WO2017159816A1 - 絶縁樹脂材料、それを用いた金属層付絶縁樹脂材料および配線基板 - Google Patents

絶縁樹脂材料、それを用いた金属層付絶縁樹脂材料および配線基板 Download PDF

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WO2017159816A1
WO2017159816A1 PCT/JP2017/010767 JP2017010767W WO2017159816A1 WO 2017159816 A1 WO2017159816 A1 WO 2017159816A1 JP 2017010767 W JP2017010767 W JP 2017010767W WO 2017159816 A1 WO2017159816 A1 WO 2017159816A1
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Prior art keywords
resin material
insulating resin
inorganic porous
metal layer
porous aggregate
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PCT/JP2017/010767
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English (en)
French (fr)
Japanese (ja)
Inventor
笠置　智之
高 植村
駿二 今村
祐矢 北川
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日東電工株式会社
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Priority claimed from JP2017047072A external-priority patent/JP7134594B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to US16/084,394 priority Critical patent/US10388425B2/en
Priority to KR1020187026248A priority patent/KR102375660B1/ko
Priority to EP17766811.8A priority patent/EP3432316B1/en
Priority to CN201780016713.9A priority patent/CN108780674B/zh
Publication of WO2017159816A1 publication Critical patent/WO2017159816A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/002—Inhomogeneous material in general
    • H01B3/006—Other inhomogeneous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0175—Inorganic, non-metallic layer, e.g. resist or dielectric for printed capacitor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Definitions

  • the present invention relates to an insulating resin material that is a material having both a low dielectric constant and a low coefficient of thermal expansion that are difficult to obtain conventionally, an insulating resin material with a metal layer using the same, and a wiring board. is there.
  • low-dielectric constant materials are required for high-frequency wiring boards and multilayer wiring boards used in such electronic devices.
  • low-dielectric constant resin materials include polyethylene, polypropylene, polystyrene, Nonpolar polymer resin materials such as tetrafluoroethylene can be used.
  • the resin material has a high coefficient of thermal expansion and is significantly different from the coefficient of thermal expansion of the metal wiring material formed on the substrate, there are problems such as peeling and cutting of the wiring due to the difference in coefficient of thermal linear expansion.
  • Patent Document 1 a technique for producing a substrate having a low relative dielectric constant and a low coefficient of thermal linear expansion using hollow inorganic particles having a hollow center portion is proposed.
  • the hollow inorganic particles are fragile when the hollow inorganic particles are mixed with a binder and formed into a certain shape. As a result, the water absorption rate of the insulating layer is increased. Therefore, when these hollow inorganic particles are used for a substrate material or a wiring board, there is a problem that the dielectric characteristics deteriorate. In order to improve this, the shell of the hollow inorganic particles has to be enlarged, and there has been a limit to obtain an insulating resin composition having a high porosity using the hollow inorganic particles.
  • Patent Document 2 a fluoropolymer dispersion containing a fine silica filler having an average particle size of 2 ⁇ m or less is dried and agglomerated to form a sheet.
  • the lowest relative dielectric constant remains at about 1.94, and it is very difficult to obtain a material having a lower relative dielectric constant with other techniques.
  • a dielectric constant has been desired for many years.
  • those that contain inorganic fillers and have pores are not enough in the amount of polymer that penetrates into the roughened surface of the metal layer, even when trying to adhere to the metal with a hot press or the like. Since there is no contact, weak adhesion is also a problem.
  • the present invention has been made in view of such circumstances, and has a low dielectric constant and a low coefficient of thermal expansion, which are difficult to obtain in the past, and provides a material that also has excellent adhesion to a metal layer. To do.
  • the present invention is an insulating resin material containing inorganic porous aggregates having pores composed of a plurality of fine particles and fibrils made of polytetrafluoroethylene, wherein the fibrils are oriented in multiple directions,
  • a first gist is an insulating resin material which is a fine network structure in which at least one of inorganic porous fine powders and fibrils is connected to each other and has a porosity of 50% or more.
  • the present invention has a second gist of an insulating resin material with a metal layer having a metal layer on at least one surface of the insulating resin material, and the metal layer of the insulating resin material with a metal layer is patterned.
  • the substrate is the third gist. Note that the metal layer is in close contact with the insulating resin material through a fluorine-based resin layer.
  • the present inventors paid attention to the long-standing problem that the low relative dielectric constant and the low thermal linear expansion coefficient are in a trade-off relationship, and it is difficult to achieve both the low relative dielectric constant and the low thermal linear expansion coefficient.
  • the research was conducted with the aim of achieving both a high thermal expansion coefficient and a low coefficient of thermal expansion.
  • the organic porous / inorganic composite technology has been studied with a view to controlling the porosity of materials.
  • inorganic porous aggregates having pores composed of a plurality of fine particles are converted into fibrils made of polytetrafluoroethylene.
  • the insulating resin material of the present invention is an insulating resin material containing inorganic porous aggregates having pores composed of a plurality of fine particles and fibrils made of polytetrafluoroethylene, wherein the fibrils are multidirectional. Oriented and at least one of the above-mentioned inorganic porous aggregates and fibrils is connected to each other, and is a fine network structure having a porosity of 50% or more, so that both an excellent low relative dielectric constant and low thermal linear expansion coefficient are achieved. be able to.
  • the BET specific surface area of the inorganic porous aggregate is 10 to 250 m 2 / g, a strong fine network structure is obtained and an excellent insulating resin material is obtained.
  • the apparent specific gravity of the inorganic porous aggregate is 100 g / L or less, a stronger fine network structure can be obtained.
  • the average particle size of the fine particles constituting the inorganic porous aggregate is 5 to 35 nm, a much stronger fine network structure can be obtained.
  • the fine particles constituting the inorganic porous aggregate are hydrophobic fine powdered silica, the relative dielectric constant and dielectric loss tangent can be obtained with high accuracy.
  • the inorganic porous aggregate is 50% by weight or more with respect to the total of the inorganic porous aggregate and the fibril, a lower thermal linear expansion coefficient can be obtained and the accuracy of the product is excellent. become.
  • the relative dielectric constant of the insulating resin material at a frequency of 10 GHz is 1.55 to 1.9 and the dielectric loss tangent is 0.01 or less, the accuracy of the obtained product becomes excellent.
  • the thermal expansion coefficient of the insulating resin composition is 15 to 50 ppm / K, the accuracy of the product obtained is further improved.
  • an insulating resin material with a metal layer as a substrate material that is excellent in a low relative dielectric constant and a low thermal expansion coefficient can be obtained.
  • the fluorine resin when the metal layer is in close contact with at least one surface of the insulating resin material through the fluorine resin layer, the fluorine resin has a roughened portion of the metal layer, a roughened portion of the insulating resin material, and an empty space. It bites into the hole, develops an anchor effect, and can be firmly attached.
  • the adhesion between the metal layer and the insulating resin material through the fluorine-based resin layer is a peel strength of 0.6 kN / m or more, a highly reliable insulating resin material with a metal layer can be obtained.
  • (A) is the scanning electron microscope (SEM) photograph (magnification 50000 times) which expanded the thickness direction section of the insulating resin material which is one of the embodiments of the present invention, and (b) expanded the surface direction section. It is a SEM photograph (magnification 3000 times). It is sectional drawing of the insulating resin material with a metal layer which is one of the embodiment of this invention. It is sectional drawing of the wiring board which is one of the embodiments of this invention.
  • SEM scanning electron microscope
  • the insulating resin material of the present invention includes an inorganic porous aggregate 2 having pores 3 composed of a plurality of fine particles, polytetrafluoro And fibrils 4 made of ethylene.
  • the fibrils 4 are oriented in multiple directions, and at least one of the inorganic porous aggregate 2 and the fibrils 4 is connected to each other. And a fine network structure having a porosity of 50% or more.
  • reference numeral 1 denotes a cross section of the fibril.
  • the insulating resin material of the present invention becomes a fine network structure by firmly bonding the inorganic porous aggregate 2 having pores 3 composed of a plurality of fine particles with the fibrils 4 made of polytetrafluoroethylene. , With many pores.
  • the fibrils 4 made of polytetrafluoroethylene.
  • the inorganic porous aggregate used in the present invention is composed of a plurality of fine particles.
  • the fine particles are primary particles and exist as aggregates in which a large number of aggregates are aggregated.
  • an inorganic porous aggregate forms a bulky aggregate by agglomerating and fusing a plurality of fine particles in a bead shape.
  • the inorganic porous aggregate is an aggregate having voids.
  • the average particle diameter of the fine particles which are the primary particles is preferably 5 to 35 nm from the viewpoint of aggregation, and more preferably 15 to 35 nm.
  • the compressive strength is lowered, so that there is a tendency for particle collapse in the processing step to occur easily. Poor porosity tends to occur.
  • inorganic porous aggregates composed of fine particles exceeding the above upper limit tend to form irregularities on the surface of the insulating resin material, and are suitable for high-frequency insulating resin materials that require a smoother surface. There is no tendency.
  • the average particle diameter was obtained by directly determining the particle diameter of a plurality of particles (100 particles) with a scanning electron microscope (SEM) or the like, and the average value was defined as the average particle diameter.
  • Secondary aggregates are aggregates obtained by further aggregating primary aggregates.
  • the primary aggregate is usually 100 to 400 nm, and the secondary aggregate is usually 1 to 100 ⁇ m.
  • the inorganic porous aggregate contained in the insulating resin material of the present invention is preferably a secondary aggregate because it is easy to form a fine three-dimensional network structure composed of fine particles.
  • the “hole” composed of a plurality of fine particles of the inorganic porous aggregate means a bulky aggregate void formed by agglomerating and fusing a plurality of fine particles in a bead shape.
  • the shape of the holes may be spherical or irregular, and is not particularly limited.
  • those composed of fine particles having a uniform particle diameter are preferable in terms of easy maintenance of pores.
  • the average pore diameter of the pores is preferably 10 to 1000 nm, and more preferably 50 to 500 nm from the viewpoint of not deteriorating the mechanical properties of the insulating resin material.
  • the above average pore diameter is obtained by directly observing with a scanning electron microscope (SEM) or the like to obtain the pore diameter of a plurality of holes (100), and the average value is taken as the average pore diameter.
  • the maximum hole diameter is the hole diameter.
  • the BET specific surface area of the inorganic porous aggregate is preferably 10 to 250 m 2 / g from the viewpoint of easily forming a bulky aggregate, and more preferably 40 to 100 m 2 / g. If it is less than the above lower limit, aggregated particles that are close to primary particles are formed, and the space composed of a plurality of fine particles is reduced, so that the porosity of the insulating resin material tends to decrease. On the other hand, when the above upper limit is exceeded, the surface of the inorganic porous aggregate is contaminated with water and other contaminants due to an increase in the number of polar functional groups on the surface, such as OH groups. It tends to increase and dielectric properties tend to deteriorate, and inorganic porous aggregates cannot be firmly bound with polytetrafluoroethylene fibrils, and the resulting insulating resin material tends to crack. There is.
  • the specific surface area of the inorganic porous aggregate is determined by the BET method (constant pressure / volume method with nitrogen gas using gas adsorption).
  • the apparent specific gravity of the inorganic porous aggregate is preferably 100 g / L or less from the viewpoint of porosity, more preferably 30 to 100 g / L, and particularly preferably 50 to 60 g / L.
  • the aggregate density of the primary particles is high or becomes an aggregated particle close to the primary particles, and the porosity of the insulating porous material itself is lowered, so the porosity of the insulating resin material is lowered and the desired low There is a tendency that it cannot be made dielectric.
  • the porosity of the inorganic porous aggregate itself increases, but the contact between the primary particles decreases, and the compressive strength tends to decrease.
  • the compressive strength is lowered, the particles of the inorganic porous aggregate are easily collapsed, and good processability cannot be obtained.
  • an insulating resin material having a lower specific dielectric constant and a low thermal linear expansion coefficient can be obtained.
  • the fine particles constituting the inorganic porous aggregate include, for example, hydrophobized porous fine powder silica, titanium oxide, alumina, etc. Among them, it is preferable to use hydrophobized porous fine powder silica. It is preferable from the viewpoint of dielectric constant and low thermal expansion coefficient.
  • the fine particles constituting the inorganic porous aggregate can be used alone or in combination of two or more.
  • porous fine powder silica In order to hydrophobize the porous fine powder silica, there is a method in which the porous fine powder silica is treated with a surface treatment agent such as dimethyldichlorosilane, hexamethyldisilazane, silicone oil, octylsilane or the like.
  • a surface treatment agent such as dimethyldichlorosilane, hexamethyldisilazane, silicone oil, octylsilane or the like.
  • the degree of hydrophobicity of porous fine powder silica can be confirmed by a powder wettability test using a methanol aqueous solution.
  • Porous fine powder silica particles have a high degree of hydrophilicity and wet and settle in water, but hydrophobic fine powder silica particles that have been hydrophobized do not settle in water but wet and settle in methanol.
  • the powder wettability test is a technique for measuring the volume of wetted porous fine powder silica particles having a high degree of hydrophobization in an aqueous solution by changing the methanol concentration of the aqueous methanol solution using this characteristic.
  • a methanol concentration of 30% by weight or more is required in the powder wettability test.
  • hydrophobized porous fine powder silica examples include amorphous silica, precipitated silica, pyrogenic silica, fumed silica, silica gel and the like.
  • fumed silica is preferably used from the viewpoint of a low relative dielectric constant and a low thermal expansion coefficient. These may be used alone or in combination of two or more.
  • the porous fine powder silica hydrophobized a commercially available thing can be used as the said porous fine powder silica hydrophobized.
  • Mizukasil series manufactured by Mizusawa Chemical Co., Ltd.
  • silicia series manufactured by Fuji Silysia Co., Ltd.
  • hydrophobic AEROSIL series manufactured by Nippon Aerosil Co., Ltd.
  • nipseal series manufactured by Tosoh Silica Corporation
  • the porous fine powder silica is preferably a hydrophobic fumed silica of a hydrophobic AEROSIL series (manufactured by Nippon Aerosil Co., Ltd.).
  • the insulating resin material of the present invention contains fibrils made of polytetrafluoroethylene in addition to the inorganic porous aggregate.
  • polytetrafluoroethylene constituting the fibril it is preferable to use polytetrafluoroethylene particles from the viewpoint of fibrillation in the resin composition stage before the production of the insulating resin material.
  • the average particle size of the polytetrafluoroethylene particles is preferably larger than the average particle size of the primary particles of the inorganic porous aggregate in order to facilitate fibrillation.
  • the aggregate of polytetrafluoroethylene particles preferably has a particle diameter of 650 ⁇ m or less from the viewpoint of dispersibility.
  • Fibrilization of polytetrafluoroethylene particles depends on several factors such as the amount of shear force applied, temperature, the presence of any lubricating fluid between the primary particles, etc. Forming fibrils during the molding step is preferable from the viewpoint of promoting fibrillation. When the degree of fibrillation of the polytetrafluoroethylene particles is high, a material having high mechanical strength can be obtained in the structure of the obtained insulating resin material.
  • the fibrils contained in the insulating resin material of the present invention are oriented in multiple directions as shown in FIG. Compared to a resin material in which fibrils are oriented only in one direction, a resin material in which fibrils are oriented in multiple directions has a three-dimensional network structure formed by fibrils, and an insulating resin material having higher mechanical strength can be obtained.
  • connection includes inorganic porous aggregates, fibrils, and a combination of inorganic porous aggregates and fibrils.
  • the combination of the three-dimensional network structure of the inorganic porous aggregate and the three-dimensional network structure of the fibrils is intertwined with each other, and the network structure is intertwined to extend vertically and horizontally, improving the strength of the insulating inorganic material, and improving the porosity. It is preferable because it contributes synergistically to the improvement.
  • the blending amount of the inorganic porous aggregate is preferably 50% by weight or more, and more preferably 50 to 75% by weight, when the total of the polytetrafluoroethylene and the inorganic porous aggregate as the constituent components of the fibril is 100% by weight. In particular, it is preferably blended in an amount of 55 to 70% by weight.
  • the thermal expansion coefficient tends to exceed 50 ppm / K.
  • the upper limit is exceeded, the effect of binding between polytetrafluoroethylene and the inorganic porous aggregate is weakened and the moldability tends to deteriorate.
  • the relative permittivity and the coefficient of thermal expansion can be adjusted by the blending ratio of the inorganic porous aggregate and polytetrafluoroethylene.
  • the degree of bonding of inorganic porous aggregates and the interconnection of at least one of the fibrils varies depending on factors such as the amount of fibrils and the magnitude of the applied shear force.
  • the insulating resin material of the present invention can contain additional material components as necessary.
  • a heat conductive material having a low relative dielectric constant such as boron nitride may be added.
  • a polymer for binding the inorganic porous aggregate may be added as necessary.
  • the additional material component can be added in the range where the relative dielectric constant does not exceed 1.9 in order to form the insulating resin material of the present invention.
  • the manufacturing method of the insulating resin material of the present invention is, for example, (I) A step of preparing a paste by mixing and drying an inorganic porous aggregate and polytetrafluoroethylene in a solvent to obtain a mixed powder, adding a volatile additive to the mixed powder and mixing them When, (II) forming a resin composition sheet using the paste, (III) a step of superposing the resin composition sheets and rolling and forming them in a multistage manner to form a rolled laminated sheet; (IV) removing the volatile additive, (V) a heating and pressing process for adding strength.
  • an insulating resin material having a fine network structure in which a plurality of pores are formed while a structure in which the inorganic porous aggregate and the fibrils made of polytetrafluoroethylene are firmly bound as shown in FIG. 1A is obtained.
  • the inorganic porous aggregate and polytetrafluoroethylene are mixed and dried in a solvent to prepare a mixed powder.
  • the solvent used here include water, lower alcohols such as methanol, ethanol, isopropanol, and butanol. These may be used alone or in combination of two or more.
  • a dispersion of polytetrafluoroethylene from the viewpoint of dispersibility, and drying is performed by a known means such as a drying furnace.
  • the paste When a paste is prepared by adding a volatile additive to the above mixed powder, the paste has an inorganic porous coagulation other than the case where the paste consists only of an inorganic porous fine powder, polytetrafluoroethylene and a volatile additive. This includes the case where the aggregate is combined with polytetrafluoroethylene and volatile additives and other auxiliary components.
  • the volatile additive is preferably a liquid having a boiling point of 300 ° C. or lower, and examples thereof include low molecular weight hydrocarbons such as polyethylene glycol, ester, isoparaffinic hydrocarbon, hexane, and dodecane. Hydrogen is preferably used. These volatile additives can be used alone or in combination of two or more.
  • step (II) a plurality of resin composition sheets are produced using the paste, and in step (III), the produced resin composition sheets are overlapped and rolled in multiple stages to form a rolled laminated sheet. To do.
  • the resin composition sheet is molded in the above step (II), for example, molding using a molding machine such as an FT die, a press machine, an extrusion molding machine, a calender roll, etc. can be mentioned. preferable.
  • a molding machine such as an FT die, a press machine, an extrusion molding machine, a calender roll, etc.
  • the “multi-stage rolling” in the step (III) will be specifically described below.
  • a plurality of (for example, 2 to 10) resin composition sheets are laminated, and the laminate is rolled to obtain a first rolled laminated sheet.
  • Two of the obtained first rolled laminated sheets are stacked one on top of another, and this laminated product is rolled to produce a second rolled laminated sheet.
  • two obtained 2nd rolling lamination sheets are piled up and laminated
  • the above-described laminating and rolling process is repeated until the desired number of constituent layers of the insulating resin material is reached. Repeating this lamination rolling process is called multistage rolling.
  • the strength of the obtained insulating resin material can be increased as the number of constituent layers is increased by rolling in multiple stages, and the number of constituent layers is preferably 10 to 1000.
  • the rolling ratio of the above rolling is preferably 100 to 20000 times from the viewpoint of forming many fibrils.
  • a plurality of rolled laminated sheets are produced by aligning the rolling direction of a plurality of sheets, and (1) the rolling direction of the obtained plurality of rolled laminated sheets is aligned, the sheet surface Is a method of rolling by rotating the sheet 90 degrees from the previous rolling direction while being parallel, (2) 90 sheets from the previous rolling direction with only some of the obtained rolled laminated sheets being parallel (3) a method in which only some of the obtained rolled laminated sheets are placed in a 180-degree folded form and rotated by 90 degrees and rolled.
  • the polytetrafluoroethylene network extends vertically and horizontally, and fibrils having a three-dimensional network structure are formed.
  • a final product having a desired thickness (for example, a thickness of about 0.1 to 2 mm) is produced by the multi-stage rolling, and then the volatile additive is removed in step (IV).
  • the removal of the volatile additive in the step (IV) can be carried out according to a method appropriately selected from known methods according to the volatile additive to be used. It is preferable that the volatile additive is volatilized by heating in a container.
  • step (V) it is preferable to sinter at a temperature within the range of the firing temperature of polytetrafluoroethylene (for example, 300 to 500 ° C.). Moreover, it is preferable from the point of a moldability that a heat press molding is based on a press machine.
  • Porous fine powder is formed by heating and pressing (for example, 40 to 500 ° C., 0.2 to 30 MPa, 5 to 60 minutes) within the range where the porosity of the insulating resin material does not become less than 50% in the step (V). And polytetrafluoroethylene can be more firmly bound.
  • an insulating resin material with a metal layer it has a step (VI) of providing a metal layer on at least one surface of the insulating resin material obtained by the above steps (I) to (V) (see FIG. 2).
  • metal layers are provided on the upper and lower surfaces of the insulating resin material).
  • a method of closely attaching a metal layer via an adhesive resin layer that can be softened and melted by heat such as a thermoplastic resin
  • examples include a method of laminating a metal foil such as copper foil, a method of laminating, a method of sputtering or plating using a metal substance, and a method of adhering a metal layer through an adhesion resin layer from the viewpoint of adhesiveness. From the viewpoint of forming a metal layer having a uniform thickness, a laminating method is preferably used.
  • an adhesion resin layer is provided between the metal layer and the insulating resin material, and then adhered with heat and pressure by a hot press or the like.
  • the resin layer is melted and bitten into the roughened portion of the metal layer, the roughened portion of the insulating resin material, and the hole portion to realize strong adhesion by the anchor effect.
  • the resin for the adhesion resin layer can be bonded as long as it is softened and melted by heat when it is bonded to a metal, but a fluororesin material is preferred from the viewpoint of dielectric properties.
  • the fluororesin is not particularly limited as long as it is a fluororesin.
  • polytetrafluoroethylene PTFE
  • tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer PFA
  • tetrafluoro Examples include ethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE), and polychlorotrifluoroethylene (PCTFE).
  • PTFE and PFA are more preferable.
  • the adhesion between the metal layer and the insulating resin material through the fluorine resin layer is preferably a peel strength of 0.6 kN / m or more from the viewpoint of reliability.
  • the method of passing the adhesive resin layer is applied by applying to the roughened portion of the metal layer and drying, preparing by dipping or drying the insulating resin material, and preparing a hot melt film as a metal. Any method such as a method of placing between the layer and the insulating resin material may be used. Further, the preferable thickness of the adhesive resin layer is preferably 10 ⁇ m or less in consideration of dielectric characteristics, thermal expansion, and the like.
  • Examples of the metal of the metal layer include gold, silver, platinum, copper, aluminum, and alloys thereof, among which copper is preferably used.
  • the thickness of the metal layer is preferably 5 to 50 ⁇ m.
  • the metal layer can be provided on one side or both sides of the sheet.
  • the patterning method for forming the wiring in the step (VII) include an additive method using a photoresist or the like, and a subtractive method by etching.
  • the insulating resin material of the present invention can be obtained, but the manufacturing method of the insulating resin material is not limited to the above.
  • the insulating resin material obtained as described above at least one of inorganic porous aggregates and fibrils are connected to each other, and a fine network structure having a porosity of 50% or more is obtained.
  • the obtained insulating resin material has both a good low relative dielectric constant and a low thermal linear expansion coefficient.
  • the dielectric constant of the insulating resin material at a frequency of 10 GHz is preferably 1.55 to 1.9, more preferably 1.55 to 1.9, from the viewpoint of the accuracy of the product to be obtained. It is preferably 1.8.
  • the relative dielectric constant is obtained by a cavity resonator contact method with a measurement frequency of 10 GHz.
  • the dielectric loss tangent is preferably 0.01 or less from the same point as described above.
  • the dielectric loss tangent is determined by a cavity resonator tangent method with a measurement frequency of 10 GHz.
  • the thermal expansion coefficient of the insulating resin material is preferably 10 to 50 ppm / K from the viewpoint of the reliability of the obtained product.
  • the thermal linear expansion coefficient is obtained by a TMA (Thermal-Mechanical-Analysis) method using an average thermal linear expansion coefficient of 30 ° C. to 100 ° C. as the thermal linear expansion coefficient.
  • the insulating resin material of the present invention achieves both a good low relative dielectric constant and a low coefficient of thermal expansion, an insulating resin material with a metal layer in which a metal layer is provided on at least one surface of the insulating resin material is low.
  • the substrate material is excellent in relative dielectric constant and low thermal expansion coefficient.
  • the wiring board on which the metal layer of the insulating resin material with a metal layer is patterned has high accuracy and high reliability
  • the wiring board of the present invention is suitable for modules such as mobile phones, computers, and antennas. Can be used.
  • the wiring board of the present invention has a low relative permittivity and a small variation in relative permittivity, the detection distance can be extended and the accuracy can be improved. It is suitably used for a substrate.
  • Example 1 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “NY50”, BET specific surface area 40 m 2 / g, apparent specific gravity 60 g / L, average particle diameter of primary particles 30 nm) as fine particles constituting the inorganic porous aggregate, Fluon® PTFE dispersion AD939E (manufactured by Asahi Glass Co., Ltd., 60 wt% solid content) is prepared as polytetrafluoroethylene (PTFE), and the inorganic porous aggregate and polytetrafluoroethylene Were mixed in a 60% methanol aqueous solution at a ratio of 60:40 (weight ratio) to form an aggregate, and the obtained aggregate was dried to obtain a mixed powder.
  • PTFE polytetrafluoroethylene
  • dodecane was added as a volatile additive so as to be 50% by weight, and a V-type mixer was used as a mixing device, the rotation speed was 10 rpm, the temperature was 24 ° C., and the mixing time was 5 minutes.
  • the mixed paste was passed through a pair of rolling rolls to obtain an elliptical mother sheet (sheet-like molded product) having a thickness of 3 mm, a width of 10 to 50 mm, and a length of 150 mm. A plurality of mother sheets were produced.
  • the two first rolled laminated sheets are aligned in the rolling direction, and the sheet surface is kept parallel and rolled by rotating the sheet 90 degrees from the previous rolling direction.
  • Produced. A plurality of second rolled laminated sheets were produced.
  • the process of laminating and rolling the sheets is repeated a total of 5 times, counting from the laminating and rolling of the mother sheet, and then rolled a plurality of times with the gap between the rolling rolls narrowed by 0.5 mm, with a thickness of about 0.
  • a sheet of 18 mm was obtained (32 constituent layers).
  • the obtained rolled laminated sheet was heated at 150 ° C. for 30 minutes to remove volatile additives, thereby producing a sheet.
  • the obtained sheet was pressure molded at 380 ° C. for 5 minutes at 4 MPa to obtain an insulating resin material of Example 1. Finally, a sheet having a thickness of about 0.15 mm was obtained.
  • the weight and volume of the insulating resin material produced as described above were measured, and the porosity was calculated based on the specific gravity and blending ratio of each component.
  • Example 2 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “NAX50”, BET specific surface area 50 m 2 / g, apparent specific gravity 60 g / L, average particle diameter of primary particles 30 nm) is used as fine particles constituting the inorganic porous aggregate.
  • An insulating resin material was prepared in the same manner as in Example 1 except that.
  • Example 3 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “RY200S”, BET specific surface area of 95 m 2 / g, apparent specific gravity of 50 g / L, average particle diameter of primary particles of 16 nm) was used as fine particles constituting the inorganic porous aggregate. Except for the above, an insulating resin material was prepared in the same manner as in Example 1.
  • Example 4 An insulating resin material was prepared by the same method except that the same inorganic porous aggregate as in Example 1 was used and the inorganic porous aggregate and polytetrafluoroethylene were blended at a weight ratio of 70:30.
  • Example 5 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “RX200”, BET specific surface area 165 m 2 / g, apparent specific gravity 50 g / L, average particle diameter of primary particles 12 nm) as an inorganic porous aggregate is used. Insulation was performed in the same manner as in Example 1 except that the agglomerate and polytetrafluoroethylene were blended in a weight ratio of 50:50 and dodecane was added as a volatile additive to 45% by weight. A resin material was prepared.
  • Example 6 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “RX300”, BET specific surface area 230 m 2 / g, apparent specific gravity 50 g / L, average particle diameter of primary particles 7 nm) as an inorganic porous aggregate is used.
  • the agglomerate and polytetrafluoroethylene were blended at a weight ratio of 50:50 and dodecane was added as a volatile additive so that the total amount was 50% by weight.
  • An insulating resin material was produced.
  • Example 1 Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd., product number “RX50”, BET specific surface area 45 m 2 / g, apparent specific gravity 170 g / L, average particle diameter of primary particles 40 nm) is used as fine particles constituting the inorganic porous aggregate.
  • An insulating resin material was produced in the same manner as in Example 1 except that.
  • ⁇ Relative permittivity / dielectric loss tangent> The measurement frequency was 10 GHz, the complex dielectric constant was measured by the cavity resonator contact method, and the real part ( ⁇ r ′) was taken as the relative dielectric constant. Further, the dielectric tangent was obtained from the ratio ( ⁇ r ′′ / ⁇ r ′) of the real part and the imaginary part ( ⁇ r ′′).
  • a relative permittivity measuring device (“Network Analyzer N5230C” manufactured by Agilent Technologies, Inc. and “Cavity Resonator 10 GHz” manufactured by Kanto Electronics Application Development Co., Ltd.), a strip-shaped sample (sample size width 2 mm ⁇ length 70 mm) ) was cut out and measured.
  • ⁇ Water absorption rate> The obtained insulating resin material (sample size width 50 mm ⁇ length 50 mm) was dried at 130 ° C. for 30 minutes, and then the weight before the test was measured. The weight after immersing this in distilled water at 23 ° C. for 24 hours was measured to determine the saturated water absorption.
  • Comparative Example 1 did not have a fine network structure with sufficient porosity, resulting in a high relative dielectric constant.
  • Comparative Example 2 the porosity was less than 50% because the hollow inorganic particles were pulverized, resulting in inferior thermal expansion coefficient. In addition, the water absorption rate of the insulating resin material also increased.
  • the insulating resin material of the present invention has a low water absorption even if it is a fine network structure, and thus can maintain a stable dielectric constant characteristic even in a moisture absorption environment. I understood.
  • the said insulating resin material with a metal layer provides the resin layer for adhesion
  • the obtained laminated sheet is pressure-molded, and a metal layer is bonded to an insulating resin material, whereby a double-sided copper-clad plate is obtained.
  • the insulating resin materials with metal layers which are the examples, are provided with an insulating resin material with excellent adhesive strength (peel strength).
  • the wiring board was obtained by carrying out the etching process of the copper foil after that with the obtained insulating resin material with a metal layer (board
  • This wiring board uses an insulating resin material that has both a good low relative dielectric constant and a low coefficient of thermal expansion, so it has excellent reliability, and when this is used for a vehicle millimeter-wave antenna, the wiring position is The result that the detection distance was extended without getting mad.
  • the insulating resin material of the present invention has both an excellent low relative dielectric constant and low thermal linear expansion coefficient, it is suitable as a high-frequency wiring board material and can be suitably used for a vehicle millimeter-wave antenna. .

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PCT/JP2017/010767 2016-03-18 2017-03-16 絶縁樹脂材料、それを用いた金属層付絶縁樹脂材料および配線基板 WO2017159816A1 (ja)

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US16/084,394 US10388425B2 (en) 2016-03-18 2017-03-16 Insulating resin material, metal layer-equipped insulating resin material using same, and wiring substrate
KR1020187026248A KR102375660B1 (ko) 2016-03-18 2017-03-16 절연 수지 재료, 그것을 이용한 금속층 구비 절연 수지 재료 및 배선 기판
EP17766811.8A EP3432316B1 (en) 2016-03-18 2017-03-16 Insulating resin material, metal-layer-attached insulating resin material using same, and wiring substrate
CN201780016713.9A CN108780674B (zh) 2016-03-18 2017-03-16 绝缘树脂材料、使用其的带金属层的绝缘树脂材料及布线基板

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WO2020027172A1 (ja) * 2018-07-31 2020-02-06 日東電工株式会社 板状の複合材料
JPWO2020213669A1 (ko) * 2019-04-19 2020-10-22
WO2023080113A1 (ja) * 2021-11-08 2023-05-11 住友電気工業株式会社 誘電体シート、高周波プリント配線板用基板及び高周波プリント配線板

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WO2020027172A1 (ja) * 2018-07-31 2020-02-06 日東電工株式会社 板状の複合材料
CN112512788A (zh) * 2018-07-31 2021-03-16 日东电工株式会社 板状的复合材料
JPWO2020027172A1 (ja) * 2018-07-31 2021-08-26 日東電工株式会社 板状の複合材料
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JPWO2020213669A1 (ko) * 2019-04-19 2020-10-22
WO2020213669A1 (ja) * 2019-04-19 2020-10-22 日東電工株式会社 板状の複合材料
WO2023080113A1 (ja) * 2021-11-08 2023-05-11 住友電気工業株式会社 誘電体シート、高周波プリント配線板用基板及び高周波プリント配線板

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