JP4983341B2 - Insulating resin sheet with copper foil, multilayer printed wiring board, method for producing multilayer printed wiring board, and semiconductor device - Google Patents

Description

The present invention relates to an insulating resin sheet with copper foil, a multilayer printed wiring board, a method for producing a multilayer printed wiring board, and a semiconductor device.

  In recent years, high-density integration of printed wiring boards is progressing as demands for high-speed transmission, miniaturization, and weight reduction of electronic devices increase. Therefore, a build-up process is often employed in which wiring is stacked while only interlayer portions of the printed wiring board are connected by via holes (VH). Among them, the process using a copper foil with resin has become the mainstream. However, since a copper foil having a thickness of 9 to 18 μm is used at present, there is a limitation in forming a fine wiring circuit. (Patent Documents 1 and 2) Next, a build-up process by a semi-additive method is attracting attention because a fine wiring circuit can be formed. In this semi-additive method, after VH is formed on the surface of the insulating layer with a laser or the like, smear of VH can be removed by plasma treatment or chemical treatment and adhesion to the subsequent electroless copper plating can be improved. (Patent Documents 3, 4, and 5) However, since Pd, which is a catalyst for electroless plating, adheres to the entire resin surface, there is a problem that the insulation reliability between the fine wiring circuits decreases. In addition, the roughening of the resin surface by chemical treatment is difficult to control, and it is difficult to control the selection of chemicals and conditions, so the versatility is poor. was there. Therefore, there is a need for an insulating resin sheet with a copper foil that is excellent in fine wiring circuit formability, high-frequency characteristics, and adhesion to an insulating layer.

Japanese Patent Laid-Open No. 7-224252 Japanese Patent Application Laid-Open No. 2002-299834 JP 2001-181375 A JP 2001-196743 A JP 2005-285540 A

An object of the present invention is to provide an insulating resin sheet with a copper foil having excellent adhesion to an insulating layer when the insulating layer of the multilayer printed wiring board is formed. In addition, an insulating resin sheet with copper foil having excellent processability, a multilayer printed wiring board capable of forming a thin and fine wiring circuit using the insulating resin sheet, and a method for manufacturing the same, and further using the multilayer printed wiring board It is an object to provide a semiconductor device having excellent reliability.

Such an object is achieved by the present invention described in the following [1] to [ 14 ].
[1] An insulating layer of a multilayer printed wiring board is formed on an electrolytic copper foil layer of a peelable copper foil obtained by laminating a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm. Obtained by laminating resin compositions ,
The resin composition includes a thermosetting resin and an inorganic filler,
The thermosetting resin includes an epoxy resin and a cyanate ester resin,
The inorganic filler der Ru copper foil with an insulating resin sheet which contains silica.
[2] The insulating resin sheet with a copper foil according to the item [ 1 ], wherein the inorganic filler includes talc.
[ 3 ] The insulating resin sheet with a copper foil according to [ 1 ] or [ 2 ], wherein the inorganic filler contains a metal hydroxide.
[ 4 ] The insulating resin sheet with a copper foil according to any one of [ 1 ] to [ 3 ], wherein the inorganic filler includes spherical silica that has been surface-treated in advance.
[ 5 ] The insulating resin sheet with copper foil according to the item [ 4 ], wherein the spherical silica that has been surface-treated in advance is 5 to 50% by weight in the total inorganic filler.
[ 6 ] The surface treatment agent for spherical silica that has been surface-treated in advance is at least one compound selected from the group consisting of functional group-containing silanes, cyclic oligosiloxanes, organohalosilanes, and alkylsilazanes. The insulating sheet with a copper foil according to the item [ 4 ] or [ 5 ].
[ 7 ] The functional group-containing silanes include epoxy silane, (meth) acryl silane, mercapto silane, amino silane, vinyl silane, isocyanate silane, ureido silane, (5-norbornene-2-yl) alkyl silane, and phenyl silane. The insulating resin sheet with copper foil according to item [ 6 ], which is at least one compound selected from the group.
[ 8 ] The [1] to [ 7 ] item, wherein the resin composition further includes at least one flame retardant selected from the group consisting of a phosphorus-containing epoxy, a condensed phosphate ester, an organic phosphorus compound, and zinc molybdate. any copper foil with an insulating resin sheet according to one of.
[ 9 ] The resin composition further includes at least one antioxidant selected from the group consisting of hindered phenols, benzotriazoles, triazines, benzophenones, coumarins, and phosphines, and / or ultraviolet absorption. copper foil with an insulating resin sheet according to any one of agents to the is [1] to include [8] term.
[10] [1] to [9] The copper foil with an insulating resin sheet according to any one of clauses, an insulating layer forming step of laminating superposed on the surface the inner layer circuit pattern is formed of an inner layer circuit board A method for producing a multilayer printed wiring board, comprising: a step of opening the insulating layer by laser irradiation; and a step of forming a conductor circuit layer.
[ 11 ] The insulating layer forming step of laminating and laminating the insulating resin sheet with copper foil on the surface of the inner layer circuit board on which the inner layer circuit pattern is formed is a step performed using a heat and pressure laminate in a vacuum [ 10 ] The manufacturing method of the multilayer printed wiring board as described in a term.
[ 12 ] The step of opening the insulating layer by laser irradiation is in a state in which the carrier foil layer of the copper foil is peeled off, and the surface of the electrolytic copper foil layer is subjected to a treatment having laser energy absorption [ 10 ] or the manufacturing method of the multilayer printed wiring board as described in a term [ 11 ].
[ 13 ] A multilayer printed wiring board obtained by the manufacturing method according to any one of items [10] to [12] .
[ 14 ] A semiconductor device comprising a chip mounted on the multilayer printed wiring board according to the item [ 13 ].

The insulating resin sheet with copper foil of the present invention is excellent in high-frequency characteristics, smear removability, fine wiring formability, line-to-line connection reliability, and semiconductor device mounting reliability.
According to the present invention, it is possible to obtain an insulating resin sheet having both high reliability and workability required as an insulating layer, and copper foil such as a multilayer printed wiring board that requires fine processing for high density It can be used as an insulating material. In addition, it is possible to obtain multilayer printed wiring boards for electronic devices that require miniaturization of parts, high-speed signal transmission, and high reliability, so that semiconductor devices with high density, thinness, and excellent reliability can be obtained. Applicable to.

  Hereinafter, an insulating resin sheet with a copper foil, a multilayer printed wiring board, a method for producing a multilayer printed wiring board, and a semiconductor device according to the present invention will be described.

The insulating resin sheet with a copper foil of the present invention uses a peelable type copper foil in which a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm are bonded together. When the insulating resin sheet with copper foil is used to form an insulating layer of a multilayer printed wiring board, the adhesion between the conductor circuit and the insulating layer is excellent. Therefore, the connection reliability between the insulating resin layers of the multilayer printed wiring board is excellent. Furthermore, since a fine wiring circuit can be formed, a multilayer printed wiring board and a semiconductor device using the multilayer printed wiring board can be reduced in thickness and weight.

The multilayer printed wiring board of the present invention is excellent in surface smoothness of the insulating resin layer, VH shape by laser irradiation, and smear removability when the insulating resin sheet with copper foil is laminated by a build-up process. Excellent. Moreover, since there is no adhesion of the Pd catalyst used in electroless copper plating between the fine wiring circuits, the insulation reliability is excellent. Further, even when lead-free solder mounting is performed at the time of manufacturing a semiconductor device, the connection reliability between the multilayer printed wiring board and the semiconductor element is excellent.

  Hereinafter, the insulating resin sheet with copper foil will be described.

  The copper foil used in the present invention is a peelable copper foil in which a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm are bonded together. Examples of the carrier foil include copper foil, aluminum foil, nickel foil, copper alloy foil, stainless steel foil, and plated composite metal foil. Among these, it is particularly preferable to use a copper foil as a carrier foil because reuse is easy after peeling. The thickness of such carrier foil is preferably 5 to 100 μm. When the thickness is less than 5 μm, the handleability of the copper foil is poor, and when it is 100 μm or more, the manufacturing cost increases. Further, “peelable” means that the carrier foil can be easily peeled after a temperature of 80 to 200 ° C. and a pressure of 0.1 to 5 MPa are applied during the production of the multilayer printed wiring board. for that reason. A bonding interface layer may be provided between the carrier foil and the electrolytic copper foil layer.

The bonding interface layer is not particularly limited as long as it has an adhesive strength that does not easily peel off the copper foil and is bonded to the carrier foil. For example, examples of the inorganic bonding interface include metals such as chromium, lead, silver, zinc, and nickel, metal oxides thereof, sulfides such as sodium sulfide, ammonium sulfide, and copper sulfide, and chromates. . Examples of the organic bonding interface include nitrogen compounds, sulfur compounds, organic silicon compounds, and carboxylic acids.

The electrolytic copper foil layer can be generally produced by a known electrolysis method, and can be obtained by controlling the deposition rate of particles. Moreover, the substantial thickness of the electrolytic copper foil layer by a weight method uses a 0.5-5.0 micrometer thing. If it is thicker than this, it is inferior in microcircuit formation.

As the resin composition used for the insulating resin sheet with copper foil of the present invention, generally known thermosetting resins can be used. For example, an epoxy resin, a cyanate ester resin, a thermosetting polyimide resin, a thermosetting polyphenylene ether resin, a phenol resin, and the like can be mentioned, and one type or two or more types are used in combination, and there is no particular limitation. Among these, it is preferable to use a highly versatile epoxy resin in terms of heat resistance, chemical resistance, workability, and the like. Further, when it is desired to improve heat resistance and migration resistance, a cyanate ester resin can be used in combination.

The epoxy resin used for the insulating resin sheet with a copper foil of the present invention is not particularly limited as long as it has three or more epoxy groups in the molecule. For example, phenol novolac type epoxy resin, cresol novolac epoxy resin, etc. novolac type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, Examples thereof include epoxy resins such as dicyclopentadiene type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, and fluorene type epoxy resins. When it is desired to improve the flame retardancy, a biphenyl aralkyl type epoxy resin, an aryl alkylene type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a phenoxy type epoxy resin, or the like can be suitably used. Moreover, when the moisture absorption solder heat resistance is improved, an epoxy resin such as a dicyclopentadiene type epoxy resin, a norbornene type epoxy resin, an adamantane type epoxy resin, or a fluorene type epoxy resin can be suitably used. These epoxy resins are used alone or in combination of two or more, and are not particularly limited.

Although content of the said epoxy resin is not specifically limited, 5-70 weight% of a resin composition is preferable, and 15-50 weight% is especially preferable. If the content is less than the lower limit, the adhesiveness of the insulating layer may be reduced or the heat resistance may be reduced. If the content exceeds the upper limit, the mechanical strength may be reduced, or the moisture resistance of the product obtained. May decrease.

The cyanate ester resin is a resin having two or more cyanate groups (—O—CN) in the molecule. For example, 2,2′-bis (4-cyanatophenyl) isopropylidene, 1,1′-bis (4-cyanatophenyl) ethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 3-bis (4-cyanatophenyl-1- (1-methylethylidene)) benzene, dicyclopentadiene type cyanate ester, phenol novolac type cyanate ester, bis (4-cyanatophenyl) thioether, bis (4-cyanato) Phenyl) ether, 1,1,1-tris (4-cyanatophenyl) ethane, tris (4-cyanatophenyl) phosphite, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-c Anatophenyl) propane, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4, 4'-dicyanatobiphenyl and other phenols Cyanate ester resins obtained by the reaction of emissions and the like.

Further, as the cyanate ester resin, a prepolymerized one can be used. That is, the cyanate ester resin may be used alone, a cyanate ester resin having a different weight average molecular weight may be used in combination, or the cyanate ester resin and its prepolymer may be used in combination.
The prepolymer is usually obtained by, for example, trimerizing the cyanate ester resin by a heat reaction or the like, and is preferably used for adjusting the moldability and fluidity of the resin composition. .
The prepolymer is not particularly limited. For example, when a prepolymer having a trimerization rate of 20 to 50% by weight is used, good moldability and fluidity can be expressed.

  Although content of the said cyanate ester resin is not specifically limited, 5 to 50 weight% of the whole said insulating resin material is preferable, and 10 to 30 weight% is especially preferable. When the content is less than the lower limit, the heat resistance may be reduced, and when the content exceeds the upper limit, the strength of the insulating resin layer may be reduced.

The inorganic filler used in the insulating resin sheet with copper foil of the present invention is not particularly limited, but for example, silicates such as talc, fired clay, unfired clay, mica, glass, titanium oxide, alumina, silica, fused silica Oxides such as, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates such as barium sulfate, calcium sulfate, calcium sulfite or the like Sulfites, zinc borate, barium metaborate, aluminum borate, calcium borate, borate such as sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, carbon nitride, strontium titanate, titanate Examples thereof include titanates such as barium. One of these can be used alone, or two or more can be used in combination. Among these, talc, silica, aluminum hydroxide, and magnesium hydroxide are particularly preferable. Talc is preferable in terms of versatility and low cost, and silica is preferable in terms of heat resistance and interlayer connection reliability. Moreover, aluminum hydroxide and magnesium hydroxide are preferable in terms of flame retardancy.

  The silica is preferably spherical silica, and the spherical silica is preferably further treated with a treatment agent for surface treatment in advance. The treating agent is preferably at least one compound selected from the group consisting of functional group-containing silanes, cyclic oligosiloxanes, organohalosilanes, and alkylsilazanes.

  Among the treatment agents, the surface treatment of the spherical silica using organohalosilanes or alkylsilazanes is suitable for hydrophobizing the silica surface, and the dispersion of the spherical silica in the resin composition It is preferable in terms of excellent properties. When using a combination of normal functional group-containing silanes and the above-mentioned organohalosilanes or alkylsilazanes, any of them may be used for the surface treatment first, but the organohalosilanes or alkylsilazanes are dispersed first. It is preferable to impart the organic material affinity to the spherical silica surface, and the surface treatment of the following functional group-containing silanes can be made effective. The ratio of the amount of the normal functional group-containing silane used here to the amount of the organohalosilane or alkylsilazane is preferably 500/1 to 50/1 (weight ratio). If it is out of the range, the mechanical strength may decrease.

The functional group-containing silanes are not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3 , 4-epoxycyclohexyl) ethyldimethoxysilane, and other epoxysilane compounds, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyldi Mercaptosilanes such as (meth) acrylic silanes such as ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane, N-phenyl 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N-2 (aminoethyl) -3- Aminopropyltriethoxysilane, N-2 (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and N- (vinylbenzyl)- Aminosilanes such as 2-aminoethyl-3-aminopropyltrimethoxysilane, vinylsilanes such as vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltrichlorosilane, isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, 3-urea Ureidosilanes such as dopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane, (5-norbornen-2-yl) trimethoxysilane, (5-norbornene-2-yl) triethoxysilane, and (5-norbornene) Examples include (5-norbornen-2-yl) alkylsilane such as -2-yl) ethyltrimethoxysilane, and phenylsilane such as phenyltrimethoxysilane. These functional group-containing silanes are suitably selected in order to improve the dispersibility of the inorganic filler and the moldability of the resin composition.

The cyclic oligosiloxanes are not particularly limited, and examples thereof include hexamethylcyclotrisiloxane and oritamethylcyclotetrasiloxane.

The organohalosilanes are not particularly limited, and examples thereof include trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane. Of these, dimethyldichlorosilane is more preferred.

The alkylsilazanes are not particularly limited, and examples thereof include hexamethyldisilazane, 1,3-divinyl 1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, and hexamethylcyclotrisilazane. Can do. Of these, hexamethyldisilazane is more preferred.

A method of treating the spherical silica with a surface treating agent in advance can be performed by a known method. For example, it can be carried out by putting spherical silica in a mixer, spraying the treatment agent with stirring in a nitrogen atmosphere, and holding at a predetermined temperature for a certain time. The treatment agent to be sprayed may be dissolved in a solvent in advance. In addition, the spherical silica and the treatment agent are put into a mixer, and a solvent is further added and stirred. In order to promote the reaction between the silanol on the silica surface and the coupling agent, heating or a small amount of water is added. Acids and alkalis can also be used.

Although the temperature at the time of the treatment depends on the kind of the treatment agent, it is necessary to perform the treatment at a temperature lower than the decomposition temperature of the treatment agent. On the other hand, if the treatment temperature is too low, the binding force between the treatment agent and spherical silica is low, and the treatment effect cannot be obtained. Therefore, it is necessary to perform the treatment at an appropriate temperature according to the treatment agent. Furthermore, the holding time can be appropriately adjusted depending on the type of processing agent or the processing temperature.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 to 10.0 μm. More preferably, it is 0.1-5.0 micrometers. When the average particle diameter of the inorganic filler is less than the lower limit, when preparing a resin varnish using the resin composition, the viscosity of the resin varnish is increased, and thus when an insulating resin sheet with copper foil is produced. May affect the workability of the. On the other hand, if the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the resin varnish. By setting the average particle size of the inorganic filler within the above range, it is possible to achieve an excellent balance of these characteristics.

As the inorganic filler, an inorganic filler having a monodispersed average particle diameter can be used, or an inorganic filler having a polydispersed average particle diameter can be used. Further, the monodisperse and / or polydisperse inorganic filler having an average particle size of one kind or two or more kinds can be used in combination, and is not particularly limited.

Although content of the said inorganic filler is not specifically limited, 20 to 80 weight% of the whole said resin composition is preferable. More preferably, by setting the content to 35 to 70% by weight, the effect of imparting low water absorption and low thermal expansion can be exhibited.

The content of the spherical silica surface-treated in advance is preferably 5 to 50% by weight in the total inorganic filler. Thereby, it is excellent in moldability and mechanical strength. If it is less than the said lower limit, there exists a possibility that mechanical strength may fall. Moreover, when more than the said upper limit, there exists a possibility that an inorganic filler may aggregate and a moldability may fall.

It is preferable that the resin composition further contains a flame retardant. Thereby, the flame retardance of a multilayer printed wiring board can be improved. Examples of the flame retardant include phosphorus-containing epoxy, condensed phosphate ester, organic phosphorus compound, and zinc molybdate. From the viewpoint of environmental safety, it is preferable to use a non-halogen flame retardant. Among these, one kind can be used alone, or two or more kinds can be used in combination, and is not particularly limited.

The resin composition preferably further contains an antioxidant and / or an ultraviolet absorber. Thereby, the long-term weather resistance improvement of a printed wiring board and ultraviolet-ray deterioration can be prevented. Examples of antioxidants and UV absorbers include hindered phenols, benzotriazoles, triazines, benzotriazoles, benzophenones, coumarins, and phosphines, one of which is used alone. It is also possible to use two or more types in combination, and there is no particular limitation.

  The resin composition may further contain a thermoplastic resin. Thereby, the flexibility of the insulating resin sheet with copper foil can be improved. Moreover, the mechanical strength of the hardened | cured material obtained from the said resin composition can be improved.

As the thermoplastic resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, thermoplastic resin such as polystyrene resin, styrene-butadiene copolymer, styrene-isoprene copolymer, etc. And thermoplastic elastomers such as polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, polyester-based elastomers, and diene-based elastomers such as polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, and methacryl-modified polybutadiene. However, the present invention is not limited to these. They can be used alone, or two or more kinds having different weight average molecular weights can be used in combination, or one kind or two or more kinds and a prepolymer thereof can be used in combination. Among these, a phenoxy resin is preferable. Thereby, heat resistance and mechanical strength can be improved.

The phenoxy resin is not particularly limited. For example, a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and bisphenol M (4,4 ′-(1,3- Phenoxy resin having phenylenediisopridiene) bisphenol) skeleton, phenoxy resin having bisphenol P (4,4 ′-(1,4) -phenylenediisopridiene) bisphenol) skeleton, bisphenol Z (4,4′- A phenoxy resin having a bisphenol skeleton, a phenoxy resin having a novolak skeleton, a phenoxy resin having an anthracene skeleton, a phenoxy resin having a fluorene skeleton, and a dicyclopentadiene skeleton. To phenoxy resins, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton include phenoxy resins having an adamantane skeleton. Further, as the phenoxy resin, a structure having a plurality of types of skeletons can be used, and phenoxy resins having different ratios of the skeletons can be used. Furthermore, a plurality of types of phenoxy resins having different skeletons can be used, a plurality of types of phenoxy resins having different weight average molecular weights can be used, or prepolymers thereof can be used in combination.

The resin composition may use a curing accelerator as necessary. The curing accelerator is not particularly limited, and examples thereof include imidazole compounds, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III). Organic metal salts, tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, phenolic compounds such as phenol, bisphenol A, nonylphenol, organic compounds such as acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid An acid or the like, or a mixture thereof can be mentioned. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.

Among the curing accelerators, an imidazole compound is particularly preferable. Thereby, the storage stability of the resin composition and the moisture absorption solder heat resistance when the insulating layer is formed can be improved. The imidazole compound has such a property that it can be dissolved up to a molecular level or dispersed to a state close to that upon dissolution in an organic solvent together with the epoxy resin.

By using such an imidazole compound, the resin composition can effectively promote the reaction of the epoxy resin, and can impart the same characteristics even if the amount of the imidazole compound is reduced. it can. Furthermore, a resin composition using such an imidazole compound can be cured with high uniformity from a minute matrix unit with a resin component. Thereby, the insulation of the insulating resin layer formed in the multilayer printed wiring board and heat resistance can be improved.

And the insulating resin layer which consists of such a resin group composition of this invention can be effectively removed, for example, when performing smear removal using oxidizing agents, such as a permanganate and a dichromate. After removing the smear, by performing metal plating on the VH wall surface and the electrolytic copper foil layer surface, the fine circuit formability is excellent. Moreover, since the electrolytic copper foil layer has an extremely minute uneven shape and has high adhesion between the insulating layer and the conductor circuit, it has excellent interlayer connection reliability.

Examples of the imidazole compound used in the resin composition of the present invention include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methyl. Imidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- (2'-undecylimidazolyl) -ethyl-s- Triazine, 2,4-diamino-6- [2'-ethyl-4-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4- Examples thereof include methyl-5-hydroxymethylimidazole.

Among these, an imidazole compound selected from 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-ethyl-4-methylimidazole is preferable. These imidazole compounds have particularly excellent compatibility, so that a highly uniform cured product can be obtained and a fine and uniform roughened surface can be formed, so that a fine conductor circuit can be easily formed. In addition, the multilayer printed wiring board can exhibit high heat resistance.

Although content of the said imidazole compound is not specifically limited, 0.01 to 5.00 weight% is preferable with respect to the whole said resin composition, and 0.05 to 3.00 weight% is especially preferable. Thereby, especially heat resistance can be improved.

The resin composition preferably further uses a coupling agent. The coupling agent is not particularly limited, and examples thereof include silane-based, titanate-based, and aluminum-based coupling agents. For example, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-amino Ethyl) aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane and N-β Aminosilane compounds such as-(N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 2- (3,4-epoxy) (Cyclohexyl) ethyltrimeth Epoxy silane compounds such as xysilane, and others include 3-mercaptopropyltrimethoxysilane, 3-mercatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-methacryloxypropyl And trimethoxysilane. One of these can be used alone, or two or more can be used in combination. By using a coupling agent, the wettability of the said epoxy resin and the interface of cyanate ester resin and an inorganic filler can be improved. As a result, heat resistance, particularly moisture-absorbing solder heat resistance, can be improved.

Although content of the said coupling agent is not specifically limited, It is preferable that it is 0.05-5.00 weight part with respect to 100 weight part of inorganic fillers. Particularly preferred is 0.01 to 2.5 parts by weight. If the content of the coupling agent is less than the lower limit, the effect of covering the inorganic filler and improving the heat resistance may not be sufficient. On the other hand, if the upper limit is exceeded, the bending strength of the insulating layer may decrease. By setting the content of the coupling agent within the above range, it is possible to achieve an excellent balance of these characteristics.

In addition, the resin composition of the present invention has various additives such as leveling agents, antifoaming agents, pigments, dyes, antifoaming agents, ions for improving various properties such as resin compatibility, stability, and workability. A scavenger, a non-reactive diluent, a reactive diluent, a thixotropic agent, a thickener and the like may be added as appropriate.

  The manufacturing method of the insulating sheet with copper foil of this invention is demonstrated. First, the resin composition is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, etc. Dissolve, mix, and stir in various organic solvents using various mixing machines such as the ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method. To prepare a resin varnish.

Although content of the resin composition in the said resin varnish is not specifically limited, 45 to 85 weight% is preferable and 55 to 75 weight% is especially preferable. Thereby, it can be set as the resin varnish of the suitable viscosity for forming an insulating resin sheet in peelable type copper foil.

Next, the resin varnish is coated on an electrolytic copper foil layer of a peelable type copper foil using various coating apparatuses, and then dried. Or after spray-coating a resin varnish on a film or metal foil with a spray apparatus, this is dried. By these methods, an insulating resin sheet with a film or a metal foil can be produced.
Although the said coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, an insulating resin sheet with a film or metal foil having a uniform insulating resin layer thickness without voids can be efficiently produced.

FIG. 1 is a cross-sectional view schematically showing an example of the insulating resin sheet with copper foil (FIG. 1) of the present invention.
Insulating resin sheet 1 with a copper foil is obtained by laminating an insulating resin layer 2 composed of the resin composition with a peelable carrier foil layer 3 and an electrolytic copper foil layer 4 having a thickness of 0.5 to 5.0 μm. It is formed on a peelable type copper foil 5. The insulating resin layer made of the resin composition is excellent in circuit step embedding, flatness after embedding, and laser processability.

Although the thickness of the insulating resin layer 2 of the said insulating resin sheet 1 with copper foil is not specifically limited, 1-60 micrometers is preferable and especially 5-40 micrometers is preferable. The thickness of the insulating resin layer is preferably equal to or greater than the lower limit for improving insulation reliability, and is preferably equal to or smaller than the upper limit for achieving thinning, which is one of the purposes in a multilayer wiring board. Thereby, when manufacturing a multilayer printed wiring board, the unevenness | corrugation of an inner layer circuit can be filled and shape | molded, and suitable insulation resin layer thickness can be ensured.

Next, the manufacturing method of a multilayer printed wiring board is demonstrated.

2 to 3 illustrate a method for producing a multilayer printed wiring board using an insulating resin sheet with a film. FIG. 2A shows an inner layer circuit board 6 in which a circuit pattern is formed on a core board (for example, a double-sided copper foil of FR-4). After the hole 8 is opened by the drilling machine and the opening 8 is provided, the opening 8 is plated by electroless plating so that both surfaces of the inner circuit board 6 are electrically connected. Then, the inner layer circuit 7 is formed by etching the copper foil.
In addition, as the inner layer circuit board used when obtaining the multilayer printed wiring board, for example, an inner layer circuit portion subjected to a roughening process such as a blackening process can be suitably used. The opening 8 can be appropriately filled with a conductor paste or a resin paste.

The material of the inner layer circuit 7 may be any material as long as it is suitable for this manufacturing method, but is preferably removable by a method such as etching or peeling in the formation of the inner layer circuit. What has chemical resistance with respect to the chemical | medical solution etc. which are used for this is preferable. Examples of the material of the inner layer circuit 7 include copper foil, copper plate, copper alloy plate, 42 alloy, nickel, and the like. In particular, the copper foil, the copper plate, and the copper alloy plate are most preferable for use as the inner layer circuit 7 because not only electrolytic plated products and rolled products can be selected, but also various thicknesses can be easily obtained.

Next, an insulating resin sheet with a copper foil is used and laminated so as to cover the inner layer circuit 7 (FIG. 2B). The method of laminating (laminating) the insulating resin sheet with copper foil is not particularly limited, but a method of laminating using a vacuum press, a normal pressure laminator, and a laminator that is heated and pressurized under vacuum is preferable, and more preferably under vacuum. This is a method using a laminator for heating and pressurizing.

Next, the formed insulating resin layer 3 is cured by heating. Although the temperature to harden | cure is not specifically limited, The range of 100 to 250 degreeC is preferable. In particular, 150 ° C to 200 ° C is preferable. Moreover, in order to facilitate the next laser irradiation and removal of the resin residue, it may be in a semi-cured state. In the next step, laser is irradiated to form the via hole 9 in the resin, but before that, the carrier foil 3 needs to be peeled off (FIG. 2C). The carrier foil 3 may be peeled off after the insulating resin layer is formed, before heat curing, or after heat curing. If the carrier foil 3 can be directly irradiated with a laser to form a via hole, the carrier foil 3 can be peeled off after electroless plating.

Next, the insulating resin layer 3 is irradiated with a laser to form a via hole 9 (FIG. 2D). As the laser, known methods such as excimer laser, UV laser and carbon dioxide laser can be used. Formation of the via hole 9 by the laser can easily form a fine via hole 9 regardless of whether the material of the insulating resin layer 2 is photosensitive or non-photosensitive. Therefore, it is particularly preferable when it is necessary to form fine openings in the insulating resin layer 2.
In addition, it is preferable to remove the resin residue etc. in VH (via hole) after laser irradiation with an oxidizing agent such as permanganate or dichromate. When the insulating resin sheet with copper foil of the present invention is used, it is only necessary to remove smear in the VH, so that smear can be removed efficiently. Moreover, since a smooth insulating resin layer is obtained, it is excellent in thickness reduction and fine circuit formability. Moreover, since the adhesiveness with an electrolytic copper foil layer is high, it is excellent in interlayer connection reliability. Moreover, it is excellent in high frequency characteristics due to fine roughening.

Next, an electroless copper plating layer 10 for interlayer connection is formed inside and on the surface of VH (FIG. 2E). The thickness of the electroless copper plating layer 10 is 0.2 to 5 μm, and 0.5 μm is preferable for the uniformity of the thickness of the plating layer. If the carrier foil 3 is peeled off after electroless plating, a fine circuit can be further formed.

Next, the outer layer circuit 11 is formed (FIG. 3F). The outer layer circuit 11 can be formed by, for example, a known method such as a semi-additive method, but the present invention is not limited thereto. For example, the outer layer circuit 11 is formed by via fill plating in the VH by electrolytic copper plating and pattern plating (FIG. 3F). Finally, the outer layer circuit 11 is formed by removing the electroless plating layer used in the power feeding layer and the electrolytic copper foil layer 4 having a thickness of 0.5 to 5.0 μm by flash etching or the like. In the step, by repeating the steps shown in FIGS. 2B to 3G, the number of layers can be further increased (FIG. 3H). When the insulating resin layer is in a semi-cured state as described above, post-curing may be performed.
When the insulating resin sheet with copper foil of the present invention is used, since the insulating resin layer other than the VH wall surface is covered with the copper foil, there is no adhesion of the Pd catalyst for electroless plating when forming a fine circuit. Therefore, the insulation reliability is excellent. Moreover, it is excellent in fine wiring formability compared with the conventional subtractive method.

Next, a solder resist 19 is formed (FIG. 3 (i)). The method of forming the solder resist 19 is not particularly limited. For example, a method of laminating a dry film type solder resist and forming it by exposure and development, or a method of forming a liquid resist printed by exposure and development Is made by In addition, the electrode part for a connection can be suitably coat | covered with metal films, such as gold plating, nickel plating, and solder plating. A multilayer wiring board can be manufactured by such a method.

As another method, VH is formed by laser irradiation using a mask (conformal mask) in which a hole pattern is formed in the electrolytic copper foil layer 4 at a position where a via is formed, and thereafter, FIG. There is a method of manufacturing by the same method as (e) to FIG. Further, there is a case where half etching is performed to further thin the electrolytic copper foil.
On the other hand, when the copper foil is etched entirely using the fact that fine irregularities on the surface of the electrolytic copper foil are transferred to the surface of the insulating resin layer, multilayer printed wiring is performed in the same manner as when using an insulating resin sheet with a film. A plate can also be manufactured. However, the adhesion between the insulating resin layer and the electroless copper plating layer and the Pd catalyst for electroless copper plating may adhere to the entire surface of the insulating resin layer, which may reduce the connection reliability of the fine wiring circuit.

Next, the semiconductor device will be described.
FIG. 4 is a sectional view showing an example of the semiconductor device 12 of the present invention.
As shown in FIG. 4, a plurality of connection electrode portions 15 are provided on one surface of the multilayer printed wiring board 16. The semiconductor element 13 having the solder bump 14 provided corresponding to the connection electrode portion of the multilayer printed wiring board is connected to the multilayer printed wiring board 16 through the solder bump 14. A liquid sealing resin 20 is filled between the multilayer printed wiring board 16 and the semiconductor element 13 to form a semiconductor device. In the multilayer printed wiring board 16, the inner layer circuit 7, the insulating layer 22, and the outer layer circuit 18 are formed on the inner layer circuit board 23, and the inner layer circuit 21 and the outer layer circuit 18 are connected via the conductor posts 17. Yes. The outermost layer is covered with a solder resist 19. The solder bump 14 is preferably made of an alloy made of tin, lead, silver, copper, bismuth, or the like. A method for connecting a semiconductor element and a multilayer printed wiring board is to use a flip chip bonder or the like to align a connection electrode portion on a substrate and a metal bump of the semiconductor element, and then an IR reflow device, a hot plate, and other heating devices The solder bumps are heated to the melting point or higher by using, and the multilayer printed wiring board on the substrate and the solder bumps are fused and connected. In order to improve connection reliability, a metal layer having a relatively low melting point, such as solder paste, may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this joining step, the connectivity can be improved by applying flux to the solder bumps and / or the surface layer of the connection electrode portion on the multilayer printed wiring board.

Examples of the insulating resin sheet with copper foil, multilayer printed wiring board, and semiconductor device of the present invention will be described below, but the present invention is not limited thereto.
( Reference Example 1)
1. Production of insulating resin sheet with copper foil 100 parts by weight of a phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-75) as a thermosetting resin, and phenol novolak (manufactured by Meiwa Kasei Co., Ltd., HF-) as a curing agent 4) 53 parts by weight, aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., BE033) 100 parts by weight, 1 part by weight of other coupling agent (manufactured by GE Toshiba Silicon Co., A-187), curing accelerator (Shikoku) 0.5 parts by weight of 2E4MZ manufactured by Kasei Co., Ltd. was mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. The ratio of the inorganic filler in the resin composition was about 39% by weight.

A peelable type copper foil (manufactured by Nippon Electrolytic Co., Ltd., YSNAP-3B) obtained by bonding the resin varnish obtained above with a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm. Carrier foil layer: Copper foil (18 μm), electrolytic copper foil layer (3 μm)) is applied to an electrolytic copper foil layer using a comma coater so that the resin layer after drying is 40 μm, and this is applied at 150 ° C. It dried for 10 minutes with the drying apparatus, and manufactured the insulating resin sheet with a copper foil.

Next, the multilayer printed wiring board produced using the obtained insulating resin sheet with copper foil will be described.

1. Opening with a drill using a double-sided copper-clad laminate (ELC-4785GS manufactured by Sumitomo Bakelite Co., Ltd.) having a total thickness of 0.3 mm and a copper foil thickness of 12 μm. Then, conduction between the upper and lower copper foils was achieved by electroless plating, and the inner layer circuit was formed on both sides by etching the copper foils on both sides.
Next, the inner layer circuit was roughened by roughening treatment (Atotech Japan Co., Ltd., bond film). Next, the insulating resin sheet with copper foil obtained above was laminated on the inner layer circuit using a vacuum laminating apparatus. Next, after heating at a temperature of 200 ° C. for 60 minutes to form an insulating resin layer, the carrier foil layer was peeled off. The conditions for laminating the insulating resin sheet with copper foil were as follows: temperature 100 ° C., pressure 1 MPa, and time 30 seconds.

2. Laser processing and formation of outer layer circuit Next, the surface electrolytic copper foil layer was subjected to blackening treatment, and then a VH of φ60 μm for interlayer connection was formed with a carbon dioxide laser. Next, it is immersed in a swelling solution at 70 ° C. (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further immersed in an aqueous solution of potassium permanganate at 80 ° C. (Concentrate Compact CP, manufactured by Atotech Japan) for 5 minutes. Then, it neutralized and the desmear process in VH was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, pattern copper plating, and then nickel The plating was performed in the order of plating and gold plating, and finally the plating resist was peeled off. Next, the entire surface was flash etched to form a pattern of L / S = 20/20 μm.
Finally, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 40 μm was formed on the circuit surface to obtain a multilayer printed wiring board.

The following evaluation was performed on the insulating resin sheet with copper foil of Reference Example 1, and the results are shown in Table 1.

<Surface roughness>
The surface roughness (Ra) was measured with a non-contact type three-dimensional optical interference type surface roughness meter. (Nippon Beiko Co., Ltd., WYKO NT1100) An evaluation sample was prepared by laminating an insulating resin sheet with a copper foil and then etching the entire surface of the electrolytic copper foil layer.

<Processability (smear removal)>
After VH formation and desmearing with a carbon dioxide laser, smear residues were confirmed on the VH bottom with a scanning electron microscope (SEM). As evaluation samples, 50 VHs subjected to the above-described laser processing and desmear treatment at the time of forming the outer layer circuit were arbitrarily selected.
Each code is as follows.
◎: Good There is no residue. ○: There is virtually no problem. There is a residue of less than 2μm from the VH wall. △: Substantially unusable. There is a residue of 2μm or more from the VH wall. ×: Unusable There is a residue on the entire VH bottom.

<Fine wiring formability>
The presence or absence of disconnection of the outer circuit pattern was observed with a metal microscope, and the wiring shape after the cross-section was cut was evaluated. In addition, the evaluation sample used what formed L / S = 20/20 micrometer pattern in laser processing and an outer layer circuit. For the wiring shape, the squeezing rate is calculated from the root wiring width of the wiring. (Constriction rate = (design value−root wiring width) / design value ÷ 2 × 100),
Each code is as follows.
◎: No disconnection, constriction rate of less than 10% ○: Virtually no problem No disconnection, constriction rate of 10% or more and less than 20% △: Virtually unusable No disconnection, constriction rate of 20% or more and less than 35% ×: Unusable disconnection Yes, constriction rate 35% or more

<Insulation reliability between lines>
A line insulation reliability test was performed under the conditions of an applied voltage of 50 VDC, a temperature of 85 ° C., and a humidity of 85%. In addition, the evaluation sample used the multilayer printed wiring board which formed 40 micrometers in thickness of the soldering resist on the board | substrate produced with the said L / S = 20/20 micrometer pattern.
The test was terminated when the insulation resistance value was less than 1 × 10 ⁸ Ω.
Each code is as follows.
◎: Good 500 hours or more ○: Virtually no problem 200 hours or more and less than 500 hours △: Virtually unusable 100 hours or more and less than 200 hours ×: Unusable less than 100 hours

Next, a semiconductor device manufactured using the multilayer printed wiring board obtained above will be described.

  The multilayer printed wiring board used was cut to a size of 50 mm × 50 mm and provided with a connecting electrode portion subjected to nickel gold plating corresponding to the solder bump arrangement of the semiconductor element. In the semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm), the solder bump is formed of a eutectic of Sn / Pb composition, and the circuit protective film is a positive photosensitive resin (CRC-8300 manufactured by Sumitomo Bakelite Co., Ltd.). What was formed in was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on a multilayer printed wiring board by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

The following evaluation items were evaluated for the insulating resin sheet with copper foil, the multilayer printed wiring board, and the semiconductor device obtained above. The results are shown in Table 1 .

(3) Mounting reliability The mounting reliability is as follows. The semiconductor device obtained above is left for 100 hours in an atmosphere of temperature 85 ° C. and humidity 85%, and then reflowed 260 ° C. three times to obtain an ultrasonic deep defect inspection device. Thus, peeling of the back surface of the semiconductor element and chipping of the solder bump were valued.
Each code is as follows.
◎: Good peeling, no bump defect ○: Virtually no problem Only minute peeling around the underfill, no bump defect △: Virtually unusable 10% or more peeling and bump defect ×: Unusable 80% peeling or more Bump defect

( Reference Example 2)
Copper foil as in Reference Example 1 except that 2 parts by weight of an antioxidant and a coumarin-based (manufactured by Kanto Chemical Co., 3- (2'-benzothiazolyl) -7-diethylaminocoumarin) were added as an ultraviolet absorber. An insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. In addition, the ratio of the inorganic filler in the resin composition was about 39% by weight.

( Reference Example 3)
As thermosetting resins, 50 parts by weight of phenol novolac epoxy resin (Nippon Kayaku Co., Ltd., EOCN-1020-75), 50 parts by weight of cyanate ester resin (1,1′-bis (4-cyanatophenyl) ethane) In addition, 100 parts by weight of talc (manufactured by Fuji Talc Kogyo Co., Ltd., LMS-400) as an inorganic filler, 15 parts by weight of phenoxy resin (manufactured by JER, EP-4275) as a thermoplastic resin, and other coupling agents (manufactured by GE Toshiba Silicon Corporation) A-187) 1 part by weight and 0.5 part by weight of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., 2E4MZ) were mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 46% by weight.

( Reference Example 4)
As a thermosetting resin, 70 parts by weight of a phenol novolac type epoxy resin (Dainippon Ink Industries, EPICLON N865), as a curing agent, 46 parts by weight of phenol novolac (Maywa Kasei Co., Ltd., HF-4), as an inorganic filler, average 180 parts by weight of spherical silica having a particle size of 0.5 μm (manufactured by Admatechs, SO-25H), phenoxy resin (J
ER, EP-4275, 20 parts by weight, phosphorus-containing epoxy (JP-A-11-279258, Example 1)
30 parts by weight of the epoxy resin), 1 part by weight of a coupling agent (manufactured by GE Toshiba Silicone, A-187) and 0.5 part by weight of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., 2E4MZ) are added to methyl ethyl ketone. Mixed and dissolved. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 52% by weight.

(Example 5)
As thermosetting resin, biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000) 50 parts by weight, cyanate ester resin (phenol novolac type cyanate ester, PT30) 50 parts by weight, average particle size 0.5 μm as inorganic filler 150 parts by weight of spherical silica (manufactured by Admatech, SO-25H), 20 parts by weight of phenoxy resin (manufactured by JER, EP-4275) as a thermoplastic resin, other coupling agent (manufactured by GE Toshiba Silicone, A-187) 1 part by weight and 0.5 part by weight of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., 1B2PZ) were mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

(Example 6)
As an inorganic filler, 135 parts by weight of spherical silica having an average particle size of 0.5 μm (manufactured by Admatech, SO-2H) and spherical silica having an average particle size of 0.5 μm whose surface was previously subjected to aminosilane treatment (manufactured by Admatech, SC2050) -KMF) was the same as Example 5 except that 15 parts by weight (silica conversion) was used. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

(Example 7)
As an inorganic filler, 75 parts by weight of spherical silica having an average particle diameter of 0.5 μm (manufactured by Admatech, SO-2H), spherical silica having an average particle diameter of 0.5 μm whose surface has been previously treated with aminosilane (manufactured by Admatech, SC2050) -KMF) was the same as Example 5 except that 75 parts by weight (silica conversion) was used. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

(Example 8)
Example 5 was used except that 150 parts by weight (in terms of silica) of spherical silica (SC2050-SE, manufactured by Admatech Co., Ltd.) having an average particle diameter of 0.5 μm whose surface was previously treated with epoxysilane was used as the inorganic filler. Made the same. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

( Reference Example 9)
The same as Reference Example 1 except that 120 parts by weight of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., BE033) and 30 parts by weight of condensed phosphate ester (manufactured by Daihachi Chemical Co., Ltd., PX-200) were used as the metal hydroxide. did. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1.
The ratio of the inorganic filler in the resin composition was about 39% by weight.

( Reference Example 10)
100 parts by weight of phenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-75) as a thermosetting resin, 53 parts by weight of phenol novolac (manufactured by Meiwa Kasei Co., Ltd., HF-4), as an inorganic filler 120 parts by weight of talc (manufactured by Fuji Talc Kogyo Co., Ltd., LMS-400), 5 parts by weight of zinc molybdate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 part by weight of a coupling agent (manufactured by GE Toshiba Silicone, A-187), curing 0.5 parts by weight of an accelerator (manufactured by Shikoku Kasei Co., Ltd., 2E4MZ) was mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 43% by weight.

( Reference Example 11)
Example 5 was the same as Example 5 except that 150 parts by weight of talc (manufactured by Fuji Talc Kogyo Co., Ltd., LMS-400) was used as the inorganic filler instead of spherical silica. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

( Reference Example 12)
Except for using 75 parts by weight of talc (Fuji Talc Kogyo Co., Ltd., LMS-400) as an inorganic filler, and 75 parts by weight of aluminum hydroxide (Nihon Light Metal Co., Ltd., BE033) as a metal hydroxide. The same as in Example 5. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 55% by weight.

(Example 13)
As thermosetting resin, biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000) 50 parts by weight, cyanate ester resin (phenol novolac type cyanate ester, PT30) 50 parts by weight, average particle size 0.5 μm as inorganic filler 100 parts by weight of spherical silica (manufactured by Admatech, SO-25H), 20 parts by weight of phenoxy resin (manufactured by JER, EP-4275) as a thermoplastic resin, an antioxidant, and a benzotriazole-based compound (Ciba 2 parts by weight of Specialty Chemical Co., TINUVIN 234), 1 part by weight of a coupling agent (GE Toshiba Silicone, A-187), 0.5 part by weight of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., 1B2PZ) It was mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 44% by weight.

(Example 14)
As thermosetting resin, biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000) 50 parts by weight, cyanate ester resin (phenol novolac type cyanate ester, PT30) 50 parts by weight, average particle size 0.5 μm as inorganic filler 100 parts by weight of spherical silica (manufactured by Admatech, SO-25H), 20 parts by weight of a phenoxy resin (manufactured by JER, EP-4275) as a thermoplastic resin, an antioxidant, and a hindered phenol compound (as a UV absorber) 2 parts by weight of Ciba Specialty Chemical Co., Irganox 1076), 0.5 parts by weight of phosphine compound (Ciba Specialty Chemical Co., Irgafos 168), 1 part by weight of other coupling agents (GE Toshiba Silicone, A-187) , Curing accelerator (manufactured by Shikoku Chemicals, 1 B2PZ) 0.5 part by weight was mixed and dissolved in methyl ethyl ketone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and adjusted the resin varnish of 70 weight% of solid content. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 44% by weight.

(Comparative Example 1)
Instead of a peelable type copper foil in which a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm are bonded together, an ordinary copper foil (manufactured by Mitsui Metal Mining Co., Ltd., 3EC-M3- The same as Reference Example 3 except that VLP-18) was used. In the same manner as in Reference Example 1, an insulating resin sheet with a copper foil was prepared, and copper plating was performed to a thickness of 22 μm by panel plating. Next, a circuit pattern of L / S = 20/20 was formed by a known subtractive method, and an insulating resin sheet with a copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 46% by weight.

(Comparative Example 2)
In place of peelable carrier foil layer and peelable copper foil with 0.5-5.0 μm thick electrolytic copper foil layer, polyethylene terephthalate (made by Mitsubishi Polyester Film Co., Ltd.) is used as a support for the insulating resin layer. , 38 μm), which was the same as Reference Example 4. A circuit pattern of L / S = 20/20 was formed by a known semi-additive method, and an insulating resin sheet with copper foil, a multilayer printed wiring board, and a semiconductor device were evaluated. The results are shown in Table 1. The ratio of the inorganic filler in the resin composition was about 52% by weight. The desmear conditions were the same as in Reference Example 1.

Table 1 shows the evaluation results of Reference Examples 1 to 4, Examples 5 to 8, Reference Examples 9 to 12, Examples 13 and 14, and Comparative Examples 1 to 2 Insulated resin sheet with copper foil, multilayer printed wiring board, and semiconductor device. Indicated.

As is clear from Table 1, Reference Examples 1 to 4, Examples 5 to 8, Reference Examples 9 to 12, and Examples 13 and 14 are good in that the surface roughness (Ra) of the insulating layer is 0.3 μm or less. Value. As a result, the insulating resin sheet with copper foil is excellent in high frequency characteristics. Further, Reference Examples 1 to 4, Examples 5 to 8, Reference Examples 9 to 12, and Examples 13 and 14 were excellent in smear removability. Examples 5 to 8, 13 and 14 were particularly excellent in smear removing properties. Further, Reference Examples 1 to 4, Examples 5 to 8, Reference Examples 9 to 12, and Examples 13 and 14 were excellent in fine wiring formability. Further, the multilayer printed wiring board was excellent in line connection reliability and semiconductor device mounting reliability. On the other hand, Comparative Example 1 is inferior in high-frequency characteristics due to its large surface roughness, and inferior in smear removability because the copper foil is thick and cannot completely penetrate the resin even when laser irradiation is performed. As a result, the fine wiring formability is inferior, the fine wiring shape is poor, the insulation between lines of the multilayer printed wiring board is inferior, and the mounting reliability of the semiconductor device is also inferior because there are many process abnormalities in the multilayer printed wiring board. It was. In Comparative Example 2, although the surface roughness was small, the smear removability in a short time was slightly inferior, and the Pd catalyst was adhered to the entire surface, resulting in inferior insulation reliability between the multilayer printed wiring boards.

ADVANTAGE OF THE INVENTION According to this invention, the insulating resin sheet with a copper foil which has high reliability and workability required as an insulating layer can be obtained. It can be used as an insulating resin sheet with a copper foil such as a multilayer printed wiring board that requires fine processing for high density. In addition, it is possible to obtain multilayer printed wiring boards for electronic devices that require miniaturization of parts, high-speed signal transmission, and high reliability, so that semiconductor devices with high density, thinness, and excellent reliability can be obtained. Applicable to.

Example of insulating resin sheet with copper foil (schematic cross-sectional view) Example of a method (schematic cross-sectional view) for producing a multilayer printed wiring board using an insulating resin sheet with copper foil Example of a method (schematic cross-sectional view) for producing a multilayer printed wiring board using an insulating resin sheet with copper foil = continuation of FIG. Example of schematic cross-sectional view of semiconductor device

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Insulation resin sheet with copper foil 2 Insulation resin layer 3 Carrier foil layer 4 Electrolytic copper foil layer 5 Peelable type copper foil 6 Inner layer circuit board 7 Inner layer circuit 8 Opening 9 Via hole 10 Electroless copper plating layer 11 Outer layer circuit 12 Semiconductor Device 13 Semiconductor element 14 Solder bump 15 Connection electrode part 16 Multilayer printed wiring board 17 Conductor post 18 Outer layer circuit 19 Solder resist 20 Liquid sealing resin 21 Inner layer circuit 22 Insulating layer 23 Inner layer circuit board

Claims (14)

Resin composition to be an insulating layer of a multilayer printed wiring board on an electrolytic copper foil layer of a peelable type copper foil obtained by laminating a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm the laminated obtained,
The resin composition includes a thermosetting resin and an inorganic filler,
The thermosetting resin includes an epoxy resin and a cyanate ester resin,
The inorganic filler der Ru copper foil with an insulating resin sheet which contains silica. Wherein the inorganic filler is a copper foil with an insulating resin sheet according to claim 1 containing talc. The said inorganic filler is an insulating resin sheet with a copper foil of Claim 1 or 2 containing a metal hydroxide. The said inorganic filler is an insulating resin sheet with a copper foil of any one of Claim 1 thru | or 3 containing the spherical silica surface-treated beforehand. The insulating resin sheet with copper foil according to claim 4 , wherein the pre-surface-treated spherical silica is 5 to 50% by weight in the total inorganic filler. Surface treatment agent of the pre-surface-treated spherical silica, functional group-containing silanes, cyclic oligosiloxane compounds, organohalosilanes, and claim 4 is at least one compound selected from the group consisting of alkyl silazane compound Or the insulating sheet with copper foil of 5 . The functional group-containing silane is selected from the group consisting of epoxy silane, (meth) acryl silane, mercapto silane, amino silane, vinyl silane, isocyanate silane, ureido silane, (5-norbornen-2-yl) alkyl silane, and phenyl silane. The insulating resin sheet with copper foil according to claim 6 , which is at least one kind of compound. Said resin composition further phosphorus-containing epoxy, condensed phosphoric acid esters, organic phosphorus compounds, and those containing at least one flame retardant selected from the group consisting of zinc molybdate in any one of claims 1 to 7 The insulating resin sheet with copper foil as described. The resin composition further contains at least one antioxidant and / or ultraviolet absorber selected from the group consisting of hindered phenols, benzotriazoles, triazines, benzophenones, coumarins, and phosphines. copper foil with an insulating resin sheet according to any one of claims 1 to 8 is Dressings. The copper foil with an insulating resin sheet according to any one of claims 1 to 9, an insulating layer forming step of laminating superposed on the surface the inner layer circuit pattern is formed of an inner layer circuit board, laser the insulating layer The manufacturing method of a multilayer printed wiring board including the process of opening a hole by irradiation, and the process of forming a conductor circuit layer. The copper foil with an insulating resin sheet, the insulating layer forming step of the inner layer circuit pattern is laminated by superimposing the formed surface of the inner layer circuit board, according to claim 1 0 is a step carried out using a heating and pressing the laminate under vacuum The manufacturing method of the multilayer printed wiring board as described in 2 ..
Wherein the step of opening the insulating layer laser irradiating, in a state was peeled off the carrier foil layer of copper foil, and electrolytic copper foil layer surface according to claim 10 or a state which has been subjected to treatment with the absorption of the laser energy The manufacturing method of the multilayer printed wiring board of 11 . The multilayer printed wiring board obtained by the manufacturing method of any one of Claims 10 thru | or 12 . A semiconductor device comprising a chip mounted on the multilayer printed wiring board according to claim 13 .