WO2022163533A1 - Procédé de production de substrat composite, et substrat composite - Google Patents

Procédé de production de substrat composite, et substrat composite Download PDF

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Publication number
WO2022163533A1
WO2022163533A1 PCT/JP2022/002236 JP2022002236W WO2022163533A1 WO 2022163533 A1 WO2022163533 A1 WO 2022163533A1 JP 2022002236 W JP2022002236 W JP 2022002236W WO 2022163533 A1 WO2022163533 A1 WO 2022163533A1
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Prior art keywords
polymer
layer
group
composite substrate
tetrafluoroethylene
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PCT/JP2022/002236
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English (en)
Japanese (ja)
Inventor
渉 笠井
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Ａｇｃ株式会社
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Priority to JP2022578332A priority Critical patent/JPWO2022163533A1/ja
Publication of WO2022163533A1 publication Critical patent/WO2022163533A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
    • H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
    • H03H3/08—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of resonators or networks using surface acoustic waves
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/25—Constructional features of resonators using surface acoustic waves
    • 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

Definitions

  • the present invention relates to a method for manufacturing a composite substrate having a ceramic substrate and a layer containing a tetrafluoroethylene-based polymer on its surface, and to such a composite substrate.
  • LTCC Low Temperature Co-fired Ceramics
  • Multilayer circuit boards also called substrates
  • LTCC substrates have a low linear expansion coefficient, low high-frequency loss, and high rigidity, so they are excellent in dimensional stability and reliability.
  • LTCC substrates have a high dielectric constant, elements can be made smaller, and modules or devices can be made smaller, they are expected to be used as wiring substrate materials for, for example, high-frequency antenna substrates and modules used under severe environmental conditions.
  • Patent Document 1 discloses a composite substrate obtained by laminating a multilayer film in which fluororesin films are laminated on both sides of a polyimide film and a glass substrate or a ceramic substrate by hot pressing.
  • the inventors of the present invention have found that even in the embodiments described in the prior art documents, there is still room for improvement in terms of the separation between the ceramic substrate and the multilayer film and the occurrence of warpage, and have made earnest studies.
  • a composite substrate is obtained by forming a fired product layer on the surface of a ceramic substrate using a dispersion containing tetrafluoroethylene-based polymer particles and a liquid dispersion medium, the dispersion contains tetrafluoroethylene having an acidic group. It has been found that when an ethylene-based polymer or other polymer having an acidic group is contained, the fired product layer has excellent uniformity of component distribution and adhesion to the ceramic substrate.
  • An object of the present invention is to provide a method for producing a composite substrate which has excellent adhesion between a ceramic substrate and a layer containing a tetrafluoroethylene-based polymer, as well as excellent electrical properties, dimensional stability, heat resistance, etc., and to provide such a composite substrate. .
  • the present invention has the following aspects. ⁇ 1> A dispersion containing particles of a tetrafluoroethylene-based polymer and a liquid dispersion medium, wherein at least part of the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having an acidic group, or A fired product containing particles of the tetrafluoroethylene-based polymer obtained by applying a dispersion liquid further containing a polymer having an acidic group, which is a polymer other than the tetrafluoroethylene-based polymer, to the surface of a ceramic substrate and heating it.
  • a method of manufacturing a composite substrate comprising forming layers to obtain a composite substrate having the ceramic substrate and the fired layer on the surface of the ceramic substrate.
  • the tetrafluoroethylene-based polymer is a hot-melt tetrafluoroethylene-based polymer.
  • the tetrafluoroethylene-based polymer has a melting temperature of 200 to 320°C.
  • the tetrafluoroethylene-based polymer has a melt flow rate of 5 to 30 g/10 minutes.
  • the tetrafluoroethylene-based polymer having an acidic group is a polymer having at least one acidic group selected from the group consisting of a sulfo group, a phosphoric acid group, a carboxyl group and an acid anhydride group, ⁇ 1> The method according to any one of ⁇ 4>.
  • the tetrafluoroethylene-based polymer having an acidic group is a hot-melt tetrafluoroethylene-based polymer having 50 to 5000 acidic groups per 1 ⁇ 10 6 carbon atoms in the main chain, ⁇ 1>- Any method of ⁇ 5>.
  • ⁇ 7> The method according to any one of ⁇ 1> to ⁇ 6>, wherein the particles have an average particle size of 0.1 to 25 ⁇ m.
  • the polymer having an acidic group which is a polymer other than the tetrafluoroethylene-based polymer, is a polymer having at least one acidic group selected from the group consisting of a sulfo group, a phosphoric acid group, a carboxyl group and an acid anhydride group.
  • ⁇ 9> The method according to any one of ⁇ 1> to ⁇ 8>, wherein the liquid dispersion medium is an aromatic hydrocarbon.
  • the ceramic substrate contains at least one element selected from the group consisting of Ba, Ti, Ca, Zr, Fe, Ni, Cu, Zn, Mn, Co, Al and Si as a constituent element, ⁇ 1> to ⁇ 9> any one method.
  • ⁇ 11> Forming a metal layer by metal paste, metal sputtering or metal plating on the surface of the fired material layer in the composite substrate obtained by any one of ⁇ 1> to ⁇ 10>, the ceramic substrate, A method for producing a metal composite substrate, comprising obtaining a metal composite substrate having the fired material layer on the surface of the ceramic substrate and the metal layer on the surface of the fired material layer.
  • ⁇ 13> The composite substrate according to ⁇ 12>, wherein the fired material layer has a porosity of 5% or more.
  • ⁇ 14> The composite substrate of ⁇ 12> or ⁇ 13>, wherein the fired layer has a thickness of 5 to 100 ⁇ m.
  • ⁇ 15> A metal having a composite substrate according to any one of ⁇ 12> to ⁇ 14> and a metal layer formed by metal paste, metal sputtering or metal plating on the surface of the fired product layer of the composite substrate.
  • a method for manufacturing a composite substrate that has excellent adhesion between a ceramic substrate and a layer containing a tetrafluoroethylene-based polymer, as well as excellent electrical properties, dimensional stability, heat resistance, etc., and such a composite substrate.
  • the resulting composite substrate is useful, for example, as a wiring substrate for automobiles, a printed substrate, a high frequency antenna substrate, an LC filter, and a bandpass filter.
  • Average particle diameter (D50) is the volume-based cumulative 50% diameter of the object (particles and filler) determined by a laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is obtained with the total volume of the group of objects as 100%, and the particle diameter at the cumulative volume of 50% on the cumulative curve.
  • the D50 of the object is obtained by dispersing the object in water and analyzing it by a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution analyzer (LA-920 measuring instrument manufactured by Horiba, Ltd.). .
  • “Melting temperature” is the temperature corresponding to the maximum melting peak of the polymer as measured by differential scanning calorimetry (DSC).
  • the “viscosity of the dispersion” is the viscosity measured using a Brookfield viscometer at 25° C. and a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the 3 measurements is taken.
  • the “thixotropic ratio” is a value calculated by dividing the viscosity ⁇ 1 of the dispersion measured at a rotation speed of 30 rpm by the viscosity ⁇ 2 measured at a rotation speed of 60 rpm. Each viscosity measurement is repeated three times, and the average value of the three measurements is taken.
  • Melt flow rate means the melt mass flow rate of a polymer as defined in JIS K 7210:1999 (ISO 1133:1997).
  • the "melt viscosity” is based on ASTM D 1238, using a flow tester and a die of 2 ⁇ -8L, and a polymer sample (2g) preheated for 5 minutes at the measurement temperature under a load of 0.7MPa. It is a value measured by holding at the measurement temperature.
  • a “unit” in a polymer means an atomic group directly formed from one molecule of a monomer by polymerization, and an atomic group obtained by converting a part of the atomic group into another structure by treating the polymer produced. .
  • units based on monomer a are also simply referred to as “monomer a units”.
  • (Meth)acrylic acid” is a generic term for acrylic acid and methacrylic acid.
  • the production method of the present invention (hereinafter also referred to as “this method”) comprises particles (hereinafter also referred to as "F particles”) of a tetrafluoroethylene polymer (hereinafter also referred to as "F polymer”) and a liquid dispersion.
  • the following dispersion containing a medium (hereinafter also referred to as “this dispersion”) is applied to the surface of the ceramic substrate and heated to form a fired product layer containing the fired product of the F particles (hereinafter referred to as "F layer” ) to obtain a composite substrate (hereinafter also referred to as "this composite substrate") having the ceramic substrate and the fired layer on the surface of the ceramic substrate.
  • the present dispersion is a dispersion containing F polymer particles and a liquid dispersion medium, and at least a part of the F polymer is an F polymer having an acidic group, or an acidic polymer other than the F polymer.
  • the dispersion further contains a polymer having a group (hereinafter also referred to as "another polymer having an acidic group").
  • the F particles are dispersed in the liquid dispersion medium.
  • the composite substrate obtained by this method has excellent adhesion between the ceramic substrate and the F layer, as well as excellent electrical properties (low dielectric loss tangent, etc.), dimensional stability, and heat resistance. Further, the F layer formed from the present dispersion has excellent uniformity of component distribution, excellent physical properties based on the F polymer such as electrical properties, and also excellent surface smoothness. The reason why these properties are exhibited and the mechanism of action are not necessarily clear, but are presumed, for example, as follows.
  • the dispersion contains an F polymer with acidic groups or another polymer with acidic groups.
  • these acidic group-containing polymers have the effect of etching the surface of the ceramic substrate due to the acidic groups. It is considered that the concave-convex structure having a regular shape (such as a rectangular shape) is formed. Since the firing of the F particles progresses on the surface having such an uneven structure, an anchor effect is exhibited between the F layer and the ceramic substrate, and it is presumed that the adhesion is improved. It is also considered that this adhesiveness effectively suppresses the linear expansion of the F polymer by the ceramic substrate, and improves the dimensional stability and heat resistance of the composite substrate.
  • the voids in the F layer formed by firing the F particles not only induce a decrease in the dielectric loss tangent of the F layer, but also exhibit the effect of buffering the linear expansion of the F polymer.
  • a composite substrate having high physical properties of both ceramics and F-polymer and having excellent electrical properties, dimensional stability and heat resistance could be formed.
  • the F polymer in this dispersion is a polymer containing units based on tetrafluoroethylene (TFE) (TFE units).
  • the F-polymer may be hot-melt or non-hot-melt, but is preferably hot-melt.
  • thermal meltability refers to a melt fluid polymer having a melt flow rate of 0.1 to 1000 g/10 minutes at a temperature 20° C. or more higher than the melting temperature of the polymer under a load of 49 N. means.
  • the melting temperature is preferably 200-320°C, more preferably 260-320°C, even more preferably 280-320°C.
  • Such a hot-melt F polymer has a conformation with a high degree of freedom in which the restrictions on molecular motion are relaxed at the level of a single molecule. and easy to improve.
  • the melt viscosity of the F polymer is preferably 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s at 380° C., more preferably 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s at 300°C.
  • the MFR of F polymer is preferably 1 to 100 g/10 min, more preferably 5 to 30 g/10 min, even more preferably 10 to 30 g/min. In this case, when the F layer is formed, the anchoring effect with the ceramic substrate is likely to be highly expressed, and the composite substrate tends to be excellent in adhesiveness, electrical properties, dimensional stability, and heat resistance between the ceramic substrate and the F layer.
  • the fluorine atom content in the F polymer is preferably 70% by mass or more, more preferably 70 to 76% by mass.
  • the glass transition point of F polymer is preferably 75 to 125°C, more preferably 80 to 100°C.
  • F polymer examples include polytetrafluoroethylene (PTFE), a polymer containing TFE units and ethylene units (ETFE), TFE units and perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE”)-based units (hereinafter referred to as “ (also referred to as "PAVE units”), polymers (PFA) containing TFE units and hexafluoropropene units (FEP).
  • PTFE polytetrafluoroethylene
  • ETFE ethylene units
  • PAVE units perfluoro(alkyl vinyl ether)
  • FEP perfluoropropene units
  • the F polymer is preferably PFA or FEP, more preferably PFA.
  • the F polymer preferably has oxygen-containing polar groups such as hydroxyl-, sulfo-, phosphono- and carbonyl-containing groups. You may have two or more types of oxygen-containing polar groups.
  • oxygen-containing polar groups such as hydroxyl-, sulfo-, phosphono- and carbonyl-containing groups.
  • the hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, and includes -CF 2 CH 2 OH, -C(CF 3 ) 2 OH and 1,2-glycol group (-CH(OH)CH 2 OH).
  • a sulfo group as used herein, also means a group containing its derivative group (-SO 2 F, sulfonate ester group, etc.).
  • Phosphono group-containing groups include phosphoric acid group [--OP(O)(OH) 2 ,], phosphorous acid (phosphonic acid) group [--P(O)(OH) 2 ], hypophosphorous acid (phosphinic acid) and groups containing the group [--PH(O)OH] or derivatives thereof ( --OP (O)Cl.sub.2, phosphate groups, etc.).
  • a carbonyl group-containing group is a group containing a carbonyl group (>C(O)), a carboxy group, an alkoxycarbonyl group, an amide group, an ester group, an isocyanate group, a carbamate group (--OC(O)NH 2 ), an acid Anhydride groups [-C(O)OC(O)-], imide groups [-C(O)NHC(O)-, etc.] and carbonate groups [-OC(O)O-] can be mentioned.
  • the oxygen-containing polar group in the F polymer is preferably an acidic group, and the acidic group is preferably a sulfo group, a phosphoric acid group, a carboxyl group and an acid anhydride group.
  • the F polymer is more preferably a heat-melting F polymer having an acidic group, and a thermal polymer having at least one acidic group selected from the group consisting of a sulfo group, a phosphoric acid group, a carboxy group and an acid anhydride group. Meltable F polymers are particularly preferred.
  • the composite substrate tends to be excellent in adhesiveness, heat resistance, dimensional stability, and electrical properties due to the mechanism of action described above.
  • the acidic group may be contained in a unit in the F polymer, or may be contained in a terminal group of the main chain of the F polymer. Examples of the latter embodiment include an F polymer having an acidic group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer having an acidic group obtained by plasma treatment or ionizing radiation treatment of the F polymer. .
  • the acidic group is more preferably a carboxy group or an acid anhydride group, and more preferably an acid anhydride group.
  • the number of acidic groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, and 800 to 1500 per 1 ⁇ 10 6 carbon atoms in the main chain. More preferred.
  • the number of acidic groups in the F polymer for example, the number of carboxy groups and acid anhydride groups, can be quantified by the method described in WO2020/145133.
  • the F polymer having an acidic group may be a heat-melting F polymer having an acidic group as described above. Polymers are preferred.
  • the proportion of the heat-melting F polymer having an acidic group in the F polymer constituting the F particles is preferably 60% by mass or more, more preferably 85% by mass or more, relative to the total amount of the F polymer, and constitutes the F particles. It is particularly preferred that the total amount of the F polymer is a hot-melt F polymer having acidic groups.
  • the F polymer constituting the F particles contains an F polymer other than the heat-melting F polymer having an acidic group
  • the F polymer includes a non-heat-melting F polymer and an oxygen-containing polar group other than the acid group.
  • examples include heat-melting F-polymers and heat-melting F-polymers containing no oxygen-containing polar groups.
  • the F polymer is preferably a polymer having acidic groups comprising TFE units and PAVE units, more preferably a polymer comprising units based on TFE units, PAVE units and monomers having acidic groups, all units
  • polymers containing 90 to 99 mol %, 0.5 to 9.97 mol % and 0.01 to 3 mol % of these units in this order are more preferable.
  • the presence of an acidic group is preferable from the viewpoint of further improving affinity and adhesion.
  • the monomer having an acidic group itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH") are preferred. Specific examples of such polymers include those described in WO2018/16644.
  • the D50 of the F particles is preferably 0.1 to 25 ⁇ m.
  • D50 of the F particles is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
  • D50 of the F particles is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more. In this range of D50, the fluidity and dispersibility of the F particles tend to be good, and a dense F layer is easily formed, so the adhesiveness, heat resistance, dimensional stability, and electrical properties of the composite substrate are particularly improved. It's easy to do.
  • the specific surface area of the F particles is preferably 1 to 25 m 2 /g, more preferably 1 to 8 m 2 /g, even more preferably 1 to 3 m 2 /g.
  • the etchability of the ceramic substrate by the F polymer and the denseness of the formed F layer are balanced, and the adhesiveness, heat resistance, dimensional stability and electrical properties of the composite substrate are particularly likely to be improved.
  • Two or more kinds of F particles may be used.
  • the F particles may contain a polymer other than the F polymer or an inorganic filler, but preferably contain the F polymer as a main component.
  • the content of the F polymer in the F particles is preferably 80% by mass or more, more preferably 100% by mass.
  • Polymers other than the F polymer include heat-resistant polymers such as aromatic polyesters, polyamideimides, (thermoplastic) polyimides, polyphenylene ethers, polyphenylene oxides, and maleimides.
  • inorganic fillers include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). .
  • the F particles containing a polymer other than the F polymer or an inorganic filler have a core-shell structure in which the F polymer is the core and the shell is the polymer other than the F polymer or the inorganic filler, or the F polymer is the shell and the inorganic filler is other than the F polymer. It may have a core-shell structure with a polymer or inorganic filler in the core.
  • Such F particles are obtained, for example, by coalescing (colliding, aggregating, etc.) particles of the F polymer and particles of a polymer other than the F polymer or particles of an inorganic filler.
  • the present dispersion When the F particles contained in the present dispersion do not contain an F polymer having an acid group, the present dispersion contains another polymer having an acid group. However, even when the F particles contain an F polymer having an acidic group, the present dispersion may contain another polymer having an acidic group.
  • the other polymer having an acidic group may be dispersed in the present dispersion liquid as particles, or may be contained in a dissolved state in the liquid dispersion medium.
  • Other polymers having acidic groups are not particularly limited, but polymers having at least one acidic group selected from the group consisting of sulfo groups, phosphoric acid groups, carboxy groups and acid anhydride groups are preferred. .
  • polymers having such acidic groups tend to have an excellent effect of etching the surface of the ceramic substrate due to the acidic groups when the present dispersion is applied to the surface of the ceramic substrate and heated. As a result, an anchor effect is exhibited between the F layer and the ceramic substrate, and adhesion is likely to be improved.
  • Another polymer having an acidic group is preferably a heat-meltable polymer or a thermosetting polymer (preferably a low-molecular-weight polymer such as an oligomer).
  • polymers having such acidic groups include, for example, aromatic polyamic acids which are aromatic polyimide precursors, (meth)acrylic acid copolymers such as ethylene-(meth)acrylic acid copolymers, polystyrene sulfonic acid, Random or graft copolymers of olefins and maleic anhydride may be mentioned.
  • the number of acidic groups in other polymers having acidic groups is preferably 10 to 5,000, more preferably 100 to 3,000, and even more preferably 800 to 1,500 per 1 ⁇ 10 6 carbon atoms in the main chain.
  • Liquid dispersion media in the present dispersion include compounds that are liquid at 25° C. under atmospheric pressure, such as aliphatic hydrocarbons, aromatic hydrocarbons, water, alcohols, amides, ketones and esters.
  • the boiling point of the liquid dispersion medium is preferably in the range of 50 to 240°C. Also, two or more liquid dispersion media may be used in combination.
  • aliphatic hydrocarbons examples include pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclooctane, cyclodecane, cyclododecane, liquid paraffin, limonene, dipentene, and myrcene. mentioned.
  • Aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, styrene, cumene, mesitylene (1,3,5-trimethylbenzene), cymene, diethylbenzene, naphthalene and the like.
  • Alcohols include methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, diethylene glycol, dipropylene glycol, glycerin, and the like. mentioned.
  • Amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy- N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphorictriamide, 1,3-dimethyl-2-imidazolidinone and the like.
  • Ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, cycloheptanone and the like.
  • Esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, ⁇ -butyrolactone, ⁇ - Valerolactone, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoacetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol monoacetate and the like.
  • the content of the liquid dispersion medium in the present dispersion is preferably 30 to 90% by mass, more preferably 50 to 80% by mass. Within this range, the dispersion stability of the present dispersion is likely to be improved.
  • This dispersion can be prepared by mixing F particles, a liquid dispersion medium, and optionally another polymer having an acidic group.
  • Mixing methods for preparing the present dispersion include, for example, mixing using a stirring device equipped with uniaxial or multiaxial blades (stirring blades) such as propeller blades, turbine blades, paddle blades, shell-shaped blades, Henschel mixer , mixing by stirring with a pressure kneader, Banbury mixer or planetary mixer, ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill (bead mill using grinding media such as glass beads or zirconium oxide beads), Dispermat, Mixing by dispersing machine using media such as SC mill, spike mill or agitator mill, using media such as high pressure homogenizer such as micro fluidizer, nanomizer, articulzer, ultrasonic homogenizer, desolver, disper, high speed impeller disperser etc. This includes mixing with a non-dispersing machine
  • the present dispersion may further contain a nonionic surfactant.
  • the hydrophilic portion of the surfactant preferably has a polyoxyalkylene group or an alcoholic hydroxyl group.
  • the polyoxyalkylene group may be composed of one oxyalkylene group, or may be composed of two or more oxyalkylene groups.
  • As the polyoxyalkylene group a polyoxyethylene group is preferred.
  • the hydrophobic portion of the surfactant preferably has an alkyl group, acetylene group, polysiloxane group, perfluoroalkyl group or perfluoroalkenyl group.
  • surfactants polyoxyalkylene alkyl ethers, acetylene-based surfactants, silicone-based surfactants and fluorine-based surfactants are preferred, and silicone-based surfactants are more preferred.
  • a silicone surfactant may be used in combination with a polyoxyalkylene alkyl ether. Specific examples of such surfactants include the "Ftergent" series (manufactured by Neos Co., Ltd.
  • Ftergent is a registered trademark
  • the "Surflon” series manufactured by AGC Seimi Chemical Co., Ltd. Surflon is a registered trademark
  • the "Megafac” series Megafac manufactured by DIC Corporation is a registered trademark
  • "Unidyne” series Unidyne manufactured by Daikin Industries, Ltd.
  • the dispersion further contains a surfactant, the amount thereof is preferably 1 to 15% by weight based on the total weight of the dispersion. In this case, the affinity between the components is enhanced, and the dispersion stability of the present dispersion is likely to be improved.
  • the present dispersion further contains a resin material other than the F polymer and other polymers having acidic groups, from the viewpoint of improving the adhesion and low linear expansion properties of the F layer (molded article) formed from the present dispersion.
  • resin materials may be thermoset or thermoplastic, may be modified, may be dissolved in the present dispersion, or may be dispersed without being dissolved.
  • resin materials include aromatic polyimides, aromatic maleimides, acrylic resins, phenol resins, liquid crystalline polyesters, liquid crystalline polyester amides, polyolefin resins, modified polyphenylene ethers, polyfunctional cyanate esters, which do not have the above-mentioned acidic groups.
  • Resins polyfunctional maleimide-cyanate ester resins, polyfunctional maleimides, aromatic elastomers such as styrene elastomers, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea cocondensation resins, polycarbonates , polyarylates, polysulfones, polyallylsulfones, aromatic polyamides, aromatic polyetheramides, polyphenylene sulfides, polyaryletherketones, polyamideimides, polyphenylene ethers, epoxy resins and the like.
  • the present dispersion further contains a resin material, the content thereof is preferably 40% by mass or less with respect to the entire mass of the present dispersion.
  • a preferred embodiment of the resin material is an aromatic polymer.
  • the aromatic polymer is preferably an aromatic polyimide, an aromatic maleimide, a polyphenylene ether, or an aromatic elastomer (such as a styrene elastomer), more preferably a thermoplastic aromatic polyimide.
  • an aromatic polyimide preferably an aromatic polyimide, an aromatic maleimide, a polyphenylene ether, or an aromatic elastomer (such as a styrene elastomer), more preferably a thermoplastic aromatic polyimide.
  • the liquid physical properties viscosity, thixotropic ratio, etc.
  • styrene elastomers examples include copolymers of styrene and conjugated dienes or (meth)acrylic acid esters (styrene-butadiene rubbers, styrene core-shell copolymers, styrene block copolymers, etc.).
  • a styrene elastomer that has both properties and is plasticized by heating to exhibit flexibility is preferred.
  • the present dispersion may further contain an inorganic filler.
  • the F layer formed from the present dispersion tends to be excellent in electrical properties and low linear expansion properties.
  • inorganic fillers nitride fillers and inorganic oxide fillers are preferred, and boron nitride fillers, beryllia fillers (beryllium oxide fillers), silicate fillers (silica fillers, wollastonite fillers, talc fillers), and Metal oxide (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) fillers are more preferred, and silica fillers are even more preferred.
  • At least part of the surface of the inorganic filler contains a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.).
  • silane coupling agent 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.
  • D50 of the inorganic filler is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. D50 is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the shape of the inorganic filler may be any of granular, needle-like (fibrous), and plate-like. Specific shapes of the inorganic filler include spherical, scaly, layered, leaf-like, apricot kernel-like, columnar, crest-like, equiaxed, leaf-like, mica-like, block-like, tabular, wedge-like, rosette-like, and mesh. shape and prismatic shape. Two or more inorganic fillers may be used in combination.
  • inorganic fillers include silica fillers (“ADMAFINE (registered trademark)” series manufactured by Admatechs, etc.), and zinc oxide surface-treated with an ester such as propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd. "FINEX (registered trademark)” series manufactured by Denka), spherical fused silica (“SFP (registered trademark)” series manufactured by Denka, etc.), titanium oxide coated with polyhydric alcohol and inorganic substances (manufactured by Ishihara Sangyo Co., Ltd.
  • Tipake registered trademark
  • JMT registered trademark
  • Talc filler Nippon Talc Co., Ltd.'s “SG” series, etc.
  • Steatite filler Nippon Talc “BST” series, etc.
  • boron nitride filler Showa Denko “UHP” series, Denka “Denka Boron Nitride” series ("GP", “HGP” grade), etc. mentioned.
  • the present dispersion contains a thixotropic agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, and an antioxidant, as long as they do not impair the effects of the present invention.
  • the viscosity of the present dispersion is preferably 10 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more.
  • the viscosity of the present dispersion is preferably 10000 mPa ⁇ s or less, more preferably 1000 mPa ⁇ s or less.
  • the thixotropic ratio of this dispersion is preferably 1.0 or more.
  • the thixotropic ratio of the present dispersion is preferably 3.0 or less, more preferably 2.0 or less.
  • the content of F particles in the present dispersion is preferably 10% by mass or more, more preferably 25% by mass or more, relative to the total mass of the present dispersion.
  • the content of the F particles is preferably 75% by mass or less, more preferably 60% by mass or less, relative to the total mass of the present dispersion. In this case, it is easy to form a smooth F layer from the present dispersion.
  • the content of such polymer in the present dispersion is preferably 0.1% by mass or more, and 1% by mass or more, relative to the total mass of the present dispersion. is more preferred.
  • the content of the other polymer having an acidic group is preferably 30% by mass or less, more preferably 10% by mass or less, relative to the total mass of the present dispersion.
  • the dispersion is applied to the surface of a ceramic substrate to form a liquid coating, the liquid coating is heated to remove the dispersion medium to form a dry coating, and the dry coating is heated to form a F
  • the particles are fired to form the F layer to obtain the present composite substrate.
  • This method causes less damage to the ceramic substrate and is less susceptible to cracks and the like than the method of separately forming the F layer and press-bonding it to the ceramic substrate.
  • an F layer that exhibits strong adhesion to a ceramic substrate can be formed, and the smoothness of the resulting F layer can be enhanced.
  • the F layer may be formed on the entire surface of the ceramic substrate surface, or may be formed on a part thereof. When the F layer is formed on part of the surface of the ceramic substrate, the F layer may be formed in a pattern.
  • the patterned F layer can be formed, for example, by applying the present dispersion to a ceramic substrate by screen printing and heating.
  • the ceramic substrate preferably contains at least one element selected from the group consisting of Ba, Ti, Ca, Zr, Fe, Ni, Cu, Zn, Mn, Co, Al and Si as its constituent element.
  • ceramics include alumina, zirconia, mullite (aluminosilicate mineral), cordierite (2MgO.2Al 2 O 3.5SiO 2 ), steatite (MgO.SiO 2 ), magnesium titanate, and calcium titanate.
  • strontium titanate aluminum nitride, silicon carbide, and silicon nitride, with alumina being preferred.
  • the shape of the ceramic substrate may be planar, curved, or uneven.
  • an LTCC multi-layer circuit board having low conduction characteristics, low dielectric characteristics and heat resistance can also be preferably used as the ceramic substrate.
  • the thickness of the ceramic substrate is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more.
  • the thickness of the ceramic substrate is preferably 10 mm or less, more preferably 3 mm or less. If the thickness of the ceramic substrate is at least the lower limit, the composite substrate tends to have excellent electrical properties, and if the thickness is at most the upper limit, the composite substrate can be made thinner.
  • the method of applying the present dispersion to the surface of the ceramic substrate may be any method as long as a stable liquid film (wet film) composed of the present dispersion is formed on the surface of the ceramic substrate. , immersion method, and coating method is preferred. By using the coating method, a liquid coating can be efficiently formed on the surface of the ceramic substrate with simple equipment. Coating methods include spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain-meyer bar method, and slot die coating. law.
  • the liquid coating When drying the liquid coating, the liquid coating is heated at a temperature at which the liquid dispersion medium volatilizes to form a dry coating on the surface of the ceramic substrate.
  • the heating temperature for such drying is preferably 100°C to 200°C. Air may be blown in the step of removing the liquid dispersion medium.
  • the liquid dispersion medium does not necessarily have to be completely volatilized, and may be volatilized to such an extent that the layer shape after retention is stable and a self-supporting film can be maintained.
  • the heating temperature is preferably 380° C. or lower, more preferably 350° C. or lower.
  • Examples of heating methods include a method using an oven, a method using a ventilation drying oven, and a method of irradiating heat rays such as infrared rays. Heating may be performed under normal pressure or under reduced pressure.
  • the heating atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), and an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.).
  • the heating time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes.
  • the thickness of the F layer is preferably 0.1-150 ⁇ m, more preferably 5-100 ⁇ m.
  • the ratio of the thickness of the F layer to the thickness of the ceramic substrate is preferably 0.01 to 1, more preferably 0.03 to 0.3.
  • the peel strength between the F layer and the ceramic substrate is preferably 5 N/cm or more, more preferably 10 N/cm or more.
  • the peel strength is preferably 100 N/cm or less.
  • the dielectric loss tangent of the composite substrate is preferably 0.010 or less, more preferably 0.0020 or less.
  • the lower limit of dielectric loss tangent is 0.0001.
  • the porosity of the F layer is preferably 5% or more, more preferably 10% or more.
  • the porosity of the F layer is preferably 30% or less, more preferably 20% or less. From this dispersion liquid, it is easy to form an F layer having such a porosity.
  • the porosity is obtained by determining the void portion of the F layer by image processing from the SEM photograph of the cross section of the molded product observed using a scanning electron microscope (SEM), and the area occupied by the void portion of the F layer. It is the ratio (%) divided by the area. The area occupied by the void portion is obtained by approximating the void portion to a circle. Since the F layer is formed of a fired product of F particles packed in a liquid coating, it tends to contain voids. It is presumed that the effect of lowering the dielectric loss tangent is also exhibited.
  • the ten-point average roughness of the surface of the F layer is more preferably 5 ⁇ m or less, and even more preferably 2 ⁇ m or less.
  • the ten-point average roughness of the surface of the F layer is preferably 0.01 ⁇ m or more.
  • the antenna or the like obtained by processing the metal composite substrate of the present invention described later which has a metal layer on the surface of the F layer of the composite substrate, tends to have excellent electrical characteristics. .
  • the ten-point average roughness is at least this lower limit, the F layer tends to have excellent adhesiveness to other materials. If the average particle size of the F particles, the specific surface area and the MFR of the F polymer are within the above-mentioned preferred ranges, the ten-point average roughness of the surface of the F layer can be easily adjusted within these ranges.
  • This dispersion may be applied to only one surface of the ceramic substrate, or may be applied to both surfaces of the ceramic substrate.
  • the former yields a ceramic substrate and a composite substrate having an F layer on one surface of the ceramic substrate, while the latter yields a ceramic substrate and a composite substrate having an F layer on both surfaces of the ceramic substrate.
  • the latter composite substrate is less likely to warp, and is therefore excellent in handleability during processing.
  • These composite substrates are excellent in various physical properties such as electrical properties, and are therefore suitable as materials for printed circuit boards and the like.
  • Another substrate may be laminated on the outermost surface of the composite substrate.
  • Other substrates include a heat-resistant resin film, a prepreg that is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer.
  • a prepreg is a sheet-like substrate obtained by impregnating a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) with a thermosetting resin or thermoplastic resin.
  • a heat-resistant resin film is a film containing one or more heat-resistant resins, and examples of heat-resistant resins include the resins described above.
  • As a lamination method there is a method of hot-pressing the present composite substrate and another substrate.
  • This composite substrate further laminates a metal layer on the surface of the F layer, a metal composite substrate (hereinafter referred to as "this metal (also referred to as a “composite substrate”).
  • This metal composite substrate has excellent adhesiveness between the F layer and the metal layer, and has excellent shape stability due to the presence of the F layer having dense voids.
  • the printed circuit board obtained by processing the present metal composite substrate has excellent electrical properties.
  • the thickness of the metal layer is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the thickness of the metal layer is preferably 50 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the metal layer may be formed by thermocompression bonding the F layer and the metal foil of the composite substrate, or may be formed on the surface of the F layer of the composite substrate by metal paste, metal sputtering, or metal plating. It is preferably formed on the surface of the F layer of the substrate by metal paste, metal sputtering or metal plating.
  • the F layer is formed of a sintered product of F particles, and an anchor effect occurs between the fine surface irregularities of the F layer and the formed metal layer, and the adhesion between the F layer and the metal layer is improved. Easier to improve. From the viewpoint of forming a dense metal layer pattern while suppressing damage to the composite substrate, it is more preferable to form the metal layer on the surface of the F layer of the composite substrate using a metal paste.
  • the metal foil includes iron, copper, nickel, titanium, aluminum, and alloys thereof (stainless steel, nickel 42 alloy, etc.).
  • the metal foil is preferably rolled copper foil or electrolytic copper foil.
  • the metal paste preferably contains a metal filler and a binder resin.
  • Metal fillers include metal powders and metal coated fillers. Preferred metals in the metal filler are silver, copper and nickel, with silver being more preferred.
  • the average particle size of the metal filler is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, from the viewpoint of electrical conductivity and conductivity of the metal layer.
  • the average particle size of the metal filler is preferably 0.01 ⁇ m or more.
  • the binder resin may be a thermosetting resin or a thermoplastic resin.
  • binder resins include epoxy resins, phenol resins, polyester resins, polyurethane resins, acrylic resins, melamine resins, polyimide resins, and polyamide-imide resins, with epoxy resins being preferred.
  • the metal paste preferably further contains a solvent that dissolves the binder resin. Ester-, ether-, ketone-, ether-ester-, alcohol-, hydrocarbon-, and amine-based organic solvents can be used as the solvent. is preferred.
  • the metal paste may further contain additives such as curing agents, curing accelerators, silane coupling agents, flame retardants and thickeners.
  • a metal layer can be formed by applying a metal paste to the surface of the F layer by a method such as screen printing and heating. Since the F polymer is excellent in heat resistance, damage to the composite substrate can be suppressed even if it is heated during the formation of the metal layer.
  • the metal layer is formed by forming a seed layer on the surface of the F layer by metal sputtering or electroless metal plating, and further electrolytic metal It is preferably formed by growing a metal on the surface of the seed layer by plating.
  • the surface of the F layer may be surface-treated before forming the seed layer. Examples of surface treatment methods include annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, and silane coupling treatment.
  • Metals in the seed layer include copper, nickel, chromium, nichrome alloys, titanium alloys, and the like.
  • the seed layer is obtained, for example, by forming a first layer on the surface of the F layer by metal sputtering and further forming a second layer on the surface of the first layer by metal sputtering. Nichrome alloys and titanium alloys are preferable as the metal contained in the first layer, and copper is preferable as the metal contained in the second layer.
  • the thickness of the first layer is preferably 1-10 nm, and the thickness of the second layer is preferably 50-200 nm. Copper and nickel are preferable as the metal when the seed layer is formed by electroless metal plating.
  • This metal composite substrate may have a metal layer on the surface of the F layer opposite to the surface in contact with the ceramic substrate, or partly between the ceramic substrate and the F layer.
  • the former metal composite substrate can be produced by forming a metal layer on part or all of the surface of the F layer of the composite substrate having the F layer on the surface.
  • the latter metal composite substrate can be produced by forming a metal layer on a portion of the surface of the ceramic substrate, applying the dispersion to the surfaces of the ceramic substrate and the metal layer, and heating the resultant.
  • This metal composite substrate is useful as a substrate for antennas (patch antennas, monopole antennas, dipole antennas, inverted F antennas, etc.).
  • the composite substrate of the present invention is a composite substrate having a ceramic substrate and a fired layer containing fired particles of tetrafluoroethylene-based polymer having acidic groups on the surface of the ceramic substrate.
  • the definitions of the ceramic substrate, the fired layer, and the composite substrate in the composite substrate of the present invention are the same as those of the ceramic substrate, the fired layer, and the composite substrate in the present method, including their preferred embodiments.
  • the composite substrate of the present invention is preferably produced by this method.
  • the metal composite substrate of the present invention is the composite substrate of the present invention, and is a metal composite having a metal layer formed by metal paste, metal sputtering, or metal plating on the surface of the fired material layer in the composite substrate of the present invention. is the substrate.
  • the definitions of the ceramic substrate, the fired layer, the composite substrate, the metal layer, and the metal composite substrate, including their preferred embodiments, are the ceramic substrate, the fired layer, the composite substrate, the metal layers, similar to those of metal composite substrates.
  • the metal composite substrate of the present invention is preferably produced by this method.
  • the present invention is not limited to the configurations of the above-described embodiments.
  • the present method, the composite substrate of the present invention, and the metal composite substrate of the present invention may be added to any other configuration in the configurations of the above embodiments, or may be replaced with any configuration that exhibits similar functions. It can be.
  • F particle 1 containing 97.9 mol%, 0.1 mol% and 2.0 mol% of TFE units, NAH units and PPVE units in this order, and acid anhydride groups per 1 ⁇ 10 6 main chain carbon atoms Particles (D50: 2.1 ⁇ m) consisting of 1000 F polymer 1 (melting temperature: 300° C., melt flow rate: 25 g/10 min) [Ceramic substrate]
  • Substrate 1 LTCC ceramic substrate (Yamamura Photonics GCS60 dielectric constant: 6.2 dielectric loss tangent: 0.0017 thickness: 0.35 mm) [metal paste]
  • Metal paste 1 Silver paste containing silver nanoparticles (MDot manufactured by Mitsuboshi Belting Co., Ltd.)
  • Example 1 A dispersion of F particles 1 using toluene as a dispersion medium (content of F particles 1: 40% by mass, viscosity: 400 mPa s) is applied to the surface of the substrate 1 by screen printing to form a wet film. did. Subsequently, the substrate 1 on which the wet film was formed was passed through a drying furnace at 120° C. for 5 minutes and dried by heating to obtain a dry film. The dry film was then heated at 380° C. for 3 minutes in a nitrogen oven.
  • a composite substrate 1 having a substrate 1 and a fired product layer (thickness: 50 ⁇ m) containing the fused and fired product of the F particles 1 on its surface was manufactured.
  • the porosity of the fired material layer of the composite substrate 1 was 10% or more.
  • the baked product layer was visually observed. No peeling was observed, and the whole was firmly adhered.
  • the dielectric loss tangent of the composite substrate 1 was measured by the SPDR (split post dielectric resonance) method at a measurement frequency of 10 GHz, and the dielectric loss tangent was less than 0.0020.
  • a rectangular test piece (length 100 mm, width 10 mm) is cut out from the composite substrate 1, the position of 50 mm from one end in the length direction of the test piece is fixed, and the tensile speed is 50 mm / min, and the test is performed from one end in the length direction. At 90° to the piece, the substrate 1 and the fired layer were separated. The maximum load applied at this time was 10 N/cm or more.
  • the metal paste 1 was applied to the surface of the fired product layer of the composite substrate 1 by screen printing in a width of 200 ⁇ m.
  • the composite substrate 1 coated with the metal paste was heated at 100° C. for 10 minutes to dry the metal paste, and further heated at 350° C. for 10 minutes to be sintered.
  • a metal composite substrate 1 having a metal layer on the surface of the fired product layer of the composite substrate 1 was obtained.
  • no peeling was observed between the fired product layer and the substrate 1 and between the fired product layer and the metal layer, and the whole was firmly adhered.
  • the composite substrate obtained by the method of the present invention has excellent adhesion between the ceramic substrate and the layer containing the tetrafluoroethylene-based polymer, as well as excellent electrical properties, heat resistance, dimensional stability, and the like.
  • Such composite substrates are useful, for example, as wiring substrates for automobiles, printed substrates, high-frequency antenna substrates such as antenna-in-package (AiP) and antenna integrated module (AiM), and high-frequency parts such as LC filters.

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Abstract

La présente invention concerne : un procédé de production d'un substrat composite qui présente une excellente adhérence entre un substrat en céramique et une couche contenant un polymère de tétrafluoroéthylène, tout en ayant des caractéristiques électriques, une stabilité dimensionnelle, une résistance à la chaleur excellentes et d'autres caractéristiques similaires excellentes ; et ce substrat composite.　Dans le procédé de production d'un substrat composite, un liquide de dispersion qui contient un milieu de dispersion liquide et des particules d'un polymère de tétrafluoroéthylène, et qui contient en outre un polymère ayant un groupe acide, le polymère étant différent du polymère de tétrafluoroéthylène, ou dans lequel au moins une partie du polymère de tétrafluoroéthylène présente un groupe acide, est appliqué sur la surface d'un substrat en céramique et ensuite chauffé, formant ainsi une couche de produit brûlé qui contient des produits brûlés des particules du polymère de tétrafluoroéthylène de façon à obtenir un substrat composite qui comprend le substrat en céramique et la couche de produit brûlé sur la surface du substrat en céramique.
PCT/JP2022/002236 2021-01-28 2022-01-21 Procédé de production de substrat composite, et substrat composite WO2022163533A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003006565A1 (fr) * 2001-06-15 2003-01-23 Daikin Industries, Ltd. Composition de revetement de fluororesine, film de revetement et objet revetu
JP2011225677A (ja) * 2010-04-16 2011-11-10 Asahi Glass Co Ltd 含フッ素共重合体粉体の製造方法および多孔性含フッ素共重合体粉体
JP2019181337A (ja) * 2018-04-04 2019-10-24 Ａｇｃ株式会社 積層体の製造方法
WO2020004339A1 (fr) * 2018-06-27 2020-01-02 Ａｇｃ株式会社 Liquide de dispersion de poudre, stratifié, film et tissu tissé imprégné

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003006565A1 (fr) * 2001-06-15 2003-01-23 Daikin Industries, Ltd. Composition de revetement de fluororesine, film de revetement et objet revetu
JP2011225677A (ja) * 2010-04-16 2011-11-10 Asahi Glass Co Ltd 含フッ素共重合体粉体の製造方法および多孔性含フッ素共重合体粉体
JP2019181337A (ja) * 2018-04-04 2019-10-24 Ａｇｃ株式会社 積層体の製造方法
WO2020004339A1 (fr) * 2018-06-27 2020-01-02 Ａｇｃ株式会社 Liquide de dispersion de poudre, stratifié, film et tissu tissé imprégné

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