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WO2019059216A1 - Feuille diélectrique, et procédé de fabrication de celle-ci - Google Patents

Feuille diélectrique, et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2019059216A1
WO2019059216A1 PCT/JP2018/034597 JP2018034597W WO2019059216A1 WO 2019059216 A1 WO2019059216 A1 WO 2019059216A1 JP 2018034597 W JP2018034597 W JP 2018034597W WO 2019059216 A1 WO2019059216 A1 WO 2019059216A1
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WO
WIPO (PCT)
Prior art keywords
dielectric sheet
mass
ceramic gel
dielectric
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/034597
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English (en)
Japanese (ja)
Inventor
翔 大高
麻貴 廣永
宮田　壮
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Lintec Corp
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Lintec Corp
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Filing date
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Priority to JP2019533120A priority Critical patent/JP6707203B2/ja
Publication of WO2019059216A1 publication Critical patent/WO2019059216A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H01B17/60—Composite insulating bodies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds

Definitions

  • the present invention relates to a dielectric sheet and a method of manufacturing the dielectric sheet.
  • high frequency devices for transmitting or receiving high frequency electromagnetic waves.
  • devices such as mobile phones, high-speed wireless LANs, non-contact IC card systems, dangerous goods detection sensors, collision avoidance systems built into automobiles, GPS (Global Positioning System) positioning systems, and equipment for industrial science and medical devices are 10 MHz. It is a high frequency device which transmits or receives the above high frequency.
  • Power consumption is one of the problems with such high frequency devices. Therefore, the material which contributes to reduction of power consumption is calculated
  • Patent Document 1 a crystalline gel containing crystal particles, which is obtained by gelling a precursor solution in which a metal alkoxide such as barium titanate is dissolved at a high concentration of 0.5 mol / L or more, is uniformly contained in a solvent
  • a coating solution for forming a thin film dispersed therein is disclosed.
  • the coating solution is coated on a silicon substrate to form a coating layer, and then the coating layer is fired at 450 to 800 ° C. together with the silicon substrate, so that the relative dielectric constant is high even in a high frequency region. It is described that a crystalline thin film having a high dielectric loss tangent can be formed.
  • the method of forming a crystalline thin film using the coating solution described in Patent Document 1 is premised on passing through a baking process at 450 to 800 ° C. Therefore, the substrate to which the coating solution can be applied is a metal such as a silicon substrate It is not possible to use the resin base material which is limited to the material and can not withstand at the high temperature in the firing process. Also, according to the study of the present inventors, a coating solution as described in Patent Document 1 is applied on a resin substrate to form a coating, and the coating is dried at about 100 ° C. to form the coating. The coating layer obtained was found to have poor solvent resistance. That is, when a solution containing a solvent is applied to form another layer on the coating layer formed by such a method, there is a problem that the coating layer is peeled off.
  • An object of the present invention is to provide a dielectric sheet which is excellent in solvent resistance and low in dielectric loss tangent in a high frequency region, and which can contribute to reduction of power consumption of a device mounted.
  • the present inventors can solve the above problems by a dielectric sheet having a ceramic gel layer formed from a coating solution containing a metal compound together with a ceramic gel synthesized by a sol-gel method using a metal alkoxide as a raw material. Found out.
  • the present invention provides the following [1] to [14].
  • [1] A substrate and a ceramic gel layer, wherein the ceramic gel layer is formed from a coating solution containing a ceramic gel (A) synthesized by a sol gel method using a metal alkoxide as a raw material and a metal compound (B) Layers, dielectric sheets.
  • the metal compound (B) is a metal complex of a metal selected from titanium, aluminum, zirconium, chromium, cobalt, iron, manganese, nickel, tin and zinc .
  • [3] The dielectric sheet according to the above [2], wherein the metal complex is a metal chelate.
  • the ceramic gel (A) comprises a barium titanate (BaTiO 3 ) gel.
  • the base material is a resin sheet containing a resin, and the resin sheet has a surface to which primer treatment has been applied, and the above-mentioned [A] has a configuration in which the ceramic gel layer is directly laminated on the surface.
  • dielectric sheet [11] The dielectric sheet according to any one of the above [1] to [10], which has a dielectric loss tangent (tan ⁇ ) at a frequency of 1 GHz of 8.0 ⁇ 10 ⁇ 2 or less.
  • the dielectric sheet of the present invention is excellent in solvent resistance and has a low dielectric loss tangent in a high frequency region, which can contribute to the reduction of the power consumption of the mounted device.
  • the dielectric sheet of the present invention has a substrate and a ceramic gel layer, but may have other layers besides these. For example, it may further have an adhesive layer on the surface of the substrate opposite to the side on which the ceramic gel layer is present.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is appropriately selected according to the application of the dielectric sheet, and examples thereof include acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives and the like.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the dielectric sheet of 1 aspect of this invention has a structure which the base material and the ceramic gel layer laminated
  • the dielectric sheet of the present invention has a high dielectric constant and a low dielectric loss tangent in a high frequency region.
  • the “high frequency region” means a region having a wavelength of usually 10 MHz or more (preferably 50 MHz or more, more preferably 100 MHz or more, still more preferably 1 GHz or more).
  • the magnitude of the power consumption can be taken as an index of the attenuation constant a indicating the degree of attenuation of the propagation signal, and the dielectric sheet having a smaller attenuation constant a is more excellent in the reduction effect of the power consumption.
  • the attenuation constant a is known to be related to the frequency f, the relative dielectric constant ⁇ ′, and the dielectric loss tangent tan ⁇ , as shown in the following equation (i).
  • a is a damping constant
  • f is a frequency
  • ⁇ ′ is a relative dielectric constant
  • tan ⁇ is a dielectric loss tangent
  • the damping constant a is considered to be particularly dependent on the value of the dielectric loss tangent tan ⁇ . Therefore, to reduce the damping constant a, it is necessary to reduce the value of the dielectric loss tangent tan ⁇ . Since the dielectric sheet of the present invention has a low dielectric loss tangent even in a high frequency region, it is considered that the value of the attenuation constant a calculated from the above equation (i) becomes small, and the power consumption is reduced.
  • the dielectric loss tangent (tan ⁇ ) at a frequency of 100 MHz of the dielectric sheet according to one embodiment of the present invention is preferably 8.0 ⁇ 10 ⁇ 2 or less, more preferably 5.0 ⁇ 10 ⁇ 2 or less, still more preferably 1.0 ⁇ It is 10 ⁇ 2 or less, and usually 1.0 ⁇ 10 ⁇ 7 or more.
  • the dielectric loss tangent (tan ⁇ ) at a frequency of 1 GHz of the dielectric sheet of one embodiment of the present invention is preferably 8.0 ⁇ 10 ⁇ 2 or less, more preferably 1.0 ⁇ 10 ⁇ 2 or less, still more preferably 8.
  • the dielectric loss tangent (tan ⁇ ) at each frequency is in the above range, the suppression effect of the power consumption of these devices is high when used for fixing the members of the devices provided with high frequency devices and distribution boards with a small distance between wires. .
  • the dielectric constant at a frequency of 100 MHz and 1 GHz is preferably independently 1.50 to 3.20, more preferably 1.60 to 3.10, and further preferably. Preferably, it is 1.70 to 3.00.
  • the dielectric constant is 1.50 or more, radio waves can be efficiently transmitted and received when applied to a high frequency device.
  • the relative dielectric constant is 3.20 or less, the power dissipation of these devices is reduced when the dielectric loss tangent is made smaller and the members of the device provided with a high frequency device or a distribution board with a small distance between wires are fixed. Can be effectively reduced.
  • the dielectric constant and dielectric loss tangent (tan-delta) in the frequency of 100 MHz or 1 GHz of a dielectric sheet mean the value measured by the method as described in an Example.
  • the total light transmittance of the dielectric sheet of one embodiment of the present invention is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, still more preferably 88% or more, and preferably Is 95% or less, more preferably 93% or less.
  • the total light transmittance of the dielectric sheet is a value measured in accordance with JIS K7361-1: 1997, and specifically, a value measured in accordance with the method described in the examples. .
  • the haze of the dielectric sheet according to one aspect of the present invention is preferably 1% or more, more preferably 1.5% or more, still more preferably 3% or more, still more preferably 5% or more, and preferably It is at most 20%, more preferably at most 15%, further preferably at most 13%.
  • the haze of the dielectric sheet is a value measured in accordance with JIS K7136: 2000, and specifically, a value measured in accordance with the method described in the examples.
  • the substrate of the dielectric sheet of one embodiment of the present invention is appropriately selected depending on the application, and may be a conductive substrate or an insulating substrate.
  • the metal base etc. which consist of iron, aluminum, gold, silver, copper etc. are mentioned, for example.
  • the insulating substrate for example, various papers such as high quality paper, art paper, coated paper, glassine paper, etc. and laminated paper obtained by laminating thermoplastic resin such as polyethylene on these paper substrates; porous materials such as non-woven fabric Material: Resin sheet containing one or more resins selected from polyolefin resin such as polyethylene resin and polypropylene resin, polyester resin such as polybutylene terephthalate resin, polyethylene terephthalate resin, acetate resin, ABS resin, polystyrene resin, vinyl chloride resin and the like A glass substrate; and the like.
  • the base material used by 1 aspect of this invention may be a single layer film or a sheet, and the multilayer film or sheet which is a laminated body of two or more layers may be sufficient.
  • the dielectric sheet of the present invention can be manufactured without having a sintering process as in the manufacturing method described later. Therefore, as a base material, the resin sheet containing resin can be chosen suitably.
  • the resin sheet which can be selected as a base material may be unstretched, or may be stretched in a uniaxial or biaxial direction such as longitudinal or transverse. Further, the resin sheet may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent and the like, in addition to the above-mentioned resin.
  • the surface of the resin sheet which is the substrate is oxidized or roughened.
  • surface treatment such as primer treatment.
  • the oxidation method include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, ozone / ultraviolet radiation treatment and the like.
  • the sand blasting method, the solvent treatment method, etc. are mentioned, for example.
  • the base material is a resin sheet containing a resin
  • the resin sheet has a surface to which primer treatment has been applied
  • the ceramic gel layer is formed on the surface It is preferable to have the structure which laminated
  • the thickness of the substrate is appropriately selected according to the application, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoint of handleability.
  • the ceramic gel layer is a layer formed from a coating solution containing a ceramic gel (A) synthesized by a sol-gel method using a metal alkoxide as a raw material and a metal compound (B).
  • the particles of the ceramic gel (A) contained in the ceramic gel layer are synthesized by a sol gel method using metal alkoxide as a raw material, and have a core-shell structure in which an amorphous is present so as to surround a core layer consisting of a crystalline phase. It is considered to be taken.
  • the functional group of the amorphous part of the particles of the ceramic gel (A) is bonded to the metal compound (B), and the particles of the ceramic gel (A) are connected via the metal compound (B) It is assumed that three-dimensional mesh structure is formed. As a result, it is considered that the dielectric properties of the ceramic gel layer are improved, and the hardenability of the ceramic gel layer is also improved.
  • the method of making it into a sheet-like thing as a ceramic precursor from the said coating film by a sol gel method is also considered.
  • the sheet-like material obtained by this method is not only inferior in dielectric properties because it is amorphous, but also has a problem in film forming property because it shrinks in volume due to a dehydration condensation reaction when it becomes a ceramic precursor.
  • the amorphous particles of the ceramic gel (A) are intertwined to form a three-dimensional network structure It is also considered possible. However, as compared with the case of bonding via the metal compound (B), the bonding strength is weak, and the curing properties of the formed ceramic gel layer tend to be inferior. In addition, when a solution containing a solvent is applied to the surface of such a ceramic gel layer, the amorphous entanglement of particles of the ceramic gel (A) is released, and the ceramic gel layer is swollen by the solvent and peeled off. There is a case.
  • the mass reduction rate calculated from the following formula when the ceramic gel layer is heated to 800 ° C. is preferably 10% or more, more preferably 12% or more, and still more preferably 15%. It is above and is usually 30% or less.
  • Mass loss ratio (%) ([mass of the ceramic gel layer before heating] ⁇ [mass of the ceramic gel layer after heating to 800 ° C.]) / [Mass of the ceramic gel layer before heating] ⁇ 100
  • the said mass decreasing rate is calculated more concretely using the method as described in an Example.
  • the amorphous part of the particles of the ceramic gel (A) is thermally decomposed to disappear and the crystalline phase remains.
  • the amorphous part burned off by the said thermal decomposition points out the unreacted hydroxyl group and alkoxy group which exist in an amorphous phase. That is, the mass reduction rate is an index indirectly indicating the proportion of the amorphous portion of the ceramic gel (A).
  • the mass is hardly reduced even when heating to 800 ° C. in the same manner, so that the mass reduction rate is around “0%”.
  • the mass reduction rate is 10% or more, the ratio of the amorphous part of the ceramic gel (A) capable of binding to the metal compound (B) is large, so the three-dimensional network structure is more easily formed, and the dielectric sheet Can further improve the dielectric properties of
  • the coating solution which is a formation material of the ceramic gel layer which the dielectric sheet of this invention has contains a ceramic gel (A) and a metallic compound (B), while improving a hardenability further, a dielectric property is improved more. From the viewpoint of forming a dielectric sheet, it is preferable to further contain an acid catalyst (C).
  • the coating solution used in one aspect of the present invention may contain an appropriately selected solvent, and may contain additives other than the components (A) to (C) as long as the effects of the present invention are not impaired. .
  • each component contained in a coating solution is demonstrated.
  • the ceramic gel (A) used in the present invention is one synthesized by a sol-gel method using a metal alkoxide as a raw material. As described above, by using the ceramic gel (A) synthesized by the sol-gel method, it binds to the metal compound (B), and the particles of the ceramic gel (A) are connected via the metal compound (B), It is presumed that a three-dimensional network structure is likely to be formed.
  • the ceramic gel (A) synthesized by the sol-gel method is presumed to have a special core-shell structure as described above, in particular, the crystalline phase of the core portion and the amorphous portion of the shell portion It is difficult to unambiguously specify the distribution aspect and the structure such as the binding form, and it is unrealistic to specify.
  • the point that “it has a structure different from particles having high crystallinity obtained by the solid phase method” can be inferred by the mass reduction rate described above, the shape of the amorphous part of the ceramic gel (A) or It has to be said that it is very difficult to specify the manner of bonding with the crystal phase itself. Therefore, in the present invention, the specification of the ceramic gel (A) is defined by a manufacturing method called "sol gel method".
  • the metal alkoxide used as a raw material of the ceramic gel (A) may be a compound represented by M (OR) p (M: metal atom, R: organic group, p: valence of M).
  • M metal atom
  • R organic group
  • p valence of M
  • Mg Mg, Ca, Sr, Ba, Sc, Y, Fe, Co, Ni, Cu, Zn, Cd, Pb, Bi, Ti, Zr, Hf, Sn, Sb, etc.
  • the organic group which can be selected as R is preferably an alkyl group having a carbon number of 1 to 4, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • the metal alkoxide is preferably Mg, Ca, Sr, Ba, Sc, Y, Fe, Co, Ni, Cu, Zn, Cd from the viewpoint of providing a dielectric sheet with further improved dielectric properties. It is preferable to include a metal alkoxide (I) containing a metal atom selected from Pb, and Bi, and a metal alkoxide (II) containing a metal atom selected from Ti, Zr, Hf, Sn, Sb.
  • the metal alkoxide (I) is preferably barium alkoxide (Ba (OR) 2 ), and the metal alkoxide (II) is preferably titanium alkoxide (Ti (OR) 4 ).
  • the compounding amount ratio [(I) / (II)] of metal alkoxide (I) to metal alkoxide (II) is preferably 0.80 to 1.20, more preferably 0.85 to 1 in molar ratio. And more preferably 0.90 to 1.10.
  • Step (i) Examples of the organic solvent used in the step (i) include alcohols such as methanol, ethanol, 2-methoxyethanol, n-propanol and isopropanol; ketones such as methyl ethyl ketone and acetone; and the like.
  • the organic solvents may be used alone or in combination of two or more. Among these, as the organic solvent, alcohols are preferable, and a mixed solvent of methanol and 2-methoxyethanol is more preferable.
  • step (i) As an inert gas used at process (i), nitrogen, argon etc. are mentioned, for example.
  • Step (ii) As a hydrolyzing agent used at process (ii), although water is preferable, you may use aqueous solution of acids or alkalis, such as an inorganic acid, an organic acid, a hydroxide, organic amines, for example.
  • the compounding amount of the hydrolyzing agent is preferably 2 to 20 moles, more preferably 4 to 15 moles, still more preferably 6 to 12 moles with respect to 1 mole of the total amount of the metal alkoxide.
  • the temperature conditions for blending the hydrolyzing agent in step (ii) are preferably -30 to 0 ° C, more preferably -20 to 0 ° C, and still more preferably -10 to 0 ° C.
  • the container is preferably ultrasonicated to prepare a solution in which the ceramic gel (A) is uniformly dispersed.
  • the ceramic gel (A) used in one embodiment of the present invention contains a barium titanate (BaTiO 3 ) gel.
  • the barium titanate (BaTiO 3 ) gel uses barium alkoxide (Ba (OR) 2 ) as the metal alkoxide (I) and titanium alkoxide (Ti (OR) 4 ) as the metal alkoxide (II).
  • Ba (OR) 2 barium alkoxide
  • Ti (OR) 4 ) titanium alkoxide
  • the content of barium titanate (BaTiO 3 ) gel in the total amount of 100% by mass of the ceramic gel (A) contained in the coating solution is preferably 70 to 100% by mass, more preferably It is 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the metal compound (B) used in the present invention is preferably a metal complex, more preferably a metal complex of a metal selected from titanium, aluminum, zirconium, chromium, cobalt, iron, manganese, nickel, tin and zinc More preferably, the metal complex is a metal chelate.
  • a titanium complex (B1) is included.
  • the content of the titanium complex (B1) in the total amount (100% by mass) of the metal compound (B) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and further preferably Preferably, it is 90 to 100% by mass, still more preferably 95 to 100% by mass.
  • titanium complex (B1) examples include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) Titanium, di-tert-buto Si-bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-
  • Ethylacetoacetate Titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tri (Ethylacetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-tert-butoxy tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) Examples include tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium and the like. These titanium complexes (B1) may be used alone or in combination of two or more.
  • the content of the metal compound (B) is preferably 1 to 35 parts by mass, more preferably 3 to 32 parts by mass, still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of component (A) in the coating solution. It is 30 parts by mass, more preferably 10 to 28 parts by mass, particularly preferably 15 to 25 parts by mass.
  • the content of the metal compound (B) is 1 part by mass or more, a dielectric sheet excellent in curability and solvent resistance can be obtained.
  • content of a metal compound (B) is 35 mass parts or less, it can be set as the dielectric sheet excellent in the optical characteristic.
  • the coating solution used in the present invention may contain an acid catalyst (C).
  • an acid catalyst (C) By containing the acid catalyst (C), bonding between the amorphous portion of the ceramic gel (A) and the metal compound (B) is promoted, and a stronger three-dimensional network structure is considered to be formed. As a result, the curability can be further improved, and the dielectric sheet can be further improved.
  • the acid catalyst preferably contains one or more selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, oxalic acid, p-toluenesulfonic acid, and trifluoroacetic acid, and hydrochloric acid It is more preferable to include. These acid catalysts may be used alone or in combination of two or more.
  • the concentration of the acid catalyst in the coating solution after compounding the acid catalyst is preferably 0.0001 to 10 M, more preferably 0.0003 to 1 M as the compounding amount of the acid catalyst, from the viewpoint of further improving the reactivity. It is appropriate to prepare so as to be more preferably 0.0005 to 0.01M.
  • the coating solution used in the present invention may contain other additives other than the components (A) to (C) within the range not impairing the effects of the present invention.
  • additives other than the components (A) to (C) include, for example, resin components, curing agents, antioxidants, light stabilizers, flame retardants, plasticizers, coloring agents, fungicides, rust inhibitors and the like.
  • the content of each of these other additives is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, based on the total amount of the active components of the coating solution. Still more preferably, it is 0 to 2% by mass.
  • the active ingredient of the coating solution refers to the components contained in the coating solution, excluding solvents such as water for dilution and organic solvents which are removed by evaporation in the process of forming the ceramic gel layer. Refers to liquid components, as well as components that are solid at normal temperature.
  • the coating solution used in one embodiment of the present invention contains the components (A) and (B) and, if necessary, the component (C) and the above-mentioned additives, but preferably further contains a solvent.
  • the solvent contained in the coating solution the solvent (water, alcohols, ketones, etc.) used at the time of synthesis of the ceramic gel (A) or the solvent in which the component (B) is dissolved may be used as it is. May be added to
  • the solvent include, in addition to water and the above-mentioned alcohols and ketones, for example, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene and the like. These solvents may be used alone or in combination of two or more.
  • the concentration of the active ingredient of the coating solution used in one embodiment of the present invention is preferably 0.5 to 15% by mass, more preferably 0.75 to 10% by mass, and still more preferably 1 to 5% by mass.
  • the method for producing a dielectric sheet of the present invention preferably includes the following steps (1) to (2).
  • Step (1) A step of blending a metal compound (B) with a ceramic gel (A) synthesized by a sol-gel method using a metal alkoxide as a raw material to prepare a coating solution.
  • Step (2) a step of applying the coating solution on the surface of a substrate to form a coating, and drying the coating to form a ceramic gel layer.
  • Step (1) the metal compound (B) is blended with the ceramic gel (A) synthesized by the sol-gel method described above to prepare a coating solution. At this time, it is preferable to further add an acid catalyst (C) together with the metal compound (B). Further, additives other than the components (A) to (C) may be blended. In this step, the metal compound (B) and the acid catalyst (C) are added to a solution of the ceramic gel (A) in which the solvent (water and the above-mentioned alcohols and ketones) used in the synthesis of the ceramic gel (A) remains. And other additives are preferably blended.
  • Step (2) At a process (2), the said coating solution is apply
  • the method of applying the coating solution include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the temperature condition for drying the formed coating film is preferably 70 to 170 ° C., more preferably 80 to 150 ° C., and still more preferably 90 to 120 ° C.
  • the drying time is preferably 6 seconds to 10 minutes, more preferably 1 to 5 minutes.
  • the dielectric sheet of the present invention can be used, for example, as a member of a device that transmits or receives an electromagnetic wave of high frequency of 10 MHz or more, or a member of a device having an integrated circuit with a distance between wires of 3 ⁇ m or less. It is effective for reducing power consumption.
  • the present invention can also provide the following apparatus.
  • devices that transmit or receive electromagnetic waves having a frequency of 10 MHz or more include, for example, mobile phones, high-speed wireless LANs, non-contact IC card systems, dangerous substance detection sensors, collision avoidance systems incorporated in automobiles, GPS (Global Positioning System) Positioning system, industrial science medical equipment and the like.
  • the dielectric sheet of the present invention has a function as a coverlay, and can reduce power consumption and prevent leaks between wires.
  • barium titanate (BaTiO 3 ) gel having an active ingredient concentration of 17% by mass.
  • a 50 ⁇ m-thick polyethylene terephthalate (PET) film product name “Cosmo Shine A4100”, product name: “Cosmo Shine A4100”
  • the coating solution (i) prepared in the above (2) is applied using an applicator onto the primer-treated surface of the PET film to form a coating, and the coating is heated at 100 ° C. for 3 minutes Then, a ceramic gel layer having a thickness of 1 ⁇ m was formed to obtain a dielectric sheet.
  • Example 2 In the preparation step of the coating solution of the above (2) of Example 1, with respect to 100 parts by mass of the active ingredient of a solution of barium titanate gel, 0.01 M hydrochloric acid is further added together with ethanol, water and a titanium complex. A coating solution (ii) having an active ingredient concentration of 2.76% by mass was prepared in the same manner as in Example 1 except that 1 part by mass was added. Then, using the coating solution (ii), in the same manner as in Example 1, a ceramic gel layer having a thickness of 1 ⁇ m was formed on the substrate, and a dielectric sheet was produced.
  • Comparative Example 1 A coating solution (iii) was prepared in the same manner as in Example 1, except that the titanium complex was not blended in the step of preparing the coating solution of the above (2) in Example 1. Then, using a coating solution (iii), in the same manner as in Example 1, a ceramic gel layer having a thickness of 1 ⁇ m was formed on a substrate to produce a dielectric sheet.
  • Comparative example 2 In the preparation process of the coating solution of the above (2) of Example 1, 196.1 parts of 0.01 M hydrochloric acid per 100 parts by mass of the active component of the solution of barium titanate gel without containing a titanium complex A coating solution (iv) was prepared in the same manner as in Example 1 except that a portion was blended. Then, using a coating solution (iv), in the same manner as in Example 1, a ceramic gel layer having a thickness of 1 ⁇ m was formed on a substrate to produce a dielectric sheet.
  • the haze is measured at three arbitrarily selected points of the surface of the test sample in the same manner as described above in accordance with JIS K 7136: 2000 using the above haze meter, and the average value thereof. As the haze of the dielectric sheet to be measured.
  • Mass loss ratio (%) ([mass of the ceramic gel layer before heating] ⁇ [mass of the ceramic gel layer after heating to 800 ° C.]) / [Mass of the ceramic gel layer before heating] ⁇ 100
  • the mass reduction rate of the commercially available barium titanate (BaTiO 3 ) filler (manufactured by Wako Pure Chemical Industries, Ltd.) was also measured as “0%” when measured under the same conditions as above.
  • the dielectric sheets produced in Examples 1 and 2 had good dielectric properties at both 100 MHz and 1 GHz, and also had good optical properties.
  • the ceramic gel layer of the dielectric sheet has excellent curability and solvent resistance.
  • the dielectric sheets produced in Comparative Examples 1 and 2 have good dielectric properties but poor solvent resistance.
  • the dielectric sheet of the present invention can be used, for example, as a member such as a device for transmitting or receiving an electromagnetic wave of high frequency of 10 MHz or more described above, and is effective for reducing the power consumption of the device. Further, as described above, the dielectric sheet of the present invention can be suitably used as a member of a device having an integrated circuit or the like having a wiring distance of 3 ⁇ m or less, and in the device, the dielectric sheet of the present invention has a function as a coverlay, Along with the reduction of power consumption, leakage between wires can be prevented.

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Abstract

L'invention concerne une feuille diélectrique et un procédé de fabrication de celle-ci. La feuille diélectrique de l'invention possède un matériau de base et une couche de gel céramique, laquelle couche de gel céramique est formée à partir d'une solution de revêtement qui comprend un gel céramique (A) obtenu par synthèse selon un procédé sol-gel avec un alcoxyde métallique pour matière première, et un composé métallique (B).
PCT/JP2018/034597 2017-09-25 2018-09-19 Feuille diélectrique, et procédé de fabrication de celle-ci Ceased WO2019059216A1 (fr)

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TWI819715B (zh) * 2021-07-26 2023-10-21 日商東洋油墨Ｓｃ控股股份有限公司 接著性樹脂片、印刷配線板及電子設備

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JP2000351623A (ja) * 1999-06-07 2000-12-19 Mitsubishi Materials Corp ペロブスカイト型酸化物薄膜形成用原料溶液
JP2002275390A (ja) * 2001-03-15 2002-09-25 Fukuoka Prefecture 結晶性ゲル分散コーティング溶液及び結晶性ゲル分散コーティング溶液を用いた薄膜形成方法
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JP2000351623A (ja) * 1999-06-07 2000-12-19 Mitsubishi Materials Corp ペロブスカイト型酸化物薄膜形成用原料溶液
JP2002275390A (ja) * 2001-03-15 2002-09-25 Fukuoka Prefecture 結晶性ゲル分散コーティング溶液及び結晶性ゲル分散コーティング溶液を用いた薄膜形成方法
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JP2005247660A (ja) * 2004-03-05 2005-09-15 Jsr Corp 誘電体膜形成用組成物、誘電体膜形成用組成物の製造方法ならびに誘電体膜および誘電体膜を含むキャパシタ

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI819715B (zh) * 2021-07-26 2023-10-21 日商東洋油墨Ｓｃ控股股份有限公司 接著性樹脂片、印刷配線板及電子設備

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