungsten compound having a halogen group, an imide group, an alkoxy group, an allyloxy group or a carbonyl group as a ligand, and an organometallic compound.
  • a catalyst as the second component and a metal carbene complex catalyst having ⁇ 2> Ru as a central metal.
  • polymerization of an alicyclic olefin polymer can be performed using the method as described in international publication 2012/090980, for example, without being specifically limited.
  • Examples of the method for adjusting the molecular weight of the alicyclic olefin polymer include a method of adding an appropriate amount of a vinyl compound or a diene compound.
  • the vinyl compound used for molecular weight adjustment will not be specifically limited if it is an organic compound which has a vinyl group,
  • the compound as described in international publication 2012/090980 can be mentioned.
  • the addition amount of the vinyl compound or diene compound can be arbitrarily selected between 0.1 and 10 mol% based on the monomer used for the polymerization, depending on the target molecular weight.
  • a polymerization catalyst for obtaining an alicyclic olefin polymer by an addition polymerization method for example, a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound described in International Publication No. 2012/090980 is preferably used. It is done. These polymerization catalysts can be used alone or in combination of two or more.
  • hydrogenation of the ring-opening polymer is usually performed using a hydrogenation catalyst.
  • the hydrogenation catalyst is not particularly limited, and a catalyst generally used for hydrogenation of an olefin compound may be appropriately employed.
  • a known catalyst described in International Publication No. 2012/090980 can be used.
  • the hydrogenation reaction is usually performed in an organic solvent.
  • the organic solvent can be appropriately selected depending on the solubility of the generated hydrogenated product, and the same organic solvent as the organic solvent used in the polymerization reaction described above can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added and reacted as it is without replacing the organic solvent.
  • aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, and aromatic ether solvents are preferable from the viewpoint of not reacting during the hydrogenation reaction.
  • a group ether solvent is more preferable.
  • it is necessary is just to select suitably hydrogenation reaction conditions according to the kind of hydrogenation catalyst to be used, for example, the conditions as described in international publication 2012/090980 can be used.
  • the alicyclic olefin polymer may be used as a polymer solution after the polymerization reaction or after the hydrogenation reaction, or may be used after removing the solvent, but when preparing the curable resin composition It is preferable to use as a polymer solution because the additive can be dissolved and dispersed well and the process can be simplified.
  • the curing agent is not particularly limited as long as it is a compound that can form a crosslinked structure in the alicyclic olefin polymer having the polar group A by heating or the like, and it is not limited to a resin composition for forming a general electrical insulating layer.
  • blended can be used.
  • a compound having preferably two or more functional groups X having reactivity with the polar group A of the polar group-containing alicyclic olefin polymer in one molecule can be suitably used.
  • the functional group X preferably includes at least one group selected from the group consisting of an epoxy group, an amino group, an isocyanate group, and an imidazole group.
  • a curing agent having two or more functional groups X in one molecule a polyvalent epoxy compound, a polyvalent isocyanate compound, a polyvalent imidazole compound, a polyvalent amine compound, a polyvalent hydrazide compound, an aziridine compound, a basic metal oxide, And organometallic halides. These may be used alone or in combination of two or more. Moreover, you may use as a hardening
  • a polyvalent epoxy compound a polyvalent isocyanate compound, a polyvalent imidazole compound, and a polyvalent amine compound are preferable. Since the reactivity with the polar group A contained in the cyclic olefin polymer is moderate and the curable resin composition can be easily handled, a polyvalent epoxy compound is preferable.
  • polyvalent epoxy compound examples include a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a cresol type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a polyphenol type epoxy compound, and a brominated bisphenol A type epoxy compound.
  • Glycidyl ether type epoxy compounds such as brominated bisphenol F type epoxy compounds and hydrogenated bisphenol A type epoxy compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, and glycidyl amine type epoxy compounds.
  • Examples of the polyvalent epoxy compound having an alicyclic olefin structure include an epoxy resin having a dicyclopentadiene skeleton [for example, trade names “Epicron (registered trademark) HP7200L, Epicron (registered trademark) HP7200, Epicron (registered trademark) HP7200H, (Registered trademark) HP7200HH "(manufactured by DIC); trade name” Tactix (registered trademark) 558 "(manufactured by Huntsman Advanced Materials); trade names” XD-1000-1L, XD-1000-2L "( As mentioned above, Nippon Kayaku Co., Ltd.)] can be mentioned.
  • an epoxy resin having a dicyclopentadiene skeleton for example, trade names “Epicron (registered trademark) HP7200L, Epicron (registered trademark) HP7200, Epicron (registered trademark) HP7200H, (Registered trademark) HP7200HH "(manufactured by
  • the blending amount of the curing agent in the curable resin composition is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer having the polar group A. More preferably, it is in the range of 10 to 50 parts by weight.
  • the curable resin composition may contain a hindered phenol compound or a hindered amine compound in addition to the above components.
  • the hindered phenol compound is a phenol compound having a hydroxyl group and having at least one hindered structure in the molecule that does not have a hydrogen atom at the ⁇ -position carbon atom of the hydroxyl group.
  • Specific examples of the hindered phenol compound include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis- (3-methyl-6- tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, And tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane.
  • the blending amount of the hindered phenol compound in the curable resin composition is not particularly limited, but is preferably 0.04 to 10 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer having the polar group A,
  • the range is more preferably 0.3 to 5 parts by weight, still more preferably 0.5 to 3 parts by weight.
  • the hindered amine compound is a compound having in the molecule at least one 2,2,6,6-tetraalkylpiperidine group having a secondary amine or a tertiary amine at the 4-position.
  • the carbon number of alkyl is usually 1 to 50.
  • a compound having at least one 2,2,6,6-tetramethylpiperidyl group having a secondary amine or a tertiary amine at the 4-position in the molecule is preferable.
  • the surface roughening treatment is performed using an aqueous solution of the above, the cured product after the surface roughening treatment can be kept at a low surface roughness even if the surface roughening treatment conditions change. .
  • hindered amine compounds include bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 [ 2- ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ⁇ ethyl] -4- ⁇ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ⁇ -2,2,6,6, -tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2, 4-dione and the like can be mentioned.
  • the amount of the hindered amine compound is not particularly limited, but is usually 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer having the polar group A. More preferably, it is 0.25 to 3 parts by weight.
  • the curable resin composition may contain a curing accelerator in addition to the above components.
  • a curing accelerator a curing accelerator blended in a general resin composition for forming an electrical insulating film may be used.
  • an imidazole derivative is preferable from the viewpoint of enhancing the storage stability when the curable resin composition is used as a varnish.
  • the imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1- Alkyl-substituted imidazole compounds such as methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 Aryl groups and aralkyl groups such as -methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, etc. And an imidazole compound substituted with
  • the blending amount of the curing accelerator may be appropriately selected according to the purpose of use, but is preferably 0.001 to 30 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the alicyclic olefin polymer having the polar group A. Is 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight.
  • the curable resin composition preferably contains a filler in addition to the above components.
  • a filler any of known inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. Specific examples of inorganic fillers 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, silica, talc, clay and the like.
  • the filler to be used may have been surface-treated in advance with a surface treatment agent such as a silane coupling agent.
  • the content of the filler in the curable resin composition is not particularly limited, but can be 1 to 50% by weight, preferably 5 to 45% by weight, more preferably in terms of solid content. Is 15 to 35% by weight.
  • the curable resin composition includes a flame retardant, a flame retardant aid, a heat stabilizer, a weather stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), a leveling agent, and an antistatic agent.
  • Known components such as an agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic substance, a dielectric property adjusting agent, and a toughening agent may be appropriately blended. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.
  • the method for producing the curable resin composition is not particularly limited, and the above components may be mixed as they are, or may be mixed in a state dissolved or dispersed in an organic solvent, or the above A composition in which a part of each component is dissolved or dispersed in an organic solvent is prepared, and the remaining components may be mixed with the composition.
  • the adhesive layer is a layer (cured product) obtained by curing a layer (molded body of the curable resin composition) formed by molding the curable resin composition into a sheet or film.
  • the curable resin composition is coated, spread, or casted on a support, optionally added with an organic solvent, and then dried. It is preferable to obtain the above.
  • the curable resin composition may be obtained by adding an organic solvent if desired, coating, spreading or casting on a glass core substrate, and then drying if desired.
  • the thickness of the layer formed into a sheet or film is preferably 0.05 to 10 ⁇ m from the viewpoint of the uniformity of the resin layer thickness.
  • Examples of the support include resin films and metal foils.
  • Examples of the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable because of excellent heat resistance, chemical resistance, and peelability.
  • Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil.
  • the curable resin composition is in an uncured or semi-cured state as a sheet-shaped or film-shaped molded body.
  • uncured as used herein means that when the molded body is immersed in a solvent capable of dissolving the polar group-containing alicyclic olefin polymer containing the polar group A used in the preparation of the composition, the polarity is substantially reduced. It means a state in which all of the polar group-containing alicyclic olefin polymer containing the group A is dissolved.
  • the semi-curing is a state in which it is cured halfway to the extent that it can be cured by further heating.
  • the polar group-containing alicyclic olefin heavy containing the polar group A used for the preparation of the composition is used.
  • Part of the polar group-containing alicyclic olefin polymer containing the polar group A in a solvent capable of dissolving the polymer specifically, an amount such that it is an amount of 7% by weight or more and a part thereof remains) ) Is dissolved, or the volume after the molded body is immersed in a solvent for 24 hours is 200% or more (swelling ratio) of the volume before immersion.
  • drying may be performed as desired.
  • the drying temperature is preferably a temperature at which the curable resin composition is not cured, and is usually 20 to 300 ° C., preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds too much, 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 sheet-like or film-like molded product used in the present invention can be obtained in a state where it is adhered to the support or peeled off from the support.
  • the heel adhesive layer can be obtained as a cured product obtained by curing a molded body formed from the curable resin composition.
  • the curing treatment can be usually performed by heating the above-described sheet-shaped or film-shaped molded body.
  • the heating temperature in the curing treatment 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.
  • the electrical insulating layer may be a laminate further including another layer formed on the adhesive layer.
  • the adhesive layer is a layer laminated on a glass core substrate constituting the electronic material substrate.
  • the other layer is a layer formed of a curable composition for another layer, and the curable composition for the other layer is not particularly limited.
  • the thermosetting resin (B1) and a filler What contains (B2) can be used suitably.
  • thermosetting resin (B1) is not particularly limited as long as it is thermosetting resin (B1) alone or in combination with a curing agent (B3) described later and exhibits thermosetting properties and electrical insulation.
  • thermosetting resin (B1) include epoxy resins, maleimide triazine resins, (meth) acrylic resins, diallyl phthalate resins, alicyclic olefin polymers, aromatic polyether polymers, benzocyclobutene polymers, and cyanates. An ester resin, a polyimide, etc. can be mentioned. These thermosetting resins (B1) are used alone or in combination of two or more.
  • thermosetting resin (B1) those containing an epoxy group (that is, epoxy resin) are preferable, and those having at least two epoxy groups (multivalent epoxy) from the viewpoint of increasing the crosslinking density and improving the resin strength. Compound) is more preferred.
  • (meth) acryl means methacryl or acryl.
  • thermosetting resin (B1) examples include a phenol novolac type epoxy compound and a cresol novolac type epoxy compound, and the skeleton thereof has an alicyclic olefin structure. Can be mentioned.
  • Examples of the compound having an alicyclic olefin structure containing at least two epoxy groups include, for example, trade names “EPICLON (registered trademark) HP7200L”, “EPICLON HP7200”, “EPICLON HP7200H”, “EPICLON HP7200HH” (above, DIC Product name “Tactix (registered trademark) 558” (manufactured by Huntsman Advanced Material); Product names “XD-1000-1L”, “XD-1000-2L” (manufactured by Nippon Kayaku Co., Ltd.) And an epoxy resin having a dicyclopentadiene skeleton.
  • thermosetting resin (B1) a group having reactivity with the thermosetting resin (B1). What is contained may be used.
  • an epoxy group-containing one epoxy resin
  • the epoxy resin is not particularly limited as long as it has an epoxy group, and includes an alicyclic olefin polymer containing an epoxy group.
  • the curing agent (B3) used for the epoxy resin is not particularly limited as long as the epoxy resin can be cured.
  • a curing catalyst such as acetylacetone iron may be used together with the curing agent.
  • Examples of the above-described amine compound, a compound synthesized from an amine compound, a hydrazide compound, a melamine compound, and an acid anhydride include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and phenolic compound. The thing as described in international publication 2010/035451 can be used.
  • the curing agent (B3) used for these epoxy resins is preferably an alicyclic olefin polymer or an active ester compound having a group that reacts with an epoxy group from the viewpoint of electrical characteristics and water resistance.
  • examples of the “group that reacts with the epoxy group” include polar groups such as a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. Of these, acid anhydride groups are particularly preferred.
  • the alicyclic olefin polymer having a group that reacts with an epoxy group can be produced using the same method as the polar group-containing alicyclic olefin polymer used in the adhesive layer described above.
  • the active ester compound is not particularly limited as long as it has an active ester group, but a compound having at least two active ester groups in the molecule is preferable.
  • the active ester compound is preferably an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of heat resistance and the like.
  • An active ester compound obtained by reacting one or more selected from the group consisting of a compound, a naphthol compound, and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group are reacted.
  • aromatic compounds obtained by polymerization and having at least two active ester groups in the molecule are particularly preferred.
  • the active ester compound may be linear or multi-branched. Exemplifying the case where the active ester compound is derived from a compound having at least two carboxylic acids in the molecule, when such a compound having at least two carboxylic acids in the molecule contains an aliphatic chain, epoxy The compatibility with the resin can be increased, and when it has an aromatic ring, the heat resistance of the resulting cured product can be increased.
  • a carboxylic acid compound a phenol compound, a naphthol compound, and a thiol compound for forming a wrinkle active ester compound
  • those described in JP2012-153858A can be used.
  • the active ester compound for example, an aromatic compound having an active ester group described in JP-A No. 2002-12650 and a polyfunctional polyester described in JP-A No. 2004-277460, or A commercially available product can be used.
  • Commercially available active ester compounds include, for example, trade names “EXB9451”, “EXB9460”, “EXB9460S”, “EPICLON HPC-8000-65T” (manufactured by DIC), and trade name “DC808” (Mitsubishi Chemical). And a trade name “YLH1026” (manufactured by Mitsubishi Chemical Corporation).
  • the production method of the active ester compound is not particularly limited and can be produced by a known method.
  • it can be obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • the blending amount of the curing agent (B3) is preferably in the range of 20 to 120 parts by weight, more preferably 40 to 100 parts by weight, and still more preferably 50 to 90 parts by weight per 100 parts by weight of the epoxy resin.
  • the epoxy group derived from an epoxy resin, and an active ester compound origin Is an equivalent ratio of “epoxy group / active ester group”, preferably 0.5 to 1.25, more preferably 0.7 to 1.1, and still more preferably 0.8 to 1.05.
  • the filler (B2) the same filler as that constituting the adhesive layer can be used.
  • the blending amount of the filler (B2) is preferably 50 parts by weight or more, more preferably 60 parts by weight or more, preferably 85 parts by weight or less, more preferably 80 parts by weight or less, per 100 parts by weight of the thermosetting resin (B1). preferable.
  • blending a filler (B3) in said range the linear expansion coefficient of the hardened
  • the curable composition for other layers includes a curing accelerator, a flame retardant, a flame retardant aid, a heat stabilizer, a weather resistance, in the same manner as the curable resin composition for the adhesive layer described above.
  • the method for producing the curable composition for other layers used in the present invention is not particularly limited, and the above components may be mixed as they are, or mixed in a state dissolved or dispersed in an organic solvent.
  • a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent is prepared, and the remaining components may be mixed with the composition.
  • a curable resin composition for an adhesive layer is applied and dried on a glass substrate, and then for other layers.
  • a method of applying and drying a curable resin composition A method of applying and drying a curable resin composition;
  • D) a glass substrate is prepared on the support.
  • a method of laminating an adhesive layer and then laminating another layer prepared on another support (E) applying and drying a curable resin composition for another layer on the support, and then adhering the adhesive layer thereon A method of laminating a laminate prepared by applying and drying a curable resin composition for glass on a glass substrate; (F) Applying and drying a curable resin composition for an adhesive layer on a support, and then laminating another layer prepared on another support on the substrate, and then laminating on a glass substrate. It is done.
  • the production method (E) is preferred because it is an easier process and is excellent in productivity.
  • the said laminated body is manufactured using the curable resin composition for contact bonding layers, and the said resin composition for other layers.
  • the laminate is prepared, for example, by the following two methods: (1) The above-described resin composition for other layers is applied, dispersed or cast on a support, and is dried as desired. A method for producing the adhesive layer by further applying or casting the above-mentioned curable resin composition for the adhesive layer and drying it if desired; (2) applying the above-described other layer resin composition on the support; , Sprayed or cast, and applied to the support with the other layer molding formed into a sheet or film obtained by drying, if desired, and the adhesive layer curable resin composition described above.
  • the production method (1) is preferred because it is an easier process and is excellent in productivity.
  • the adhesive layer When the resin composition for other layers is applied, spread or cast on the support, and the other layer resin composition which has been applied, spread or cast, the adhesive layer
  • the curable resin composition for coating is applied, dispersed or cast, or in the production method of the above (2)
  • the resin composition for other layers and the curable resin composition for the adhesive layer are formed into a sheet or film.
  • an organic solvent is added to the resin composition for the other layer or the curable resin composition for the adhesive layer as desired. It is preferable to apply, spread or cast on the support.
  • Examples of the support used at that time include resin films and metal foils.
  • the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable from the viewpoint of heat resistance, chemical resistance, peelability, and the like.
  • the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil.
  • the average surface roughness Ra of the support is usually 300 nm or less, preferably 150 nm or less, more preferably 100 nm or less.
  • the thickness of the other layer resin composition and the curable resin composition for the adhesive layer, or the other layer molded body and the adhesive layer in the production method (2) is not particularly limited, but the thickness of the other layers in the laminated body is preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and further preferably 15 to 40 ⁇ m. The thickness is preferably 1 to 10 ⁇ m, more preferably 1.5 to 8 ⁇ m, and even more preferably 2 to 5 ⁇ m. If the thickness of the adhesive layer is too thin, the laminate with the glass core substrate may break in the process, while if the thickness of the adhesive layer is too thick, the cured product obtained by curing the laminate. There is a risk of expansion.
  • Examples of methods for applying other layer resin compositions and adhesive layer curable resin compositions include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.
  • drying may be performed.
  • the drying temperature is preferably a temperature at which the composition of the other layer and the adhesive layer is not cured, and is usually 20 to 300 ° C., preferably 30 to 200 ° C.
  • the drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.
  • the other layers may include a fiber base material.
  • the fiber base material include organic fibers such as polyamide fiber, polyaramid fiber and polyester fiber, and inorganic fibers such as glass fiber and carbon fiber.
  • the form of woven fabrics such as a plain weave or a twill weave, the form of a nonwoven fabric, etc. are mentioned.
  • the thickness of the fiber substrate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, more preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less from the viewpoint of easy handling.
  • the adhesive layer and other layers can be obtained by curing the resin composition constituting them.
  • the curing treatment can be usually performed by heating the above-described film or the film in the laminate.
  • 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.
  • the film or laminate is provided on the core substrate. Two or more may be bonded and laminated.
  • a conductor layer may be formed on the electrical insulating layer in the electronic material substrate of the present invention.
  • Metal plating can be used as such a conductor layer.
  • the metal plating material include gold, silver, copper, rhodium, palladium, nickel, and tin.
  • the core substrate is a substrate mainly made of glass, and includes a glass base material and a surface treatment layer formed on at least one surface of the glass base material.
  • the material constituting the glass substrate include alkali-free or low-alkali glass, such as quartz glass or borosilicate glass, and heat (240 to 260) at the time of solder mounting reflow on a mounting substrate (mother substrate). Any glass can be used as long as it is heat resistant glass.
  • alkali-free or low-alkali glass whose linear expansion coefficient is an intermediate value between the semiconductor chip and the mounting substrate is desirable in terms of reliability.
  • the thickness of the glass substrate is usually 0.01 to 5 mm.
  • the glass substrate is thicker than 5 mm, it takes time to form through-holes and the electrical insulating layer may be peeled off. If it is less than 0.01 mm, problems such as cracks occur during processing. May occur.
  • the thickness of the glass substrate is more preferably 0.02 to 3 mm, and further preferably 0.02 to 1 mm.
  • a glass substrate having a surface roughness Ra of 0.05 to 50 nm can be suitably used.
  • the surface treatment layer includes a layer formed of the surface treatment layer composition, and the surface treatment layer composition comprises a silane coupling agent containing a functional group Y having reactivity with the polar group A. Including.
  • the alkoxysilane portion constituting the silane coupling agent is in close contact with the glass, while the functional group Y contained in the silane coupling agent.
  • the adhesion between the glass substrate and the adhesive layer can be enhanced, and as a result, the adhesion between the glass and the electrical insulating layer is enhanced. be able to.
  • the functional group Y contained in the silane coupling agent is not particularly limited as long as it is a functional group having reactivity with the polar group A.
  • a functional group having reactivity with the polar group A for example, from the group consisting of an epoxy group, an amino group, an isocyanate group, and an imidazole group
  • the silane coupling agent having such a functional group Y include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane.
  • Examples include ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, [3- (1H-imidazol-1-yl) propyl] triethoxysilane, and the like.
  • a silane coupling agent containing a functional group Y having reactivity with the polar group A is sprayed or applied to the surface of a glass substrate made of glass, and a core substrate is prepared.
  • a via hole penetrating the electrical insulating layer and the core substrate is formed on the cured product obtained by laminating the film (adhesive layer or laminate) or the like on the surface treatment layer and curing the film to form the electrical insulating layer.
  • a through hole (through hole) is formed. The via hole is formed to connect the conductor layers constituting the multilayer circuit board when the multilayer circuit board is formed.
  • the via hole or the through hole can be formed by chemical processing such as photolithography, or physical processing such as drilling, laser light irradiation, plasma etching, or the like. Among these, it is desirable to open a through hole by irradiating a laser beam from the viewpoint that a small diameter through hole can be easily formed. Moreover, when using a support body when obtaining the said film, it is good also as an aspect which forms a through-hole by irradiating a laser beam from the support body side, before peeling a support body.
  • the electronic material substrate of the present invention may be manufactured by the following method. That is, a silane coupling agent containing a functional group Y having reactivity with the polar group A is applied to the surface of a glass substrate made of glass and dried to prepare a core substrate. Next, via holes and through holes are formed in the core substrate in the same manner as described above. Next, the film (adhesive layer or laminate) or the like may be laminated on the surface treatment layer and cured to form an electrical insulating layer.
  • a surface roughening treatment is performed to roughen the surface of the cured electrically insulating layer, specifically, the surface of the cured film adhesive layer or other layer.
  • the surface roughening treatment is performed in order to improve the adhesion with the conductor layer formed on the electrical insulating layer.
  • the surface average roughness Ra of the electrical insulating layer is preferably less than 0.3 ⁇ m, more preferably less than 0.2 ⁇ m. Note that the lower limit of the surface average roughness Ra of the electrical insulating layer can be 0.05 ⁇ m or more.
  • the surface ten-point average roughness Rzjis is preferably 0.3 ⁇ m or more and less than 4 ⁇ m, more preferably 0.5 ⁇ m or more and 2 ⁇ m or less.
  • Ra is the arithmetic average roughness shown in JISJB0601-2001
  • the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.
  • the surface roughening treatment method is not particularly limited, and examples thereof include a method of bringing the surface of the electrical insulating layer into contact with an oxidizing compound.
  • the oxidizing compound include known compounds having oxidizing ability, such as inorganic oxidizing compounds and organic oxidizing compounds.
  • an inorganic oxidizing compound or an organic oxidizing compound In view of easy control of the average surface roughness of the electrical insulating layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound.
  • inorganic oxidizing compounds include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, and the like.
  • the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, and ozone.
  • a conductor layer is formed on the surface of the electrical insulating layer and the inner wall surface of the via hole or the through hole.
  • the formation method of a conductor layer is not specifically limited, It is preferable to carry out by the electroless-plating method from a viewpoint that the conductor layer excellent in adhesiveness can be formed.
  • catalyst nuclei such as silver, palladium, zinc, and cobalt are formed on the electrical insulation layer. It is common to attach.
  • the method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited.
  • a metal compound such as silver, palladium, zinc, or cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform to 0.001.
  • Examples include a method of reducing a metal after being immersed in a solution (contained with an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved at a concentration of ⁇ 10% by mass.
  • 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 is not particularly limited.
  • the substrate surface can be brought into contact with a rust inhibitor and subjected to rust prevention treatment.
  • a metal thin film can also be heated in order to improve adhesiveness.
  • the heating temperature is usually 50 to 350 ° C., preferably 80 to 250 ° C. In this case, heating may be performed under a pressurized condition.
  • a pressurizing method at this time for example, a method using a physical pressurizing means such as a hot press machine or a pressurizing and heating roll machine can be cited.
  • the applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.
  • a resist pattern for plating is formed on the metal thin film thus formed, and further, plating is grown thereon by wet plating such as electrolytic plating (thick plating), then the resist is removed, and further etched.
  • the metal thin film is etched into a pattern to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal thin film and plating grown thereon.
  • the composite body thus obtained (multi-layer circuit board as an example of the composite body) has an electrical insulating layer constituting the electronic material substrate of the present invention, and the electrical insulating layer has excellent adhesion.
  • the composite can be suitably used for various applications.
  • Electronic materials substrates are mobile phones, PHS, notebook computers, PDAs (personal digital assistants), mobile video phones, personal computers, supercomputers, servers, routers, liquid crystal projectors, engineering workstations (EWS), pagers, word processors. It can be suitably used for various electronic devices such as televisions, viewfinder type or monitor direct view type video tape recorders, electronic notebooks, electronic desk calculators, car navigation devices, POS terminals, and devices equipped with touch panels.
  • the resulting polymer (P-1) had a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution of 2.
  • the hydrogenation rate was 95%, and the content of monomer units having a carboxylic anhydride group was 30 mol%.
  • the solid content concentration of the polymer (P-1) solution was 20% by mass.
  • thermosetting resin B1
  • active ester compound EPICLON HPC-8000-
  • curing agent B3
  • silica silica as an inorganic filler
  • SC2500-SXJ average particle size 0
  • IRGANOX 3114 hindered phenolic antioxidant
  • the varnish of the curable resin composition for the adhesive layer obtained above is applied to the surface of the other layer forming molded body 1 in the intermediate of the obtained film molded body with a support by a doctor blade.
  • a tester industry company make and an auto film applicator (a tester industry company make) apply
  • a film molded body with a support on which was formed a laminate of the molded body 1 and the adhesive layer-forming molded body 2 was obtained.
  • the film-formed product with the support was formed in the order of the support, the other layer-formed product 1, and the adhesive layer-formed product 2.
  • the film-formed product with the support obtained above was cut into 125 mm square, and the surface on the side of the curable resin composition for the adhesive layer (on the side of the molded product 2 for forming the adhesive layer).
  • the primary press is thermocompression bonding at a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom.
  • thermocompression bonding was performed at a pressure bonding temperature of 110 ° C. and a pressure of 1 MPa for 90 seconds.
  • substrate and a laminated body was obtained by peeling a support body.
  • the obtained composite is left to stand at 180 ° C. for 60 minutes in an air atmosphere to cure the layers made of the respective resin compositions in the laminate, and to have a cured product of the laminate on the core substrate.
  • a treated complex was obtained.
  • a swollen composite was prepared by adding water to a mixture of 500 mL of an aqueous solution of permanganate (“Concentrate Compact CP”, manufactured by Atotech) and 40 g of sodium hydroxide to a total of 1 L.
  • the obtained aqueous solution was brought to 80 ° C., immersed in this aqueous solution for 20 minutes, and then washed with water.
  • the swollen-treated composite was prepared so as to be a hydroxyamine sulfate aqueous solution (“Reduction Securigant P 500”, manufactured by Atotech, “Securigant” is a registered trademark) 100 mL / L, and sulfuric acid 35 mL / L 60 It was immersed in an aqueous solution at 5 ° C. for 5 minutes, neutralized and reduced, and then washed with water.
  • Reduction Securigant P 500 manufactured by Atotech, “Securigant” is a registered trademark
  • a peel strength test (adhesion test 2) was performed on the obtained neutralized and reduced treated composite based on JIS K5600-5-6 adhesion (cross-cut method). Evaluation was made according to the following criteria. The results are shown in Table 1. ⁇ : Peel strength is 4 N / cm or more ⁇ : Peel strength is less than 4 N / cm
  • Alcup Activator MAT-1-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) at 200 mL / L
  • Alcup Activator MAT-1-B (trade name, Made by Uemura Kogyo Co., Ltd., “ALCUP” is a registered trademark) of 30 mL / L and sodium hydroxide was adjusted to 0.35 g / L, soaked in a 60 ° C. Pd salt-containing plating catalyst aqueous solution for 5 minutes, and then washed with water. .
  • the composite having been subjected to the catalyst application treatment was Alcap Redeusa MAB-4-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “ALCUP” is a registered trademark), 20 mL / L, Alcup Redeusa MAB-4-B (Product) Name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) was immersed in an aqueous solution adjusted to 200 mL / L at 35 ° C. for 3 minutes to reduce the plating catalyst, and then washed with water.
  • Alcap Redeusa MAB-4-A trade name, manufactured by Uemura Kogyo Co., Ltd., “ALCUP” is a registered trademark
  • Alcup Redeusa MAB-4-B Product
  • Sulcup PEA-6-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Sulcup” is a registered trademark)
  • Sulcup PEA-6-B-2X Product name, manufactured by Uemura Kogyo Co., Ltd.
  • Sulcup PEA-6-C (trade name, manufactured by Uemura Kogyo Co., Ltd.) 14 mL / L
  • Sulcup PEA-6-D trade name, manufactured by Uemura Kogyo Co., Ltd.
  • Sulcup PEA-6-E (trade name, manufactured by Uemura Kogyo Co., Ltd.) 50 mL / L, 37% formalin aqueous solution 5 mL / L prepared for electroless copper plating solution at a temperature of 36 ° C.
  • the electroless copper plating process was performed by immersion, and an electroless plating film was formed on the surfaces of the electrical insulating layer and the through hole. Next, annealing was performed at 150 ° C. for 30 minutes in an air atmosphere.
  • the composite subjected to the annealing treatment was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 30 ⁇ m.
  • the electrical insulating layer on which the electrolytic copper plating film is formed is heat-treated at 180 ° C. for 60 minutes to form a multilayer in which a conductive layer made of the metal thin film layer and the electrolytic copper plating film is formed on the surface of the electrical insulating layer and the through hole.
  • a circuit board was obtained.
  • the obtained multilayer circuit board was subjected to cross-sectional polishing of the through hole and confirmed with an optical microscope whether or not a defect such as peeling of the electrical insulating layer occurred in the vicinity of the through hole. Evaluation was made according to the following criteria. The results are shown in Table 1. ⁇ : No peeling ⁇ : There is peeling
  • Example 2 A cured composite was obtained in the same manner as in Example 1 except that the varnish of the resin composition for other layers was not applied (laminated).
  • Example 1 A cured composite was obtained in the same manner as in Example 1 except that the varnish of the curable resin composition for the adhesive layer was not applied (laminated).

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Abstract

　La présente invention porte sur un substrat pour un matériau électronique, comportant un substrat central réalisé en verre, et une couche d'isolation électrique formée sur le substrat central. Le substrat central comporte un matériau de base en verre, et une couche de traitement de surface formée sur au moins une surface du matériau de base en verre. La couche d'isolation électrique comprend une couche adhésive formée par une composition de résine durcissable, et la couche de traitement de surface comprend une couche formée par une composition de couche de traitement de surface. La composition de résine durcissable comprend un polymère d'oléfine alicyclique contenant un groupe polaire contenant un groupe polaire A, et un agent de durcissement contenant un groupe fonctionnel X ayant une réactivité avec le groupe polaire A. La composition de couche de traitement de surface comprend un agent de couplage de silane contenant un groupe fonctionnel Y ayant une réactivité avec le groupe polaire A.
PCT/JP2014/069789 2013-07-30 2014-07-28 Substrat pour matériau électronique Ceased WO2015016165A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2002092903A1 (fr) * 2001-05-15 2002-11-21 Asahi-Schwebel Co., Ltd. Tissu de verre et utilisation de celui-ci
JP2012046755A (ja) * 2011-09-26 2012-03-08 Sumitomo Bakelite Co Ltd 絶縁性樹脂組成物、その製造方法及び電子部品
JP2013010895A (ja) * 2011-06-30 2013-01-17 Nippon Zeon Co Ltd 絶縁性接着フィルム、積層体、硬化物、及び複合体

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