Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits

Definitions

• the present invention relates to a specific resin composition. Furthermore, it is related with the adhesive film, prepreg, multilayer printed wiring board, and semiconductor device containing the said resin composition.
• Patent Document 1 discloses resin compositions containing organic-inorganic hybrids, and describes that these compositions improve the glass transition point.
• Patent Documents 2 to 4 general compounding studies are also conducted. However, its performance was not always satisfactory.
• the plated conductor is not only a low arithmetic mean roughness (Ra value) but also a low root mean square roughness (Rq value) on the insulating layer surface after the wet roughening step. It is to provide a novel resin composition in which the layer exhibits a sufficiently high peel strength.
• the present inventors can solve the above problems by using a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with an epoxy resin. As a result, the present invention has been completed.
• a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with an epoxy resin.
• a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with an epoxy resin.
• the above [C] characterized in that the inorganic filler surface-treated with (C) the epoxy resin is surface-treated with 0.05 to 3% by mass of the epoxy resin with respect to 100% by mass of the inorganic filler.
• the resin composition according to the above. [3] The above [1] or [2], wherein the inorganic filler surface-treated with the epoxy resin (C) has an average temperature of 20 to 100 ° C. during the surface treatment with the epoxy resin. Resin composition.
• the epoxy resin of the inorganic filler surface-treated with an epoxy resin is a naphthalene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a glycerol type epoxy resin or a p-aminophenol type epoxy.
• the group in which the inorganic filler surface-treated with (C) epoxy resin further comprises a silane coupling agent, an alkoxysilane, an alkoxy oligomer, an aluminum coupling agent, a titanium coupling agent, and a zirconium coupling agent.
• the resin composition is cured to form an insulating layer, the arithmetic average roughness after roughening the surface of the insulating layer is 10 nm to 330 nm, and the root mean square roughness is 10 to 480 nm.
• the peel strength between the conductor layer and the insulating layer obtained by plating on the surface of the insulating layer after the roughening treatment is 0.4 kgf / cm to 1.0 kgf / cm.
• An adhesive film in which the resin composition according to any one of [1] to [13] is formed as a resin composition layer on a support.
• a new resin composition can be provided in which the plated conductor layer exhibits a sufficiently high peel strength even when it has not only a low arithmetic average roughness (Ra value) but also a low root mean square roughness (Rq value). became.
• the present invention is a resin composition
• a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with an epoxy resin.
• the epoxy resin used in the present invention is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol.
• Type epoxy resin naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy having butadiene structure Resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy Butter, and the like can be mentioned. These may be used alone or in combination of two or more.
• bisphenol A type epoxy resin bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy from the viewpoint of improving heat resistance, insulation reliability, and adhesion to metal foil.
• a resin and an epoxy resin having a butadiene structure are preferred.
• bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a butadiene structure (“PB-3600”, “Epolide PB” manufactured by Daicel Chemical Industries, Ltd.), epoxy resins having a biphenyl structure (Nippon Kayaku) “NC3000H”, “NC3000L”, “NC3100” "YX4000”, “YX4000H”, “YX4000HK”, “YL6121”) manufactured by Mitsubishi Chemical Corporation, cyclohex
• Two or more epoxy resins may be used in combination, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule.
• a solid aromatic epoxy resin is used in combination.
• the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule
• the resin composition When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, when using the resin composition in the form of an adhesive film, the resin composition has an appropriate flexibility and the cured product of the resin composition has an appropriate breaking strength. Therefore, the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 2, more preferably in the range of 1: 0.3 to 1.8, and 1: A range of 0.6 to 1.5 is more preferable.
• the content of the epoxy resin is 3 to 3%. It is preferably 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10 to 30% by mass.
• the curing agent used in the present invention is not particularly limited, but phenolic curing agent, naphthol curing agent, active ester curing agent, benzoxazine curing agent, cyanate ester curing agent, acid anhydride curing agent, etc. Among them, a phenolic curing agent, a naphthol curing agent, an active ester curing agent or a cyanate ester curing agent is preferable. These may be used alone or in combination of two or more.
• the phenolic curing agent and the naphtholic curing agent are not particularly limited, and examples thereof include a phenolic curing agent having a novolak structure and a naphtholic curing agent having a novolac structure, such as a phenol novolac resin, a triazine skeleton-containing phenol novolac resin, Naphthol novolac resins, naphthol aralkyl type resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferred.
• a phenolic curing agent having a novolak structure such as a phenol novolac resin, a triazine skeleton-containing phenol novolac resin, Naphthol novolac resins, naphthol aralkyl type resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferred.
• ester groups with high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule.
• a compound having two or more in the above is preferably used.
• the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
• an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
• the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.
• an active ester curing agent an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used.
• Commercially available active ester curing agents include those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, benzoylated phenol novolacs, etc. Among them, dicyclopentadienyl diphenol structures are preferred. The inclusion is more preferable.
• HPC-8000-65T (manufactured by DIC Corporation, active group equivalent of about 223) as a dicyclopentadienyl diphenol structure
• DC808 Mitsubishi Chemical Co., Ltd., active group equivalent of about 149
• YLH1026 Mitsubishi Chemical Co., Ltd., active group equivalent of about 200
• YLH1030 Mitsubishi Chemical Co., Ltd., active group equivalent
• YLH1048 manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 245
• HPC-8000-65T is preferable from the viewpoint of the storage stability of the varnish and the thermal expansion coefficient of the cured product.
• examples of the active ester curing agent containing a dicyclopentadienyl diphenol structure include those represented by the following formula (1).
• R is a phenyl group or a naphthyl group
• k represents 0 or 1
• n is 0.05 to 2.5 on an average of repeating units.
• R is preferably a naphthyl group, while k is preferably 0 and n is preferably 0.25 to 1.5.
• cyanate ester type hardening curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines.
• the weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000.
• cyanate ester curing agent examples include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins
• cyanate ester resins examples include phenol novolac polyfunctional cyanate ester resins represented by the following formula (2) (Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and the following formula (3): Prepolymer (part Lona Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene represented by the following formula (4): a part or all of the bisphenol A dicyanate represented by triazine Structure-containing cyanate ester resin (Lonza Japan Co., Ltd., T-4000, DT-7000), and the like.
• formula (2) Lionza Japan Co., Ltd., PT30, cyanate equivalent 124
• Prepolymer part Lona Japan Co., Ltd., BA230, cyanate equivalent 232
• dicyclopentadiene represented by the following formula (4): a part or all of the bisphenol A dicyanate represented by triazine Structure-containing cyanate ester resin (Lonza Japan Co., Ltd
• n represents an arbitrary number (preferably 0 to 20) as an average value.
• n represents a number of 0 to 5 as an average value.
• the acid anhydride curing agent is not particularly limited, but phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride Hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3 ' -4
• the total number of epoxy groups of the epoxy resin and (B) the total of reactive groups of the curing agent is preferably 1: 0.2 to 2, more preferably 1: 0.3 to 1.5, and still more preferably 1: 0.4 to 1.
• the total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent.
• the total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.
• the content of the curing agent is 3 to It is preferably 30% by mass, more preferably 5 to 25% by mass, and even more preferably 7 to 20% by mass.
• the inorganic filler used in the present invention is not particularly limited.
• examples thereof include boron, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
• silica is preferable.
• silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, and hollow silica is preferable, and fused silica is more preferable.
• the silica is preferably spherical. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.
• the average particle size of the inorganic filler is not particularly limited, but is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less, from the viewpoint of forming fine wiring on the insulating layer. 7 ⁇ m or less is even more preferable, 0.5 ⁇ m or less is particularly preferable, 0.4 ⁇ m or less is particularly preferable, and 0.3 ⁇ m or less is particularly preferable.
• the epoxy resin composition is a resin varnish, it is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing.
• the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter.
• an inorganic filler dispersed in water by ultrasonic waves can be preferably used.
• a laser diffraction type particle size distribution measuring device LA-500, 750, 950, etc. manufactured by Horiba Ltd. can be used.
• the liquid epoxy resin preferably has a viscosity at 25 ° C. of 0.01 to 50 Pa ⁇ s, and more preferably 0.05 to 35 Pa ⁇ s. Viscosity was measured using an E-type viscometer (RE-80 manufactured by Toki Sangyo Co., Ltd.), and about 0.2 ml of the liquid epoxy resin was measured using a syringe in an apparatus adjusted to 25 ° C. It can be measured at a rotational speed set to 5 to 20 rpm.
• E-type viscometer RE-80 manufactured by Toki Sangyo Co., Ltd.
• a polyfunctional epoxy resin is preferable, and a polyfunctional epoxy resin having an epoxy equivalent of 50 to 300 is more preferable.
• the “polyfunctional epoxy resin” referred to here is an epoxy resin having two or more epoxy groups in one molecule.
• the epoxy equivalent (g / eq) is a value obtained by dividing the average molecular weight by the number of epoxy groups per molecule.
• Specific examples of the epoxy resin include naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycerol type epoxy resin, p-aminophenol type epoxy resin, biphenyl type epoxy resin, glycidyl methacrylate resin, glycidyl.
• Acrylate resin cyclohexanedimethanol type epoxy resin, biphenyldimethanol type epoxy resin, benzenedimethanol type epoxy resin, propylene glycol type epoxy resin, alicyclic epoxy resin, methacrylate having alicyclic epoxy group, having methyl glycidyl group And methacrylate.
• at least one selected from the group consisting of naphthalene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycerol type epoxy resins and p-aminophenol type epoxy resins is preferable.
• Examples of the method for surface-treating the inorganic filler with an epoxy resin include a method in which the inorganic filler is put into a stirrer and the inorganic filler is stirred for 5 to 30 minutes while spraying the epoxy resin. At that time, the viscosity may be adjusted by dissolving in an organic solvent so that the epoxy resin can be easily sprayed.
• the average temperature during the surface treatment with the epoxy resin is preferably 20 ° C or higher, more preferably 25 ° C or higher, further preferably 30 ° C or higher, and further 35 ° C or higher. More preferred is 40 ° C. or higher, particularly preferred is 45 ° C. or higher.
• the average temperature during the surface treatment with the epoxy resin is preferably 100 ° C. or less, more preferably 95 ° C. or less, and further preferably 90 ° C. or less.
• the maximum temperature achieved during the surface treatment is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, and even more preferably 65 ° C. or higher. It is particularly preferable that the temperature is not lower than ° C.
• the maximum temperature achieved when the surface treatment is performed with the epoxy resin is preferably 150 ° C.
• the agitator include a rotary mixer, a drum mixer, a rocking mixer, a vibrating fluidized bed, and a powder dryer, and the rotary mixer is preferable in that it can be easily performed.
• a Henschel-type powder mixer can be used as the rotary mixer.
• the content of the epoxy resin is preferably 0.05% by mass or more with respect to 100% by mass of the inorganic filler from the viewpoint of improving the dispersibility of the resin varnish and improving the coverage of the inorganic filler.
• 0.1% by mass or more is more preferable, 0.15% by mass or more is further preferable, 0.2% by mass or more is further more preferable, 0.25% by mass or more is particularly preferable, and 0.3% by mass or more is particularly preferable. preferable.
• the surface treatment is preferably 3% by mass or less, more preferably 2.8% by mass or less, and further 2.6% by mass or less.
• 2.4 mass% or less is still more preferable, 2.2 mass% or less is especially preferable, and 2 mass% or less is especially preferable.
• (C) The content in the case of blending the inorganic filler surface-treated with an epoxy resin, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of reducing the thermal expansion coefficient of the cured product, 20 mass% or more is preferable, 30 mass% or more is more preferable, 40 mass% or more is further more preferable, and 50 mass% or more is still more preferable. Moreover, from a viewpoint of the mechanical characteristic improvement of hardened
• the inorganic filler is preferably an inorganic filler that has been surface-treated with a silazane compound in advance. After surface treatment with a silazane compound, surface treatment with an epoxy resin is advantageous in terms of improving dispersibility and improving affinity with a conductor layer.
• silazane compound examples include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (t-butyl) disilazane, hexabutyldisilazane, hexaoctyldi.
• Silazane 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3- Diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethyl Silazane, trisilazane, cyclotrisilazane, 1,1,3 5,5 hexamethylcyclotrisilazane, etc.
• hexamethyldisilazane can be mentioned, particularly preferably hexamethyldisilazane. You may use these 1 type or in combination of 2 or more types.
• Examples of spherical fused silica surface-treated with hexamethyldisilazane include “SC2050-SQ” manufactured by Admatechs.
• the amount of the silazane compound is preferably 0.001 to 0.3% by mass with respect to 100% by mass of the inorganic filler, and 0.005 to 0.2% by mass. % Is more preferable, 0.01 to 0.1% by mass is further preferable, and 0.02 to 0.04% by mass is even more preferable.
• (C) From the viewpoint of improving hydrophobicity and further improving dispersibility by reacting an inorganic filler surface-treated with an epoxy resin with an unreacted silanol group, a silane coupling agent, alkoxysilane, alkoxy oligomer, aluminum
• the surface treatment is preferably carried out with at least one selected from the group consisting of a system coupling agent, a titanium coupling agent and a zirconium coupling agent. This surface treatment may be performed directly on the inorganic filler surface-treated with the epoxy resin (C) or may be added to the resin varnish.
• silane coupling agent an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, or the like can be used. You may use these 1 type or in combination of 2 or more types. Specifically, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.
• Epoxysilane coupling agents aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, aminosilane coupling agents such as N-2 (aminoethyl) aminopropyltrimethoxysilane, Examples include mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
• alkoxysilane methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, or the like can be used. You may use these 1 type or in combination of 2 or more types.
• An alkoxy oligomer refers to a low molecular resin having both an organic group and an alkoxysilyl group, and includes a methyl group-containing alkoxy oligomer, a phenyl group-containing alkoxy oligomer, a methyl / phenyl group-containing alkoxy oligomer, an epoxy group-containing alkoxy oligomer, and a mercapto group-containing alkoxy.
• alkoxy oligomers examples include oligomers, amino group-containing alkoxy oligomers, acrylic group-containing alkoxy oligomers, methacryl group-containing alkoxy oligomers, ureido group-containing alkoxy oligomers, isocyanate group-containing alkoxy oligomers, vinyl group-containing alkoxy oligomers. You may use these 1 type or in combination of 2 or more types.
• the alkoxy oligomer can be represented by the structure of the following general formula (5).
• R 1, R 2 and R 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms. More preferably a straight chain or branched chain having 1 to 4 carbon atoms, still more preferably a methyl group, an ethyl group or a propyl group, still more preferably a methyl group or an ethyl group.
• X includes a lower alkyl group, a glycidoxyalkyl group, an aminoalkyl group, a mercaptoalkyl group, an acryloxyalkyl group, a methacryloxyalkyl group, a ureidoalkyl group, an isocyanate alkyl group, and a vinylalkyl group.
• Glycidoxypropyl group aminopropyl group, N-2- (aminoethyl) -3-aminopropyl group, N-phenyl-3-aminopropyl group, methacryloxypropyl group, acryloxypropyl group, mercaptopropyl group, A ureidopropyl group and an isocyanatepropyl group are preferable, and a glycidoxypropyl group, an aminopropyl group, an N-2- (aminoethyl) -3-aminopropyl group, an N-phenyl-3-aminopropyl group, and a mercaptopropyl group are more preferable.
• an aminopropyl group, N-2- (a Aminoethyl) -3-aminopropyl group, N- phenyl-3-aminopropyl group are more preferable.
• n is an integer of 2 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and further preferably an integer of 3 to 5.
• Aluminum coupling agents include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum Diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide stearate, cyclic aluminum oxide octylate, cyclic aluminum Examples thereof include oxide stearate. You may use these 1 type or in combination of 2 or more types.
• Titanium coupling agents include butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditri) Decylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite Isopropyl trioctanoyl titanate, isopropyl tric
• Zirconium-based coupling agents include zirconium IV (2,2-bis (2-propenolatemethyl) butanolate, trisneodecanolate), zirconium IV (2,2-bis (2-propenolatemethyl) butanolate).
• the peel strength between the conductor layer and the insulating layer obtained by curing the resin composition of the present invention to form an insulating layer and plating the surface of the insulating layer after the roughening treatment is described below. It can be grasped by the measurement method described in Measurement of Peel Strength (Peel Strength)>.
• the peel strength is preferably 0.8 kgf / cm or less, more preferably 0.9 kgf / cm or less, still more preferably 1.0 kgf / cm or less, and even more preferably 1.5 kgf / cm or less.
• the peel strength is preferably 0.4 kgf / cm or more, and more preferably 0.5 kgf / cm or more.
• the arithmetic average roughness (Ra value) and the root mean square roughness (Rq value) after curing the resin composition of the present invention to form an insulating layer and roughening the surface of the insulating layer will be described later. It can be grasped by the measuring method described in the section “Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening>.
• the arithmetic average roughness (Ra value) is preferably 330 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, still more preferably 220 nm or less, and even more preferably 200 nm or less in order to reduce transmission loss of electrical signals. 180 nm or less is particularly preferable.
• the arithmetic average roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, still more preferably 40 nm or more, and even more preferably 50 nm or more from the viewpoint of improving peel strength. .
• the Rq value is preferably 480 nm or less, more preferably 460 nm or less, still more preferably 440 nm or less, still more preferably 420 nm or less, even more preferably 400 nm or less, particularly preferably 380 nm or less, in order to obtain a smooth insulating layer surface. 360 nm or less is particularly preferable, and 340 nm or less is even more preferable.
• the Rq value is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, still more preferably 70 nm or more, and particularly preferably 90 nm or more.
• the elongation of the cured product of the resin composition of the present invention can be grasped by the measurement method described in ⁇ Measurement of elongation> described later. From the viewpoint that the handleability of the cured product can be improved by improving the elongation and cracks and cracks can be prevented, preferably 2.4% or more, more preferably 2.6% or more. 8% or more is further preferable, and 3.0% or more is even more preferable. On the other hand, from the viewpoint of reducing the coefficient of thermal expansion of the cured product, 5% or less is preferable, and 4% or less is more preferable.
• the minimum melt viscosity of the resin composition layer of the adhesive film of the present invention can be determined by the measurement method described in ⁇ Measurement of minimum melt viscosity> described later. From the viewpoint of improving the laminating property of the adhesive film, improving the embedding property, and suppressing bleeding, 500 to 14000 poise is preferable, 1000 to 13000 poise is more preferable, 2000 to 12000 poise is further preferable, 3000 to 11000 poise is still more preferable, and 4000 to 10,000 poise is further preferable. Particularly preferred.
• the resin composition of this invention can harden an epoxy resin and a hardening
• a hardening accelerator An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.
• the amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). Phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU) and the like. You may use these 1 type or in combination of 2 or more types.
• trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl).
• Phenol, 1,8-diazabicyclo (5,4,0) -undecene hereinafter abbreviated as DBU
• guanidine type hardening accelerator Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido
• the imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate 1-cyanoethyl-2-phenylimidazolium trimellitate,
• Triphenylphosphine a phosphonium borate compound
• tetraphenylphosphonium tetraphenylborate n-butylphosphonium tetraphenylborate
• tetrabutylphosphonium decanoate 4- Methylphenyl triphenylphosphonium thiocyanate
• tetraphenylphosphonium thiocyanate butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.
• the content of the curing accelerator (excluding the metal curing accelerator) is in the range of 0.005 to 1% by mass when the nonvolatile content in the resin composition is 100% by mass.
• the range of 0.01 to 0.5% by mass is more preferable. If it is less than 0.005% by mass, curing tends to be slow and a long thermosetting time is required, and if it exceeds 1% by mass, the storage stability of the resin composition tends to decrease.
• organometallic complex or organometallic salt of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin
• organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
• Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
• organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.
• the addition amount of the metal-based curing accelerator is such that the metal content based on the metal-based curing catalyst is in the range of 25 to 500 ppm when the nonvolatile content in the resin composition is 100% by mass.
• the range of 40 to 200 ppm is more preferable. If it is less than 25 ppm, it tends to be difficult to form a conductor layer excellent in adhesion to the surface of the insulating layer having a low arithmetic average roughness. If it exceeds 500 ppm, the storage stability and insulation of the resin composition are lowered. Tend to.
• thermoplastic resin The resin composition of the present invention can further improve the mechanical strength of the cured product by further containing (E) a thermoplastic resin, and further improve the film molding ability when used in the form of an adhesive film. You can also.
• thermoplastic resins include phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Can do. These thermoplastic resins may be used alone or in combination of two or more.
• the weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000 from the viewpoints of improving film molding ability, mechanical strength, and compatibility of the resin varnish.
• the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).
• GPC gel permeation chromatography
• the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
• the content of the thermoplastic resin in the resin composition is not particularly limited, but the nonvolatile content in the resin composition is not limited. 0.1 to 10% by mass is preferable with respect to 100% by mass, and 1 to 5% by mass is more preferable. If the content of the thermoplastic resin is too small, the effect of improving the film forming ability and mechanical strength tends to not be exhibited. If the content is too large, the melt viscosity increases and the arithmetic average roughness of the insulating layer surface after the wet roughening process is low. It tends to increase.
• the resin composition of the present invention can further improve plating peel strength by containing (F) rubber particles, and can also improve drill workability, decrease dielectric loss tangent, and obtain stress relaxation effects.
• the rubber particles that can be used in the present invention are, for example, those that do not dissolve in the organic solvent used when preparing the varnish of the resin composition, and are incompatible with the essential components such as cyanate ester resin and epoxy resin. is there. Accordingly, the rubber particles exist in a dispersed state in the varnish of the resin composition of the present invention.
• Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.
• Preferable examples of rubber particles that can be used in the present invention include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles.
• the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
• a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer.
• the glassy polymer layer is made of, for example, a polymer of methyl methacrylate
• the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
• Two or more rubber particles may be used in combination.
• Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, IM-401 modified 1, IM-401 modified 7-17 (trade name, manufactured by Ganz Kasei Co., Ltd.), Metabrene KW-4426 (trade name, Mitsubishi) Rayon Co., Ltd.).
• Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 ⁇ m, manufactured by JSR Corporation).
• SBR crosslinked styrene butadiene rubber
• acrylic rubber particles include Methbrene W300A (average particle size 0.1 ⁇ m) and W450A (average particle size 0.2 ⁇ m) (manufactured by Mitsubishi Rayon Co., Ltd.).
• the average particle size of the rubber particles is preferably in the range of 0.005 to 1 ⁇ m, more preferably in the range of 0.2 to 0.6 ⁇ m.
• the average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.
• FPAR-1000 concentrated particle size analyzer
• the content of the rubber particles is preferably 1 to 10% by mass, more preferably 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
• the resin composition of the present invention can impart flame retardancy by further containing (G) a flame retardant.
• the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
• organophosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Nikko Corporation, and phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Leophos 30, 50, 65, 90, 110 manufactured by Ajinomoto Fine Techno Co., Ltd.
• organic nitrogen-containing phosphorus compounds include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Pharmaceutical Co., Ltd.
• Phosphazene compounds such as As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.
• the content of the flame retardant is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 8% by mass, where the nonvolatile content in the resin composition is 100% by mass. A range of mass% is more preferred.
• thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds
• organic fillers such as silicon powder, nylon powder, and fluorine powder
• thickeners such as Orben and Benton
• adhesion-imparting agents such as imidazole compounds, thiazole compounds, triazole compounds, silane coupling agents, alkoxy oligomers
• phthalocyanine blue, phthalocyanine green, and iodin -Colorants such as green, disazo yellow, and carbon black can be listed.
• the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.
• the use of the resin composition of the present invention is not particularly limited, but sheet-like laminated materials such as adhesive films and prepregs, circuit boards (laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials
• a resin composition is required, such as a semiconductor sealing material, hole-filling resin, and component-filling resin.
• a resin composition for multilayer printed wiring boards it can be suitably used as a resin composition for forming an insulating layer, and more preferably as a resin composition for forming a conductor layer by plating. Can be used.
• the resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. .
• the softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminating property of the sheet-like laminated material.
• the adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. Alternatively, the resin composition layer is formed by drying the organic solvent by blowing hot air or the like. Thereby, the adhesive film by which the resin composition was formed as a resin composition layer on a support body can be manufactured.
• organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
• aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.
• the drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less.
• the amount of the organic solvent in the varnish and the boiling point of the organic solvent for example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, the resin composition is supported on the support.
• An adhesive film having a layer formed thereon can be formed.
• the thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the resin composition layer preferably has a thickness of 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m.
• the support examples include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films.
• PET polyethylene terephthalate
• polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films.
• release foil metal foil, such as copper foil and aluminum foil.
• the support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment.
• the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
• the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
• a protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact.
• the thickness of the protective film is not particularly limited, but is, for example, 1 to 40 ⁇ m. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
• the adhesive film can also be stored in a roll.
• an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator.
• the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like.
• a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards.
• one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board.
• the surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.
• the adhesive film when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp.
• a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used.
• the laminating conditions are not particularly limited.
• the pressure bonding temperature laminating temperature is preferably 70 to 140 ° C.
• the laminating method may be a batch method or a continuous method using a roll.
• the vacuum lamination can be performed using a commercially available vacuum laminator.
• Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
• the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine.
• a general vacuum hot press machine For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.
• the pressing condition is that the degree of vacuum is usually 1 ⁇ 10 ⁇ 2 MPa or less, preferably 1 ⁇ 10 ⁇ 3 MPa or less.
• heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin.
• the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2
• the second stage press has a temperature of 150 to 200 ° C.
• a pressure in a range of 1 to 40 kgf / cm 2 Preferably it is done.
• the time for each stage is preferably 30 to 120 minutes.
• Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.
• thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C.
• the support is not peeled off after the insulating layer is formed, it is peeled off here.
• holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.
• a conductor layer is formed on the insulating layer by dry plating or wet plating.
• dry plating a known method such as vapor deposition, sputtering, or ion plating can be used.
• wet plating the surface of the insulating layer is subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order to form an uneven anchor.
• the swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes, preferably at 55 to 65 ° C. for 5 to 10 minutes.
• Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable.
• Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
• Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securiganth P), Swelling Dip Securigans SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan Co., Ltd. be able to.
• the roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes, preferably at 70 to 80 ° C. for 10 to 20 minutes.
• the oxidizing agent examples include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can.
• the concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight.
• Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan.
• the neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes, preferably at 35 to 45 ° C. for 3 to 8 minutes.
• As the neutralizing solution an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.
• a conductor layer is formed by combining electroless plating and electrolytic plating.
• a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
• a subsequent pattern formation method for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
• the prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which the resin composition of this invention impregnated the sheet-like reinforcement base material.
• a sheet-like reinforcement base material what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example.
• the resin is once coated on a coated paper having good releasability from the resin without dissolving it in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or the resin is used in an organic solvent.
• This is a method for producing a prepreg by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it.
• a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.
• ⁇ Multilayer printed wiring board using prepreg> an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described.
• One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and vacuum press laminated under pressure and heating conditions.
• the pressurizing and heating conditions are preferably a pressure of 5 to 40 kgf / cm 2 (49 ⁇ 10 4 to 392 ⁇ 10 4 N / m 2 ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes.
• the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.
• a semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention.
• a semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention.
• the “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location.
• the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
• the semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps.
• Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
• “Mounting method by buildup layer without bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a multilayer printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. Furthermore, the method is roughly divided into the following BBUL method 1) and BBUL method 2). BBUL method 1) Mounting method in which semiconductor chip is mounted in recess of multilayer printed wiring board using underfill agent BBUL method 2) Mounting method in which semiconductor chip is mounted in recess of multilayer printed wiring board using adhesive film or prepreg
• the BBUL method 1) specifically includes the following steps.
• Step 1) A multi-layer printed wiring board with a conductor layer removed from both sides is provided, and a through hole is formed by a laser or a mechanical drill.
• Step 2) Adhesive tape is attached to one side of the multilayer printed wiring board, and the bottom surface of the semiconductor chip is disposed in the through hole so as to be fixed on the adhesive tape.
• the semiconductor chip at this time is preferably lower than the height of the through hole.
• Step 3) The semiconductor chip is fixed to the through hole by injecting and filling an underfill agent into the gap between the through hole and the semiconductor chip.
• Step 4) The adhesive tape is then peeled off to expose the bottom surface of the semiconductor chip.
• Step 5) The adhesive film or prepreg of the present invention is laminated on the bottom surface side of the semiconductor chip to cover the semiconductor chip.
• Step 6) After curing the adhesive film or prepreg, drill with a laser to expose the bonding pad on the bottom surface of the semiconductor chip, and connect with wiring by performing the roughening treatment, electroless plating, and electrolytic plating described above To do. You may laminate
• the BBUL method 2) specifically includes the following steps.
• Step 1) A photoresist film is formed on the conductor layers on both sides of the multilayer printed wiring board, and an opening is formed only on one side of the photoresist film by a photolithography method.
• Step 2) The conductor layer exposed in the opening is removed with an etching solution to expose the insulating layer, and then the resist films on both sides are removed.
• Step 3) Using a laser or a drill, all of the exposed insulating layer is removed and drilled to form a recess.
• the laser energy is preferably a laser whose energy can be adjusted so as to lower the laser absorption rate of copper and increase the laser absorption rate of the insulating layer, and more preferably a carbon dioxide laser.
• Step 4) The bottom surface of the semiconductor chip is placed in the recess with the opening side facing, the adhesive film or prepreg of the present invention is laminated from the opening side, the semiconductor chip is covered, and the gap between the semiconductor chip and the recess is formed. Embed.
• the semiconductor chip at this time is preferably lower than the height of the recess.
• Step 5) After the adhesive film or prepreg is cured, holes are formed with a laser to expose the bonding pad on the bottom surface of the semiconductor chip.
• Step 6) By performing the roughening treatment, electroless plating, and electrolytic plating described above, the wiring is connected, and if necessary, an adhesive film or a prepreg is further laminated.
• the semiconductor device is miniaturized and transmission loss is reduced, and since no solder is used, the semiconductor chip does not have its thermal history, and solder and resin distortion may occur in the future.
• a mounting method using a bumpless build-up layer (BBUL) is preferable, the BBUL method 1) and the BBUL method 2) are more preferable, and the BBUL method 2) is more preferable.
• the inner layer circuit board was applied to an electroless copper plating solution containing PdCl 2 at 40 ° C. It was immersed for 5 minutes and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After annealing for 30 minutes at 150 ° C., an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 35 ⁇ 5 ⁇ m. Next, annealing was performed at 200 ° C. for 60 minutes. The circuit board was measured for peel strength (peel strength) of the plated conductor layer.
• peel strength peel strength of plated conductor layer
• a gripping tool TSE Co., Ltd., Autocom type testing machine AC-50C-SL
• the load kgf / cm when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured.
• Ra value and Rq value were obtained from numerical values obtained with a measurement range of 121 ⁇ m ⁇ 92 ⁇ m by a VSI contact mode and a 50 ⁇ lens. And it measured by calculating
• melt viscosities of the resin composition layers in the adhesive films prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were measured. Using a model Rheosol-G3000 manufactured by UBM Co., Ltd., using a parallel plate having a resin amount of 1 g and a diameter of 18 mm, a starting temperature of 60 ° C. to 200 ° C., a heating rate of 5 ° C./min, The melt viscosity was measured under measurement conditions of a measurement temperature interval of 2.5 ° C. and vibration of 1 Hz / deg.
• the product 1 was produced by stirring.
• the maximum temperature reached during the surface treatment was about 80 ° C., and the average temperature was about 70 ° C.
• the maximum temperature reached during the surface treatment was about 80 ° C., and the average temperature was about 65 ° C.
• SC2050-SQ manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
• Methyltrimethoxysilane (“MTMS-A” manufactured by Tama Chemical Co., Ltd.) (0.3 parts by mass) was stirred for 5 minutes while sprayed to produce Product 4.
• the maximum temperature reached during the surface treatment was about 90 ° C., and the average temperature was about 75 ° C.
• ⁇ Production Example 5 100 parts by mass of spherical silica (“SC2050-SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m) was charged into a Henschel-type powder mixer, and a liquid polyfunctional epoxy resin (“HP4032SS” manufactured by DIC Corporation), Naphthalene type epoxy resin, MEK solution having a viscosity at 25 ° C. of 32 Pa ⁇ s, an epoxy equivalent of 144 and a non-volatile content of 80% by mass) was stirred for 10 minutes while spraying 2 parts by mass of N-phenyl-3-amino.
• SC2050-SQ spherical silica manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
• HP4032SS liquid polyfunctional epoxy resin
• MEK solution having a viscosity at 25 ° C. of 32 Pa ⁇ s, an epoxy equivalent of 144 and a non-volatile content of 80% by mass
• the product 5 was produced by stirring for 5 minutes while spraying 0.6 parts by mass of a propyl group-containing alkoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C. of 1000 mm 2 / s).
• the maximum temperature reached during the surface treatment was about 95 ° C., and the average temperature was about 85 ° C.
• Example 1 5 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, “HP4700” manufactured by DIC Corporation), 14 parts by mass of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy 14 parts by mass of resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 parts by mass of solvent naphtha with stirring, and then cooled to room temperature.
• a naphthalene type epoxy resin epoxy equivalent 144, “HP4700” manufactured by DIC Corporation
• liquid bisphenol A type epoxy resin epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation
• biphenyl type epoxy 14 parts by mass of resin epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.
• a phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, methyl ethyl ketone (hereinafter abbreviated as “MEK”) solution having a non-volatile content of 60% by mass of phenolic hydroxyl group equivalent 124), naphthalene-based Phenol resin (phenolic hydroxyl group equivalent 215, “SN485” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a nonvolatile content of 60% by mass), 10 parts by mass, phenoxy resin (weight average molecular weight 35000, manufactured by Mitsubishi Chemical Co., Ltd.
• LA-7054 methyl ethyl ketone
• the resin varnish was prepared by uniformly dispersing with a rotary mixer. Next, the resin varnish is uniformly applied by a die coater on the release surface of a polyethylene terephthalate film with a alkyd release treatment (thickness 38 ⁇ m) so that the thickness of the resin composition layer after drying is 40 ⁇ m. And dried at 80 to 110 ° C.
• Example 2 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 2. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• Example 3 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 3. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• Example 4 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 4. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• Example 5 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 5. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• Example 6 Except that 0.6 parts by mass of N-phenyl-3-aminopropyl group-containing alkoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C. of 1000 mm 2 / s) was further added to the resin varnish of Example 1. A resin varnish was prepared in exactly the same manner. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 2 parts by mass of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), modified naphthalene type 18 parts by mass of an epoxy resin (epoxy equivalent: about 330, “ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.) was heated and dissolved in 25 parts by mass of solvent naphtha, and then cooled to room temperature.
• naphthalene type epoxy resin epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation
• bixylenol type epoxy resin epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation
• modified naphthalene type 18 parts by mass of an epoxy resin (epoxy equivalent: about 330, “ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.) was heated and dissolved in 25 parts
• an active ester curing agent (“PCC-8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223), a prepolymer of bisphenol A dicyanate (Lonza Japan ( "BA230S75” manufactured by Co., Ltd., 30 parts by mass of a MEK solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass, a phenoxy resin (weight average molecular weight 35000, MEK having a non-volatile content of 30% by mass, Mitsubishi Chemical Corporation "YL7553” (1: 1 solution of cyclohexanone) 10 parts by weight, 1 part by weight of 4% by weight MEK solution of 4-dimethylaminopyridine as a curing accelerator, 1% by weight of cobalt (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 parts
• Example 1 A resin varnish was prepared in exactly the same manner except that the product 1 of Example 1 was changed to 100 parts by mass of spherical silica (“SC2050-SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m). Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• SC2050-SQ spherical silica
• Example 2 The product 1 of Example 1 was changed to 100 parts by mass of spherical silica (“SC2050-SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m), and an epoxy resin (epoxy equivalent 144, manufactured by DIC Corporation) HP4032SS ”) A resin varnish was prepared in the same manner except that 2 parts by mass were added. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
• SC2050-SQ spherical silica manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
• an epoxy resin epoxy equivalent 144, manufactured by DIC Corporation
• the resin compositions of Examples 1 to 7 have sufficient values of peel strength with low arithmetic average roughness and low root mean square roughness. Moreover, it turns out that elongation improves and the handleability is improving. Furthermore, it turns out that melt viscosity falls and the handleability of an adhesive film is improving. Note that the Rq value reflects a local state on the surface of the insulating layer, and thus it can be seen that the Rq value is reduced to a dense rough surface. On the other hand, in Comparative Examples 1 to 3, the arithmetic average roughness and the root mean square roughness were large, the plating was swollen, and the peel strength was extremely small.
• the plated conductor layer exhibits sufficiently high peel strength.
• a new resin composition can be provided.
• an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device using the same can be provided.
• electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

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• 2012
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