CN100348661C - Resin composition, cured resin, sheet-like cured resin, laminated body, prepreg, electronic parts and multilayer boards - Google Patents

Resin composition, cured resin, sheet-like cured resin, laminated body, prepreg, electronic parts and multilayer boards Download PDF

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CN100348661C
CN100348661C CNB2003801077778A CN200380107777A CN100348661C CN 100348661 C CN100348661 C CN 100348661C CN B2003801077778 A CNB2003801077778 A CN B2003801077778A CN 200380107777 A CN200380107777 A CN 200380107777A CN 100348661 C CN100348661 C CN 100348661C
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electron device
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resin
dielectric layer
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CN1732224A (en
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高谷稔
远藤敏一
川畑贤一
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/1901—Structure
    • H01L2924/1904—Component type
    • H01L2924/19041—Component type being a capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/191—Disposition
    • H01L2924/19101—Disposition of discrete passive components
    • H01L2924/19105—Disposition of discrete passive components in a side-by-side arrangement on a common die mounting substrate

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Abstract

The invention provides electronic parts which comprise a composite dielectric layer composed of an organic insulating material and a dielectric ceramic powder having a larger relative dielectric constant than the organic insulating material, and which also comprise conductive element sections forming inductor elements, etc., wherein the organic insulating material comprises a cured resin obtained by curing reaction of an epoxy resin with an active ester compound obtained by reaction between a compound with two or more carboxyl groups and a compound with a phenolic hydroxyl group. The dielectric ceramic powders of the described electronic parts have larger relative dielectric constants than the organic insulating materials, and the organic insulating materials have low dielectric loss tangents. It is possible to adequately reduce time-dependent dielectric constant changes in the high-frequency range of 100 MHz and above even with prolonged use at high temperatures of 100 DEG C. and higher, while it is also possible to satisfactorily prevent deformation and other damage to the electronic parts during their handling.

Description

Resin combination, cured resin, laminar cured resin, layered product, prepreg, electron device and multilager base plate
Technical field
The present invention relates to resin combination, cured resin, laminar cured resin, layered product, prepreg, electron device and multilager base plate, in more detail, relate to useful resin combination, cured resin, laminar cured resin, layered product, prepreg, electron device and multilager base plate in the high frequency field more than 100Mz.
Background technology
In recent years, along with the urgency of the communication information increases, people expect miniaturization, the lightweight of communicating machine consumingly, and people expect miniaturization, the lightweight of electron device thus.On the other hand, use the electric wave in the high frequency field of gigabit Hz band in portable type mobile communication, the satellite communications.
For the electric wave in the above-mentioned high frequency field of correspondence, require the power loss of electron device or conveyance loss little.That is, in electron device, produce the conveyance loss in course of conveying be called as dielectric loss, but this conveyance loss is consumed in electron device as thermal energy, becomes the reason of electron device heating, so not preferred.
Following formula is used in conveyance loss usually:
Conveyance loss=coefficient * frequency * (specific inductivity) 1/2* tangent of the dielectric loss angle
Expression is so in order to reduce conveyance loss, need make specific inductivity, tangent of the dielectric loss angle diminish.
On the other hand, for miniaturization, the lightweight that realizes electron device, need to improve the static capacity value of unit surface and electrode area is diminished.
The static capacity value is used following formula usually:
Relative permittivity * the electrode area of the specific inductivity * material of static capacity value=vacuum/thickness of insulating layer
So expression is in order to improve the relative permittivity that the static capacity value need improve material.
Therefore, for the reduction of all reaching the conveyance loss in the high frequency field and miniaturization, the lightweight of electron device, people's expectation obtains the equilibrated material that improves specific inductivity and reduce tangent of the dielectric loss angle.
With regard to the high material of specific inductivity, usually the known multipolymer that poly(vinylidene fluoride), trifluoro-ethylene-tetrafluoroethylene arranged, contain the polymkeric substance of cyano group etc., but existing problem aspect frequency response characteristic, low-dielectric loss tangent, the thermotolerance, the not talkative insulating material that constitutes electron device that is suitable as.
In addition, with regard to the low material of specific inductivity, known have a polyolefine, vinyl chloride resin, fluoro-resin, syndiotactic polystyrene, the thermoplastic resin of aromatic polyester resins etc., unsaturated polyester resin, polyimide resin, Resins, epoxy, bismaleimide-triazine resin (BT resin), bridging property polyphenylene oxide, solidified nature polyphenylene oxide, polyvinyl benzylic ether resin, various resins such as benzocyclobutane olefine resin, but these resins not only can not corresponding be used in the electric wave in high frequency field as described above, and its reality is all to satisfy thermotolerance, processing film, resistance to chemical reagents, insulativity, low-dielectric loss angle tangent, the desired fundamental property of electron devices such as low water absorption, in addition, in fact only use above-mentioned resin to be difficult to realize high specific inductivity, and low tangent of the dielectric loss angle.
Therefore, reach the high-k and the low-dielectric loss angle tangent of composite dielectric layer when satisfying the desired fundamental property of electron device, as the insulating material of the composite dielectric layer that constitutes electron device, known have dielectric ceramic powder is distributed to material (the Japanese Patent spy opens the 2001-247733 communique) in the polyvinyl benzylic ether compound.
Summary of the invention
Present inventors find, use the electron device of the composite dielectric layer that above-mentioned existing communique puts down in writing also to have room for improvement on characteristic.
That is, use the electron device of the composite dielectric layer that above-mentioned communique puts down in writing only to demonstrate high-k and low-dielectric loss angle tangent, its flexural strength and the dielectric characteristics aspect when at high temperature using also have room for improvement.That is, above-mentioned existing electron device also has the leeway of improvement aspect keeping in operability, performance when high temperature uses.
In addition, stating in the use in the electron device of the composite dielectric layer that communique puts down in writing, only is that the electrical characteristic of the specific inductivity of composite dielectric layer and tangent of the dielectric loss angle (tan δ) etc. are good, and this material might not be good aspect intensity.Therefore, the electron device put down in writing of above-mentioned communique also has the leeway of improvement aspect intensity.
In addition, not talkative its flexural strength of above-mentioned composite dielectric layer and crooked elastic rate are abundant, and the cementability (stripping strength etc.) of Copper Foil is also had room for improvement.
And above-mentioned composite dielectric layer is not talkative, and for example to become the second-order transition temperature of thermotolerance index fully high, and its characteristic has room for improvement.Such situation also is identical in the situation of reinforcing fiber being added in the composite dielectric layer.
Therefore, the object of the present invention is to provide resin combination, cured resin, laminar cured resin, layered product, prepreg, electron device and the multilager base plate that can fully improve the characteristic of electron device.
In order to achieve the above object, the invention provides and contain hardening mixtures that is made of active ester compound and Resins, epoxy and the resin combination that adds the dielectric ceramic powder in the above-mentioned hardening mixtures to, this active ester compound makes the compound with phenolic hydroxyl group and has the plural compound that forms the base of ester bond with the reaction of this phenolic hydroxyl group and reacts and form.
Resins, epoxy in the resin combination of the present invention and active ester compound generate the high-molecular weight resultant of reaction by reaction (curing reaction).Therefore, the above-mentioned hardening mixtures that is made of Resins, epoxy and active ester compound is the hardening mixtures that should become binder (matrix) resin by reaction, behind curing reaction, dielectric ceramic powder exists with the state that is dispersed in this binder resin.
The specific inductivity and the tangent of the dielectric loss angle of above-mentioned resultant of reaction are low, dielectric ceramic powder is dispersed in this resultant of reaction, so the cured article of resin combination all demonstrates high-k and low-dielectric loss angle tangent in the frequency field of gigabit Hz.In addition, use the active ester compound for the curing of Resins, epoxy, result from the hydroxyl of epoxy ring-opening so do not produce when curing reaction, capacitance characteristic is difficult to by temperature or humidity effect.
And, the resultant of reaction of Resins, epoxy and active ester compound has than the big molecular weight of above-mentioned polyvinyl benzylic ether, also can import crosslinking structure, so the cured article of resin combination of the present invention demonstrates high thermotolerance, second-order transition temperature and disassemble start-point temperature and also be improved.And, owing to the Resins, epoxy that contains substrate adherence excellences such as tinsels, so resin combination of the present invention is to the excellent binding property of tinsel performance.
In the present invention, the active ester compound is preferably the fragrant family active ester compound with following general formula (1) expression.
Figure C20038010777700071
(in the formula, k represents 2～4 integer; R 1Expression can be selected from the naphthyl of at least a replacement of halogen atom and alkyl, or expression can be selected from the phenyl of at least a replacement of halogen atom, alkyl and phenyl (this phenyl can be replaced by halogen atom and/or alkyl); R 2Expression contains the base of 2～4 valencys of 1～3 aromatic nucleus (this aromatic nucleus can be replaced by halogen atom and/or alkyl); But, work as R 2When containing a plurality of aromatic nucleus, this a plurality of aromatic nucleus or form condensed ring, or link by being selected from ehter bond, thioether bond, sulfone key, carbonyl key and single bonded at least a key.)
By using above-mentioned fragrant family active ester compound as the active ester compound, specific inductivity in the high frequency field of gigabit Hz is improved and make the reduction of tangent of the dielectric loss angle more remarkable, and since the existence of aromatic nucleus also further improve thermotolerance, second-order transition temperature and disassemble start-point temperature.
Dielectric ceramic powder is the metal oxide powder that contains at least a metal that is selected from magnesium, silicon, aluminium, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, bismuth, lithium, samarium and tantalum, be preferably specific inductivity and be 3.7～300, the Q value is 500～100,000 metal oxide powder.In addition, above-mentioned specific inductivity and Q value are the values in gigabit Hz band, and in the present invention, so-called gigabit Hz band is meant the frequency band of 100MHz～10GHz.On the other hand, the content of dielectric ceramic powder is preferably 5～185 parts by volume with respect to total 100 parts by volume of Resins, epoxy and active ester compound.By using above-mentioned dielectric ceramic powder, and the content by making dielectric ceramic powder can improve specific inductivity and improve the degree that tangent of the dielectric loss angle reduces in above-mentioned scope.And the viscosity of resin combination becomes the viscosity that is suitable for operating.
Resin combination of the present invention also preferably contains polyarylate (polyarylate),
This polyarylate is the material (X of this structure unit and the Y of structure unit of a plurality of existence both can be the same or different separately) that the repeating unit by being expressed as of constituting of X of structure unit and the Y of structure unit-X-Y-repeatedly forms repeatedly; the X of said structure unit is preferably the phthalyl with above-mentioned formula (2) expression; isophthaloyl or paraphenylene terephthalamide are (with respect to this phthalyl; isophthaloyl and paraphenylene terephthalamide's total mole number; paraphenylene terephthalamide's mole number is discontented with 40 moles of %), the Y of said structure unit is preferably the divalent radical with following general formula (3) expression.
Figure C20038010777700081
In the above-mentioned formula, R 11And R 12Alkyl, alkoxyl group or the halogen atom of representing carbonatoms 1～4 respectively independently, Z are represented singly-bound, ehter bond, thioether bond, sulfone key or carbonyl key, and p and q represent 0～4 integer respectively independently.But, in above-mentioned polyarylate, when there being a plurality of R 11, R 12And during Z, R 11, R 12And Z both can be the same or different separately.In addition, be preferably R especially 11And R 12For methyl, Z are singly-bound.By polyarylate is added in the resin combination, the flexible and bendability under the B scalariform attitude rises, and operability is good.
When resin combination contained polyarylate, the content of dielectric ceramic powder was preferably 5～185 parts by volume with respect to total 100 parts by volume of Resins, epoxy, active ester compound and polyarylate.Content by making dielectric ceramic powder can further improve specific inductivity, further reduce tangent of the dielectric loss angle in above-mentioned scope.In addition, the viscosity of resin combination becomes the viscosity that is suitable for operating.
Can add at least a additive that is selected from coupler, curing catalyst, fire retardant, flexible imparting agent and organic solvent in the resin combination of the present invention, when adding coupler, at least a portion that is preferably coupler in conjunction with or be adsorbed on the surface of dielectric ceramic powder.
By adding coupler, can improve the wettability or the surface bonding of dielectric ceramic powder in resin combination and the cured article thereof, curing catalyst quickens the curing reaction of Resins, epoxy and active ester compound.In addition, can improve flame retardant resistance,, when improving the operability of resin combination and cured article thereof, can improve the fragility of cured article and give toughness by adding flexible imparting agent by adding fire retardant.
The present invention also provides the curing reaction of the Resins, epoxy that makes in the above-mentioned resin combination and active ester compound partly to finish and the cured resin that forms, and the laminar resin combination that becomes lamella shape and made by this cured resin.The thickness of laminar cured resin can be 5～200 μ m, also tinsel can be bonded on the one or both sides of this laminar cured resin as layered product.Above-mentioned cured resin is the so-called B b stage resin b that the curing reaction of Resins, epoxy and active ester compound partly finishes, so can be used as prepreg.
The present invention also provides the curing reaction of the Resins, epoxy that makes in the above-mentioned resin combination and active ester compound to finish and the cured resin that forms, and the laminar resin combination that becomes lamella shape and made by this cured resin.The thickness of laminar cured resin can be 5～1000 μ m, also tinsel can be bonded on the one or both sides of this laminar cured resin as layered product.Above-mentioned cured resin demonstrates high-k and low-dielectric loss angle tangent at gigabit Hz frequency field, and dielectric characteristic is difficult to be arrived by temperature or humidity effect.In addition, demonstrate high thermotolerance, second-order transition temperature and disassemble start-point temperature.And in above-mentioned layered product, the cementability of laminar cured resin and tinsel is good especially.
In order to achieve the above object, the invention provides to make and contain the hardening mixtures that is made of active ester compound and Resins, epoxy and add dielectric ceramic powder in the hardening mixtures to and the resin combination semicure of reinforcing fiber and the prepreg that forms, this active ester compound makes the compound with phenolic hydroxyl group and has the plural compound that forms the base of ester bond with this phenolic hydroxyl group reaction and reacts and form.
The present invention also provides a kind of prepreg, and this prepreg possesses: weaving reinforcing fiber and reinforcing fiber fabric that forms and the resin layer that forms on the two sides of this reinforcing fiber fabric; Above-mentioned resin layer is, make and contain the hardening mixtures that is made of active ester compound and Resins, epoxy and add the resin combination semicure of the dielectric ceramic powder in this hardening mixtures to and the resin layer that forms, this active ester compound makes the compound with phenolic hydroxyl group and has the plural compound that forms the base of ester bond with this phenolic hydroxyl group reaction and reacts and form.In addition, in this prepreg, resin layer is preferably the thickness with 5～100 μ m, and the reinforcing fiber fabric is preferably the thickness with 20～300 μ m.
In above-mentioned prepreg of the present invention, Resins, epoxy and active ester compound constitute hardening mixtures.That is, Resins, epoxy and active ester compound react (curing reaction) generation high-molecular weight resultant of reaction.
The specific inductivity and the tangent of the dielectric loss angle of above-mentioned resultant of reaction are low, by in this resultant of reaction, disperseing dielectric ceramic powder, adding reinforcing fiber, the cured article of prepreg is as all, demonstrates high-k, low-dielectric loss angle tangent at the frequency field of gigabit Hz.In addition, use the active ester compound in order to make epoxy resin cure, result from the hydroxyl of epoxy ring-opening so do not have to produce when curing reaction, dielectric characteristics is difficult to be arrived by temperature or humidity effect.
And, the resultant of reaction of Resins, epoxy and active ester compound has than the big molecular weight of above-mentioned polyvinyl benzylic ether, also can import crosslinking structure, so the cured article of prepreg of the present invention demonstrates high thermotolerance, second-order transition temperature also is improved.And, owing to the Resins, epoxy that contains the binding property excellence of base materials such as tinsel, so prepreg of the present invention is being brought into play excellent cementability to tinsel.
In the present invention, the active ester compound is preferably the fragrant family active ester compound with following general formula (1) expression.
Figure C20038010777700101
(in the formula, k represents 2～4 integer; R 1Expression can be selected from the naphthyl of at least a replacement of halogen atom and alkyl, or expression can be selected from the phenyl of at least a replacement of halogen atom, alkyl and phenyl (this phenyl can be replaced by halogen atom and/or alkyl); R 2Expression contains the base of 2～4 valencys of 1～3 aromatic nucleus (this aromatic nucleus can be replaced by halogen atom and/or alkyl); But, work as R 2When containing a plurality of aromatic nucleus, this a plurality of aromatic nucleus or form condensed ring, or link by being selected from ehter bond, thioether bond, sulfone key, carbonyl key and single bonded at least a key.)
By using above-mentioned fragrant family active ester compound as the active ester compound, the specific inductivity of the frequency field of gigabit Hz is improved and make the reduction of tangent of the dielectric loss angle more remarkable, because the existence of aromatic nucleus also further improves second-order transition temperature.
Dielectric ceramic powder is the metal oxide powder that contains at least a metal that is selected from magnesium, silicon, aluminium, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, bismuth, lithium, samarium and tantalum, preferred specific inductivity is 3.7～300, the Q value is 500～100,000 metal oxide powder.In addition, above-mentioned specific inductivity and Q value are the values at gigabit Hz band, and in the present invention, so-called gigabit Hz band is meant the frequency band of 100MHz～10GHz.On the other hand, the content of dielectric ceramic powder is preferably 5～100 parts by volume with respect to total 100 parts by volume of Resins, epoxy and active ester compound.By using above-mentioned dielectric ceramic powder, but also the content by making dielectric ceramic powder can improve specific inductivity and improve the degree that tangent of the dielectric loss angle reduces in above-mentioned scope.And the viscosity of prepreg becomes and is suitable for operating viscosity.
Resin combination in the prepreg of the present invention also preferably contains polyarylate; this polyarylate is the material (X of this structure unit and the Y of structure unit of a plurality of existence both can be the same or different separately) that the repeating unit by being expressed as of constituting of X of structure unit and the Y of structure unit-X-Y-repeatedly forms repeatedly; the X of said structure unit is preferably the phthalyl with above-mentioned formula (2) expression; isophthaloyl or terephthaloyl are (with respect to this phthalyl; the total mole number of isophthaloyl and terephthaloyl; the mole number of terephthaloyl is discontented with 40 moles of %), the Y of said structure unit is preferably the divalent radical with following general formula (3) expression.
Figure C20038010777700111
In the above-mentioned formula, R 11And R 12Alkyl, alkoxyl group or the halogen atom of representing carbonatoms 1～4 respectively independently, Z are represented singly-bound, ehter bond, thioether bond, sulfone key or carbonyl key, and p and q represent 0～4 integer respectively independently.But, in above-mentioned polyarylate, when there being a plurality of R 11, R 12And during Z, R 11, R 12And Z both can be the same or different separately.In addition, preferred especially R 11And R 12For methyl, z are singly-bound.By polyarylate is added in the prepreg, can give toughness to prepreg, improve operability.
Resin combination in prepreg contains under the situation of polyarylate, and the content of dielectric ceramic powder is, with respect to total 100 parts by volume of Resins, epoxy, active ester compound and polyarylate, preferred 5～100 parts by volume.Content by making dielectric ceramic powder can further improve specific inductivity, further reduce tangent of the dielectric loss angle in above-mentioned scope.In addition, the viscosity of prepreg becomes the viscosity that is suitable for operating.
Can add at least a additive that is selected from coupler, curing catalyst, fire retardant and flexible imparting agent in the resin combination, when adding coupler, at least a portion that is preferably coupler in conjunction with or be adsorbed on the surface of dielectric ceramic powder.
By adding coupler, can improve the wettability or the surface bonding of dielectric ceramic powder in prepreg and the cured article thereof, curing catalyst quickens the curing reaction of Resins, epoxy and active ester compound.In addition, can improve flame retardant resistance,, when improving the operability of prepreg and cured article thereof, can improve the fragility of cured article and give toughness by adding flexible imparting agent by adding fire retardant.
Above-mentioned reinforcing fiber is preferably at least a reinforcing fiber that is selected from E glass fibre, D glass fibre, NE glass fibre, H glass fibre, T glass fibre and aromatic polyamide fibre.This is because dispersed good in above-mentioned resin combination of such reinforcing fiber, but also can improve the intensity of solidified prepreg.
The laminar cured resin that the present invention also provides to be become lamella shape, made by the cured article of above-mentioned prepreg.The thickness of laminar cured resin can be 30～10000 μ m, tinsel can be bonded on the one or both sides of this laminar cured resin as layered product.Laminar cured resin demonstrates high-k and low-dielectric loss angle tangent at gigabit Hz frequency field, and temperature or humidity are difficult to influence dielectric characteristics.In addition, demonstrate high thermotolerance and second-order transition temperature.And in above-mentioned layered product, the cementability of laminar cured resin and tinsel is good especially.
In order to achieve the above object, present inventors are conceived to constitute the material of the composite dielectric layer of electron device especially, wholwe-hearted research and development have been proceeded, found that dielectric ceramic powder added in the organic insulation that contains specific cured resin to solve above-mentioned problem, thereby finished the present invention.
That is, the present invention is a kind of electron device, it is characterized in that possessing: contain organic insulation and at least a composite dielectric layer with dielectric ceramic powder of the relative permittivity bigger than above-mentioned organic insulation; Be arranged on the above-mentioned composite dielectric layer, constitute at least a conductive element portion of capacitor element or inductor element; Wherein, above-mentioned organic insulation contains, the compound that the cured resin that makes Resins, epoxy and active ester compound be cured reaction and form, this active ester compound make the compound with plural carboxyl and have a phenolic hydroxyl group reacts and forms.In addition, the present invention is a kind of electron device, it is characterized in that possessing: contain organic insulation and at least a composite dielectric layer with dielectric ceramic powder of the relative permittivity bigger than above-mentioned organic insulation; Be arranged at least a conductive element portion on the above-mentioned composite dielectric layer; Be connected electrically in the electronic component in the above-mentioned conductive element portion; Wherein, above-mentioned organic insulation contains the cured resin that makes Resins, epoxy and active ester compound be cured reaction and form, and the compound that this active ester compound makes the compound with plural carboxyl and has a phenolic hydroxyl group reacts and forms.In addition, in electron device of the present invention, the active ester compound also can be make compound with phenolic hydroxyl group with having that the plural compound that forms the base of ester bond with this phenolic hydroxyl group reaction reacts the active ester compound that forms.Here, as reacting the base that forms ester bond, can enumerate carboxyl, halogen formyl radical (chloroformyl etc.) with phenolic hydroxyl group.
Because dielectric ceramic powder has the relative permittivity bigger than the organic insulation that contains cured resin, organic insulation has low-dielectric loss angle tangent, even so this electron device in the high frequency field of gigabit Hz, composite dielectric layer also demonstrates high-k and low-dielectric loss angle tangent.Therefore, reduced the conveyance loss of electron device, made the miniaturization of electron device, lightweight become possibility.In addition, even under the high temperature more than 100 ℃, use for a long time, also can fully be reduced in relative permittivity in the above high frequency field of 100MHz through the time change.And this electron device so the operability of electron device is improved, can fully prevent the damaged and even distortion of electron device etc. because flexural strength becomes big.
Active ester compound in the above-mentioned electron device is preferably the fragrant family active ester compound with following general formula (1) expression.
Figure C20038010777700131
(in the formula, k represents 2～4 integer; R 1Expression can be selected from the naphthyl of at least a replacement of halogen atom and alkyl, or expression can be selected from the phenyl of at least a replacement of halogen atom, alkyl and phenyl (this phenyl can be replaced by halogen atom and/or alkyl); R 2Expression contains the base of 2～4 valencys of 1～3 aromatic nucleus (this aromatic nucleus can be replaced by halogen atom and/or alkyl); But, work as R 2When containing a plurality of aromatic nucleus, this a plurality of aromatic nucleus or form condensed ring, or link by being selected from ehter bond, thioether bond, sulfone key, carbonyl key and single bonded at least a key.)
By using above-mentioned fragrant family active ester compound as the active ester compound, not only make the reduction of the tangent of the dielectric loss angle in the frequency field of gigabit Hz of cured resin more remarkable, because the existence of aromatic nucleus also further improves thermotolerance, the second-order transition temperature of cured resin and disassembles start-point temperature.
In above-mentioned electron device, above-mentioned dielectric ceramic powder is the metal oxide powder that contains at least a metal that is selected from magnesium, silicon, aluminium, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, bismuth, lithium, samarium and tantalum, preferred relative permittivity is 3.7～300, the Q value is 500～100,000 metal oxide powder, above-mentioned dielectric ceramic powder preferably adds 5～185 parts by volume with respect to above-mentioned organic insulation 100 parts by volume.In addition, above-mentioned relative permittivity and Q value are the values in gigabit Hz band, and in the present invention, so-called gigabit Hz band is meant the frequency band of 100MHz～10GHz.
In above-mentioned electron device, by using above-mentioned dielectric ceramic powder, but also, can improve specific inductivity and improve the degree that tangent of the dielectric loss angle reduces by making addition with respect to the dielectric ceramic powder of organic insulation in above-mentioned scope.
Above-mentioned cured resin is to make above-mentioned Resins, epoxy and above-mentioned active ester compound be cured reaction and formation in the presence of additive, and above-mentioned additive can be at least a additive that is selected from curing catalyst, surface treatment agent, fire retardant and flexible imparting agent.
Curing catalyst quickens the curing reaction of Resins, epoxy and active ester compound.In addition, by adding surface treatment agent, can improve the wettability and the surface bonding of the dielectric ceramic powder in the cured resin.In addition, can improve flame retardant resistance,, when improving the operability of cured resin, can improve the fragility of cured resin and give toughness by adding flexible imparting agent by adding fire retardant.
In above-mentioned electron device, above-mentioned organic insulation also preferably contains polyarylate.At this moment, the flexible and bendability under the B scalariform attitude rises, and operability is good.
In addition; above-mentioned polyarylate is the material (X of this structure unit and the Y of structure unit of a plurality of existence both can be the same or different separately) that the repeating unit by being expressed as of constituting of X of structure unit and the Y of structure unit-X-Y-repeatedly forms repeatedly; the X of said structure unit is preferably the phthalyl with above-mentioned formula (2) expression; isophthaloyl or paraphenylene terephthalamide are (with respect to this phthalyl; isophthaloyl and paraphenylene terephthalamide's total mole number; paraphenylene terephthalamide's mole number is discontented with 40 moles of %)
Figure C20038010777700141
The Y of said structure unit is preferably the divalent radical with following general formula (3) expression.
Figure C20038010777700142
(in the formula, R 11And R 12Alkyl, alkoxyl group or the halogen atom of representing carbonatoms 1～4 respectively independently, Z are represented singly-bound, ehter bond, thioether bond, sulfone key or carbonyl key, and p and q represent 0～4 integer respectively independently.But, in above-mentioned polyarylate, when there being a plurality of R 11, R 12And during Z, R 11, R 12And Z both can be the same or different separately.)
Polyarylate is compared with the polyarylate with above-mentioned formation formation in addition by becoming above-mentioned formation, can give prepreg toughness and operability and be improved.
In above-mentioned general formula (3), above-mentioned R 11And above-mentioned R 12Be preferably methyl, Z is preferably singly-bound.
At this moment, can give prepreg toughness and operability especially is improved.
Above-mentioned composite dielectric layer also preferably contains the magnetic substance powder that is distributed in the above-mentioned organic insulation.
At this moment,, can give the composite dielectric layer magnetic properties, reduce linear expansivity, improve the strength of materials by the magnetic substance powder.
Above-mentioned composite dielectric layer also preferably contains the cloth that is made of reinforcing fiber.
At this moment, by the cloth that constitutes by reinforcing fiber, strengthened the flexural strength of composite dielectric layer.Therefore, fully prevented the distortion of electron device or damaged etc.
In addition, present inventors carry out wholwe-hearted result of study discovery in order to achieve the above object: become following formation by making multilager base plate and electron device, also can solve above-mentioned problem, thereby finish the present invention.
Promptly, the present invention relates to a kind of multilager base plate and electron device, it is characterized in that: to the 1st dielectric layer of one deck at least that contains resin, contain the 2nd dielectric layer of one deck at least of resin and one deck conductor layer at least, carry out lamination and constitute, the tangent of the dielectric loss angle tan δ of above-mentioned the 2nd dielectric layer is below 0.01, and the limit amount of deflection of above-mentioned the 1st dielectric layer is more than 1.3 times of above-mentioned the 2nd dielectric layer.
As long as utilize this multilager base plate and electron device, the limit amount of deflection of the 1st dielectric layer is more than 1.3 times of the 2nd dielectric layer, and the tangent of the dielectric loss angle tan δ of the 2nd dielectric layer is below 0.01.That is, multilager base plate of the present invention and electron device comprise the dielectric layer that physical strength is good and the dielectric layer of good electric performance.Therefore, even at the after-applied excessive load of goodsization, when also can keep electrical characteristic well, can fully prevent the damaged generation in multilager base plate or the electron device.
Above-mentioned the 2nd dielectric layer can also contain compares the big ceramic powder of specific inductivity with above-mentioned resin.At this moment, even under the situation of using the little resin of specific inductivity, also can keep good electrical characteristic.
Above-mentioned multilager base plate and electron device are preferably: have two-layer outermost layer, above-mentioned two outermost one decks at least are made of above-mentioned the 1st dielectric layer, dispose the 2nd above-mentioned dielectric layer of one deck at least between above-mentioned two-layer outermost layer.At this moment, even multilager base plate and electron device are applied excessive load, also can prevent the damaged generation of multilager base plate or electron device more fully.
In above-mentioned multilager base plate and electron device, the stripping strength of above-mentioned the 1st dielectric layer is preferably more than 1.5 times of stripping strength of above-mentioned the 2nd dielectric layer.At this moment, even at the after-applied excessive load of goodsization, when also can keep good electrical characteristic, can prevent the damaged generation of multilager base plate or electron device more fully.
In addition, the invention still further relates to a kind of multilager base plate and electron device, it is characterized in that: to two-layer the 1st dielectric layer that contains resin, be configured between above-mentioned two-layer the 1st dielectric layer and contain the 2nd dielectric layer of one deck at least of resin and one deck conductor layer at least, carry out lamination and constitute, one deck at least of above-mentioned two-layer the 1st dielectric layer constitutes outermost layer, the tangent of the dielectric loss angle tan δ of above-mentioned the 2nd dielectric layer is below 0.01, and the stripping strength of above-mentioned the 1st dielectric layer is more than 1.5 times of stripping strength of above-mentioned the 2nd dielectric layer.As long as utilize these multilager base plates and electron device, stripping strength is more than 1.5 times of stripping strength of above-mentioned the 2nd dielectric layer, and the tangent of the dielectric loss angle tan δ of the 2nd dielectric layer is below 0.01.That is, multilager base plate of the present invention and electron device comprise the dielectric layer that physical strength is good and the dielectric layer of good electric performance.Therefore, even at the after-applied excessive load of goodsization, when also can keep electrical characteristic well, can fully prevent the damaged generation in multilager base plate or the electron device.
In above-mentioned multilager base plate and electron device, the stripping strength of above-mentioned the 1st dielectric layer is preferably more than the 8N/cm.At this moment, be discontented with the situation of 8N/cm with the stripping strength of the 1st dielectric layer and compare, further improve passive device and the constant intensity of active member and the pole strength of stripping strength, multilager base plate and electron device of actual installation.
In addition, the invention still further relates to the electron device that possesses above-mentioned multilager base plate and be arranged on the electronic component on the multilager base plate.In this case, because multilager base plate comprises dielectric layer and the outstanding dielectric layer of electrical characteristic that physical strength is outstanding, even so after goodsization, electron device is applied excessive load, when also can keep electrical characteristic well, can fully prevent the damaged generation in multilager base plate or the electron device.
In addition, in multilager base plate of the present invention and electron device, so-called limit amount of deflection is meant, plate object to the Cu paper tinsel of laminate thickness 12 μ m on the 1st dielectric layer of the rectangular flat shape of long 100mm, wide 75mm, thick 0.6mm or the 2nd dielectric layer, when increasing the weight of to make its deflection, the 1st dielectric layer or the 2nd dielectric layer destroy or the 1st dielectric layer or the 2nd dielectric layer amount of deflection when damaged (crack) takes place, and amount of deflection is meant by measuring the amount of deflection that (determination of test method of the flexural strength of being put down in writing according to JIS C6481) three-point bending obtains.In addition, so-called stripping strength is meant defined stripping strength in JIS C6481.
Description of drawings
Figure 1A is the sectional view of an embodiment of expression resin combination of the present invention.
Figure 1B is the sectional view of the 1st embodiment of expression laminar cured resin of the present invention.
Fig. 1 C is the sectional view of the 1st embodiment of expression layered product of the present invention.
Fig. 1 D is the sectional view of an embodiment of expression prepreg of the present invention.
Fig. 1 E is the sectional view of the 2nd embodiment of expression laminar cured resin of the present invention.
Fig. 1 F is the sectional view of the 2nd embodiment of expression layered product of the present invention.
Fig. 1 G is the perspective oblique drawing of inducer of the 1st embodiment of expression electron device of the present invention.
Fig. 2 is the sectional view of inducer of the 1st embodiment of expression electron device of the present invention.
Fig. 3 is the perspective oblique drawing of inducer of the 2nd embodiment of expression electron device of the present invention.
Fig. 4 is the sectional view of inducer of the 2nd embodiment of expression electron device of the present invention.
Fig. 5 is the perspective oblique drawing of inducer of the 3rd embodiment of expression electron device of the present invention.
Fig. 6 is the sectional view of inducer of the 3rd embodiment of expression electron device of the present invention.
Fig. 7 is the perspective oblique drawing of inducer of the 4th embodiment of expression electron device of the present invention.
Fig. 8 is the sectional view of inducer of the 4th embodiment of expression electron device of the present invention.
Fig. 9 is the perspective oblique drawing of inducer of the 5th embodiment of expression electron device of the present invention.
Figure 10 is the equivalent-circuit diagram of inducer of the 1st, the 5th embodiment of expression electron device of the present invention.
Figure 11 is the perspective oblique drawing of electrical condenser of the 6th embodiment of expression electron device of the present invention.
Figure 12 is the sectional view of electrical condenser of the 6th embodiment of expression electron device of the present invention.
Figure 13 is the perspective oblique drawing of electrical condenser of the 7th embodiment of expression electron device of the present invention.
Figure 14 is the equivalent-circuit diagram of electrical condenser of the 7th embodiment of expression electron device of the present invention.
Figure 15 is the perspective oblique drawing of balanced-to-unbalanced transformer of the 8th embodiment of expression electron device of the present invention.
Figure 16 is the sectional view of balanced-to-unbalanced transformer of the 8th embodiment of expression electron device of the present invention.
Figure 17 is the stratified decomposition view of each structure of balanced-to-unbalanced transformer of the 8th embodiment of expression electron device of the present invention.
Figure 18 is the equivalent-circuit diagram of balanced-to-unbalanced transformer of the 8th embodiment of expression electron device of the present invention.
Figure 19 is the oblique drawing of laminated filter of the 9th embodiment of expression electron device of the present invention.
Figure 20 is the exploded perspective view of laminated filter of the 9th embodiment of expression electron device of the present invention.
Figure 21 is the equivalent-circuit diagram of laminated filter of the 9th embodiment of expression electron device of the present invention.
Figure 22 is the graphic representation of reception and registration characteristic of laminated filter of the 9th embodiment of expression electron device of the present invention.
Figure 23 is the oblique drawing of laminated filter of the 10th embodiment of expression electron device of the present invention.
Figure 24 is the exploded perspective view of laminated filter of the 10th embodiment of expression electron device of the present invention.
Figure 25 is the equivalent-circuit diagram of laminated filter of the 10th embodiment of expression electron device of the present invention.
Figure 26 is the graphic representation of reception and registration characteristic of laminated filter of the 10th embodiment of expression electron device of the present invention.
Figure 27 is the oblique drawing of stop filter of the 11st embodiment of expression electron device of the present invention.
Figure 28 is the front cross-sectional view of stop filter of the 11st embodiment of expression electron device of the present invention.
Figure 29 is the side cross-sectional views of stop filter of the 11st embodiment of expression electron device of the present invention.
Figure 30 is the plan cross-sectional view of stop filter of the 11st embodiment of expression electron device of the present invention.
Figure 31 is the equivalent-circuit diagram of stop filter of the 11st embodiment of expression electron device of the present invention.
Figure 32 is the fragmentary cross sectional view of metal die of the stop filter of expression the 11st embodiment that is used to make electron device of the present invention.
Figure 33 is the perspective oblique drawing of unitor of the 12nd embodiment of expression electron device of the present invention.
Figure 34 is the sectional view of unitor of the 12nd embodiment of expression electron device of the present invention.
Figure 35 is the stratified exploded perspective view of each structure of unitor of the 12nd embodiment of expression electron device of the present invention.
Figure 36 is the cut-away view of unitor of the 12nd embodiment of expression electron device of the present invention.
Figure 37 is the equivalent-circuit diagram of unitor of the 12nd embodiment of expression electron device of the present invention.
Figure 38 is the perspective oblique drawing of antenna of the 13rd embodiment of expression electron device of the present invention.
Figure 39 is the figure of antenna of the 13rd embodiment of expression electron device of the present invention, (a) is orthographic plan, (b) is side cross-sectional, view, (c) is elevational sectional view.
Figure 40 is the stratified exploded perspective view of each structure of antenna of the 13rd embodiment of expression electron device of the present invention.
Figure 41 is the perspective oblique drawing of antenna of the 14th embodiment of expression electron device of the present invention.
Figure 42 is the exploded perspective view of antenna of the 14th embodiment of expression electron device of the present invention.
Figure 43 is the perspective oblique drawing of patch antenna of the 15th embodiment of expression electron device of the present invention.
Figure 44 is the sectional view of patch antenna of the 15th embodiment of expression electron device of the present invention.
Figure 45 is the perspective oblique drawing of patch antenna of the 16th embodiment of expression electron device of the present invention.
Figure 46 is the sectional view of patch antenna of the 16th embodiment of expression electron device of the present invention.
Figure 47 is the perspective oblique drawing of patch antenna of the 17th embodiment of expression electron device of the present invention.
Figure 48 is the sectional view of patch antenna of the 17th embodiment of expression electron device of the present invention.
Figure 49 is the perspective oblique drawing of patch antenna of the 18th embodiment of expression electron device of the present invention.
Figure 50 is the sectional view of patch antenna of the 18th embodiment of expression electron device of the present invention.
Figure 51 is the perspective oblique drawing of VCO of the 19th embodiment of expression electron device of the present invention.
Figure 52 is the sectional view of VCO of the 19th embodiment of expression electron device of the present invention.
Figure 53 is the equivalent-circuit diagram of VCO of the 19th embodiment of expression electron device of the present invention.
Figure 54 is the stratified exploded perspective view of each structure of power amplifier of the 20th embodiment of expression electron device of the present invention.
Figure 55 is the sectional view of power amplifier of the 20th embodiment of expression electron device of the present invention.
Figure 56 is the equivalent-circuit diagram of power amplifier of the 20th embodiment of expression electron device of the present invention.
Figure 57 is the stratified decomposition view of each structure of overlapping element of the 21st embodiment of expression electron device of the present invention.
Figure 58 is the sectional view of overlapping element of the 21st embodiment of expression electron device of the present invention.
Figure 59 is the equivalent-circuit diagram of overlapping element of the 21st embodiment of expression electron device of the present invention.
Figure 60 is the oblique drawing of RF assembly of the 22nd embodiment of expression electron device of the present invention.
Figure 61 is the oblique drawing of the RF assembly under the state of the exterior member that takes off Figure 60.
Figure 62 is the stratified exploded perspective view of each structure of RF assembly of the 22nd embodiment of expression electron device of the present invention.
Figure 63 is the sectional view of RF assembly of the 22nd embodiment of expression electron device of the present invention.
Figure 64 is the perspective oblique drawing of syntonizer of the 23rd embodiment of expression electron device of the present invention.
Figure 65 is the sectional view of syntonizer of the 23rd embodiment of expression electron device of the present invention.
Figure 66 is the perspective oblique drawing of syntonizer of the 24th embodiment of expression electron device of the present invention.
Figure 67 is the sectional view of syntonizer of the 24th embodiment of expression electron device of the present invention.
Figure 68 is the perspective oblique drawing of syntonizer of the 25th embodiment of expression electron device of the present invention.
Figure 69 is the perspective oblique drawing of syntonizer of the 26th embodiment of expression electron device of the present invention.
Figure 70 is the equivalent-circuit diagram of syntonizer of the 23rd～26 embodiment of expression electron device of the present invention.
Figure 71 is the square pie graph that the high frequency of carried terminal machine of the 27th embodiment of expression electron device of the present invention is commanded troops.
Figure 72 is the schema of the formation example of the attached copper clad laminate of expression.
Figure 73 is the process picture sheet of the formation example of the attached copper clad laminate of expression.
Figure 74 is the schema of the formation example of expression multilager base plate.
Figure 75 is the process picture sheet of the formation example of expression multilager base plate.
Figure 76 is the partial cross section figure of the 28th embodiment of expression electron device of the present invention.
Figure 77 is the perspective oblique drawing of electrical condenser of the 29th embodiment of expression electron device of the present invention.
Figure 78 is the partial cross section figure of electrical condenser of the 29th embodiment of expression electron device of the present invention.
Figure 79 is the perspective oblique drawing of inducer of the 30th embodiment of expression electron device of the present invention.
Figure 80 is the partial cross section figure of inducer of the 30th embodiment of expression electron device of the present invention.
Figure 81 be when being illustrated in the cured article of 125 ℃ of heating resin combinations through the time specific inductivity figure that rises.
Figure 82 is the partial cross section figure of the electron device of expression embodiment 13.
Embodiment
Below, resin combination of the present invention, cured resin, laminar cured resin, layered product, electron device and multilager base plate are described preferred embodiment.
At first, resin combination of the present invention is described.Figure 1A is the sectional view of an embodiment of expression resin combination of the present invention.Shown in Figure 1A, resin combination 18 comprises hardening mixtures 19 and the dielectric ceramic powder 3 that adds in the hardening mixtures 19.
Hardening mixtures 19 is made of active ester compound and Resins, epoxy, this active ester compound be make compound with phenolic hydroxyl group and have plural and the reaction of this phenolic hydroxyl group form ester bond base the compound reaction and form.
Constitute the Resins, epoxy of hardening mixtures 19 so long as to have a compound of more than one epoxy group(ing) just passable, but, be preferably compound with plural epoxy group(ing) from the viewpoint of molecular weight and degree of crosslinking.
As above-mentioned Resins, epoxy, the phenol that can enumerate cresols-phenol aldehyde type epoxy resin, phenol-phenol aldehyde type epoxy resin, naphthol-modified phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, diphenyl type Resins, epoxy, terphenyl type Resins, epoxy etc. is the Racemic glycidol ether type epoxy; The alcohol of polypropylene glycol glycidyl ether, hydrogenation bisphenol A type epoxy resin etc. is the Racemic glycidol ether type epoxy; Dicyclopentadiene-type epoxy resin with Dicyclopentadiene (DCPD) framework; Naphthalene type Resins, epoxy with naphthalene framework; Dihydroxyl benzo pyranose form Resins, epoxy; Dihydroxyl dinaphthyl type Resins, epoxy; With hexahydro phthalic anhydride or dimeracid etc. is the glycidyl ester type epoxy resin of raw material; Polyamine with tetramethyl triaminotriphenyl methane NH2 etc. is the glycidyl amine type epoxy resin of raw material; Cycloaliphatic epoxy resin; Brominated epoxy resin and composition thereof etc.They both can use separately also can use simultaneously two or more.
The active ester compound that constitutes hardening mixtures 19 is, with the reaction of above-mentioned Resins, epoxy, for example, obtain the compound of the cured article of Resins, epoxy through reaction process shown below, be to make compound and have plural the reaction and form the compound reaction of base of ester bond and available compound with this phenolic hydroxyl group with phenolic hydroxyl group.Here, form the base of ester bond as reacting, can enumerate carboxyl or halogen formyl radical (chloroformyl etc.) with phenolic hydroxyl group.In addition, the compound with following general formula (a) expression is equivalent to Resins, epoxy, R 10The organic radical of expression divalent, in addition, the compound of representing with following general formula (b) is equivalent to active ester compound, R 1And R 2With above-mentioned synonym.And, be the resultant of reaction (cured article) that the reaction by two compounds generates with the compound of following general formula (c) expression.
Following reaction process represents that the typical reaction when reacting with the compound of (b) expression of 1 mole with the compound of (a) expression of 2 moles is routine, by the chemical structure of (c) as can be known, does not produce hydroxyl by the epoxy group(ing) of reacting open loop.Like this, the ester bond in epoxy group(ing) in the Resins, epoxy and the active ester compound is 1: 1, helps reaction.
As the active ester compound that constitutes hardening mixtures 19, be preferably fragrant family active ester compound with above-mentioned general formula (1) expression.And, with regard to the R in the general formula (1) 1, be preferably any of following base especially.In addition, in following base, A and B represent halogen atom or alkyl, m respectively independently 1The integer of expression 0～5, m 2The integer of expression 0～4, m 3The integer of expression 0～3.
Figure C20038010777700241
In general formula (1), when k is 2, R 2Be preferably any of following base especially.
Figure C20038010777700242
In addition, in general formula (1), when k is 3, R 2Be preferably following base,
Figure C20038010777700243
When k is 4, R 2Be preferably any of following base.
Figure C20038010777700244
In above-mentioned formula, D, E and G represent halogen atom or alkyl respectively independently, and T represents ehter bond (O-), thioether bond (S-), sulfone key (SO 2-) or the carbonyl key is (CO-).In addition, n 1, n 2And n 3Represent 0～4 integer respectively independently, n 4And n 5Represent 0～3 integer respectively independently, n 6The integer of expression 0～2.
As the synthesis method of active ester compound, can adopt known synthesis methods such as acetic anhydride method, surperficial method, direct method.
In the acetic anhydride method; after utilizing for example superfluous acetic anhydride to carry out acetylize to compound (hereinafter referred to as " phenol based compound "), obtain the active ester compound by taking off acetic acid reaction with the compound with plural carboxyl (hereinafter referred to as " polycarboxylic acid ") with phenolic hydroxyl group.In order to carry out sufficient acetylize, the above acetic anhydride of mole such as preferred use and phenolic hydroxyl group.
In surperficial method, the organic phase that for example makes the acyl chlorides that contains polycarboxylic acid contacts with, the water that contains the phenol based compound, obtains the active ester compound.As the employed solvent of organic phase, can use the water-insoluble solvent of the acyl chlorides of dissolving polycarboxylic acid, for example be preferably toluene, hexane etc.
As the polycarboxylic acid that is used for the composite reactive ester cpds, can enumerate fatty family polycarboxylic acid and fragrant family polycarboxylic acid.When using fatty family polycarboxylic acid, can improve intermiscibility with Resins, epoxy as polycarboxylic acid; When using fragrant family polynary, not only can improve the thermotolerance of the cured article of resin combination 18, and then can improve the thermotolerance of the composite dielectric layer that is used for electron device described later.
As fatty family polycarboxylic acid, can enumerate propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, fumaric acid, toxilic acid, methylene-succinic acid, equisetic acid, tricarballylic acid, 1,2,3,4-BTCA, 4-methyl-4-tetrahydrobenzene-1,2-dicarboxylic acid, 1,2,3,4-pentamethylene tetracarboxylic acid, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-cyclohexyl alkene-1, saturated or undersaturated aliphatics polycarboxylic acid or its acid anhydrides or the acyl chlorides of 2-dicarboxylic anhydride etc.
As fragrant family polycarboxylic acid, can enumerate phenylformic acid, tolyl acid, mesitylenic acid, the benzoic acids of trimethylbenzoic acid etc., the 1-naphthoic acid, the naphthoic acid class of 2-naphthoic acid etc., phthalic acid, m-phthalic acid, the phthalic acid of terephthalic acid etc. or its acid anhydrides or acyl chlorides, trihemellitic acid, tricarboxylic acid or its acid anhydrides or the acyl chlorides of the equal tricarboxylic acid of benzene etc., the equal tetracarboxylic acid of benzene or 3,3 ', 4, the tetracarboxylic acid of 4 '-biphenyltetracarboxyacid acid etc. or its acid anhydrides, 1, the 4-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, 2, naphthalene dicarboxylic acids or its acid anhydrides of 3-naphthalene dicarboxylic acids etc., 3,3 ', 4,4 '-benzophenone tetracarboxylic acid or its acid anhydrides etc.
Phenol based compound as the raw material that is used as the active ester compound, from the thermotolerance of the cured article of resin combination 18 or prepreg described later 6 and the reactive viewpoint curing reaction, be preferably phenol based compound with 1～3 aromatic nucleus.
As aromatics, can enumerate the phenol of phenol, cresols, xylenol etc., the dihydroxy-benzene class of Resorcinol, Resorcinol, pyrocatechol, methyl hydroquinone etc. with phenolic hydroxyl group, the benzenetriol class of Phloroglucinol etc., the aphthols of naphthyl alcohol, 2-Naphthol etc., naphthalenediol class, orthoxenol, 2,2 '-dihydroxybiphenyl, 2,2 ', 4, the bisphenols of 4 '-tetramethyl-bis-phenol etc., 2,2 ', 4,4 '-tetrahydroxybenzophenone etc.
Then, the dielectric ceramic powder 3 that contained of specification tree oil/fat composition 18.
Dielectric ceramic powder 3 is preferably, in the high frequency field that more than 100MHz, (is preferably gigabit Hz band), demonstrate than the resultant of reaction of above-mentioned Resins, epoxy and active ester compound and add the big specific inductivity of the polyarylate of composition and the dielectric ceramic powder of Q value (inverse of tangent of the dielectric loss angle) arbitrarily, can use one or more.
As this dielectric ceramic powder 3, can enumerate the metal oxide powder that contains at least a metal that is selected from magnesium, silicon, aluminium, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, bismuth, lithium, samarium and tantalum.Dielectric ceramic powder 3 is these metal oxide powders, is preferably relative permittivity and is 3.7～300, the Q value is 500～100,000 metal oxide powder.
The relative permittivity of metal oxide powder is discontented with at 3.7 o'clock, can not improve the relative permittivity of the composite dielectric layer in the electron device described later, and the miniaturization that is difficult to realize electron device, light-weighted tendency are arranged.When the relative permittivity of metal oxide powder surpasses 300, Q value is discontented 500 the time, the tendency of conveyance loss reduction when electron device produces superfluous heat is in use arranged.In addition, above-mentioned dielectric ceramic powder 3 constitutes with single crystal or many crystallizations usually.
As preferred dielectric ceramic powder, can enumerate single crystal powder or many crystalline alumina powders such as sapphire, as preferred powder, can enumerate with Mg 2SiO 4[ε=7, Q=20000], Al 2O 3[ε=9.8, Q=40000], MgTiO 3[ε=17, Q=22000], ZnTiO 3[ε=26, Q=800], Zn 2TiO 4[ε=15, Q=700], TiO 2[ε=104, Q=15000], CaTiO 3[ε=170, Q=1800], SrTiO 3[ε=255, Q=700], SrZrO 3[ε=30, Q=1200], BaTi 2O 5[ε=42, Q=5700], BaTi 4O 9[ε=38, Q=9000], Ba 2Ti 9O 20[ε=39, Q=9000], Ba 2(Ti, Sn) 9O 20[ε=37, Q=5000], ZrTiO 4[ε=39, Q=7000], (Zr, Sn) TiO 4[ε=38, Q=7000], BaNd 2Ti 5O 14[ε=83, Q=2100], BaNd 2Ti 4O 12[ε=92, Q=1700], BaSm 2TiO 14[ε=74, Q=2400], Bi 2O 3-BaO-Nd 2O 3-TiO 2System [ε=88, Q=2000], PbO-BaO-Nd 2O 3-TiO 2System [ε=90, Q=5200], (Bi 2O 3, PbO)-BaO-Nd 2O 3-TiO 2System [ε=105, Q=2500], La 2Ti 2O 7[ε=44, Q=4000], Nd 2Ti 2O 7[ε=37, Q=1100], (Li, Sm) TiO 3[ε=81, Q=2050], Ba (Mg 1/3Ta 2/3) O 3[ε=25, Q=35000], Ba (Zn 1/3Ta 2/3) O 3[ε=30, Q=14000], Ba (Zn 1/3Nb 2/3) O 3[ε=41, Q=9200], Sr (Zn 1/3Nb 2/3) O 3[ε=40, Q=4000], Ba (Mg 1/3Nb 2/3) O 3[ε=12, Q=24000], Ba (Co 1/3Mg 1/3Nb 1/3) O 3[ε=32, Q=11500], Ba (Co 1/3Mg 1/3Ta 1/3) O 3[ε=24, Q=38500], BaO-CaO-Nd 2O 3-TiO 2[ε=90, Q=2200], BaO-SrO-Nd 2O 3-TiO 2[ε=90, Q=1700], BaO-Nd 2O 3, MgO-TiO 2, MgO-SiO 2[ε=6.1, Q=5000], ZnO-TiO 2[ε=26, Q=840], BaTiO 3[ε=1500, Q=100], (Ba, Pb) TiO 3[ε=6000], Ba (Ti, Zr) O 3[ε=9000] or (Ba, Sr) TiO 3The dielectric ceramic powder that consists of major ingredient of [ε=7000], but be not limited thereto.In addition, above-mentioned ε value and Q value are the values of utilizing the dielectric resonator method to measure at gigabit Hz band.
From Q value height and the ε value reason bigger than cured article described later 2, as dielectric ceramic powder 3 especially preferably with TiO 2, CaTiO 3, SrTiO 3, BaO-Nd 2O 3-TiO 2System, BaO-CaO-Nd 2O 3-TiO 2System, BaO-SrO-Nd 2O 3-TiO 2System, BaO-Sm 2O 3-TiO 2, BaTi 4O 9, Ba 2Ti 9O 20, Ba 2(Ti, Sn) 9O 20System, MgO-TiO 2System, ZnO-TiO 2System, MgO-SiO 2System, Al 2O 3The dielectric ceramic powder that consists of major ingredient.With above-mentioned composition is that the dielectric ceramic powder of major ingredient both can use separately also and can use simultaneously more than two kinds.
The median size of dielectric ceramic powder 3 is preferably 0.01～100 μ m, more preferably 0.2～20 μ m.When median size was discontented with 0.01 μ m, resin combination 18 or prepreg described later 6 produced the situation that viscosity increases or flowability reduces sometimes, and the tendency that is difficult to as the laminar cured resin of demonstration cementability is arranged.On the other hand, when median size surpasses 100 μ m, the possibility that produces problems such as dielectric ceramic powder 3 sedimentations is arranged when making resin combination 18 or prepreg 6 described later.
In addition, resin combination 18 also preferably contains polyarylate.In other words, be preferably polyarylate (aromatic polyester) is added in the hardening mixtures 19 that resin combination 18 contained.
Above-mentioned polyarylate more preferably as described above by-material that unit repeatedly that X-Y-constitutes constitutes, is preferably the low material of specific inductivity and tangent of the dielectric loss angle especially.Polyarylate can obtain by interfacial polymerization or solution polymerization process, but owing to can obtain the low polyarylate of purity height and tangent of the dielectric loss angle at short notice, so preferably obtain by interfacial polymerization.
In interfacial polymerization, preferably make be selected from phthalic acid, m-phthalic acid, terephthalic acid more than one dicarboxylic acid halogenide and organic solvent solution and contact, produce surperficial polycondensation and obtain polyarylate with the phenolate ion of the binary oxybenzene compound of following general formula (3a) expression.In addition, the R in the general formula (3a) 11, R 12, Z, p and q and above-mentioned synonym.In addition, in above-mentioned reaction, the halid ratio of the terephthalic acid in the di-carboxylic acid halogenide is necessary for 40 moles below the %.
Figure C20038010777700281
Above-mentioned reaction more preferably makes di-carboxylic acid halogenide be dissolved in the organic solvents such as toluene or methylene dichloride, above-mentioned binary phenol is dissolved in the alkali-metal aqueous solution, by making this two kinds of solution contacts, make dicarboxylic acid halogenide and binary phenol carry out interfacial polymerization.
At this moment, preferably alternate moving catalyst is added in the organic solvent to promote reaction.As alternate moving catalyst, can enumerate the ammonium salt of methyl trioctylphosphine ammonium chloride, benzyltriethylammoinium chloride etc., the microcosmic salt of tetrabutyl phosphonium bromide phosphorus etc.
Preferably remove the oxygen in the employed water when carrying out interfacial polymerization in advance.Can suppress painted to the arylide that obtains by removing deoxidation.
In addition, also can add tensio-active agent in the reaction system.The polycondensation mode both can be that intermittent type also can be a continous way, and temperature of reaction is preferably the temperature of-5～100 ℃ the boiling point that is no more than organic solvent, is preferably 0～80 ℃ especially.
Then, illustrate with respect to must composition Resins, epoxy, the addition of any interpolation composition polyarylate of the solidified nature cured article 19 that contained of active ester compound and dielectric ceramic powder 3 and resin combination 18.
The addition of active ester compound is preferably the ester equivalent becomes the amount of 0.3～4.0 times of equivalent of the epoxy equivalent (weight) of Resins, epoxy (0.8～3.0 times of equivalent more preferably).When the discontented 0.3 times of equivalent of the ester equivalent of active ester compound, the curing of the Resins, epoxy inadequate tendency that becomes is arranged; When surpassing 4.0 times of equivalents, the specific inductivity of the resultant of reaction of Resins, epoxy and active ester compound has insufficient low tendency that becomes.
When adding polyarylate, the addition of polyarylate is preferably 5～70 weight parts with respect to total 100 weight parts of Resins, epoxy and active ester compound.When the addition of polyarylate is discontented with 5 weight parts, can fully not uprise although added the viscosity of polyarylate resin combination 18, on coating, have problems sometimes.When the addition of polyarylate surpasses 70 weight parts, mobile excessively reduction of resin combination 18 and make cementability etc. insufficient sometimes.
The addition of dielectric ceramic powder 3 with respect to total 100 parts by volume of Resins, epoxy and active ester compound (when containing polyarylate, Resins, epoxy, active ester compound and polyarylate add up to 100 parts by volume) be preferably 5～185 parts by volume, more preferably 10～150 parts by volume.
In addition, in the hardening mixtures 19 that resin combination 18 is contained, can add at least a additive that is selected from coupler, curing catalyst, fire retardant, flexible imparting agent and organic solvent.
By coupler being added in the hardening mixtures 19 that resin combination 18 contained, can improve the binding property of dielectric ceramic powder 3 and, Resins, epoxy or active ester compound or these resultant of reaction, can suppress suction.
As the coupler that is fit to, can enumerate chlorosilane system, alkoxyl silicone methane series, organic functional silane and be, silazane is silane coupling agent, titanate is a coupler, aluminium is coupler etc.Coupler both can use separately also and can use simultaneously more than two kinds according to needed characteristic.When resin combination of the present invention is applicable in printed base plate, electron device, the element etc., because the thermotolerance of the stream (reflow) of will negating etc., so preferably use organic functional silane system, alkoxyl silicone methane series coupler.
At least a portion preferred combination of coupler or be adsorbed on the surface of dielectric ceramic powder 3.That is, coupler preferably is present in the interface of dielectric ceramic powder 3 and, Resins, epoxy or active ester compound or their resultant of reaction (or hardening mixtures 19 or its cured article).By making coupler be present in the interface, can improve the wettability and the cementability at interface, in the strength of materials of the cured article that can improve resin combination 18 or prepreg described later 6, also can suppress suction etc.
In conjunction with or be adsorbed on the amount of the coupler on the dielectric ceramic powder 3, can be according to the suitably decisions such as kind of the coupler of the particle diameter of employed dielectric ceramic powder 3 and shape, interpolation, but be preferably 0.1～5 weight part with respect to dielectric ceramic powder 100 weight parts.In addition, as make coupler in conjunction with or be adsorbed on method (surface treatment method) on the dielectric ceramic powder 3, can enumerate drying process, damp process, gunite, whole hybrid system etc.
By curing catalyst being added in the hardening mixtures 19 that resin combination 18 contained, can promote the reaction of Resins, epoxy and active ester compound.
As the curing catalyst that can use, the common curing catalyst of Resins, epoxy can be used, imidazolium compoundss such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2-undecyl imidazole can be enumerated particularly; Organic phosphine compound such as triphenylphosphine, tributylphosphine; Organophosphorous compounds such as trimethylammonium phosphide, triethyl phosphatization thing; Microcosmic salts such as Ethyltriphenylphosphonium brimide, tetraphenylphosphonium tetraphenyl borate salts; Trialkylamine such as triethylamine, Tributylamine; 1,8-diazacyclo (5.4.0)-undecylene-7 amines such as (DBU); DBU and terephthalic acid or 2, the salt of 6-naphthalene monocarboxylic acid; Quaternary ammonium salts such as etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, four hexyl brometo de amonios, benzyl trimethyl ammonium chloride; 3-phenyl-1,1-dimethyl urea, 3-(4-aminomethyl phenyl)-1,1-dimethyl urea, 3-(4-chloro-phenyl-)-1,1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-urea compounds such as dimethyl urea; Bases such as sodium hydroxide, potassium hydroxide; Crown ether salt such as (benzene) phenol potassium or Potassium ethanoate etc.They can use separately or use as two or more mixtures.
The addition of curing catalyst is preferably 0.005～10.0 weight part with respect to total 100 weight parts of Resins, epoxy and active ester compound.When the addition of curing catalyst was discontented with 0.005 weight part, curing reaction was slow; When surpassing 10.0 weight parts, the self-polymerization of the storage stability of resin combination 18 reduction sometimes, preferential initial ring epoxy resins.
When resin combination 18 or prepreg described later 6 or its cured article are applicable to the purposes that requires flame retardant resistance, preferably fire retardant is added in the hardening mixtures 19.The kind of fire retardant roughly is divided into the reaction flame retardant and adds flame retardant.As the reaction flame retardant, can enumerate the fire retardant that is suitable for as host: brominated bisphenol type Resins, epoxy, bromination phenolic resin, bromination phenol-phenol aldehyde type epoxy resin; The fire retardant that is suitable for as solidifying agent: hexachloroendomethylene-tetrahvdrophthalic anhydride, tetrabromophthalic anhydride.On the other hand, as adding flame retardant, can enumerate the fire retardant of halogen system, phosphoric acid system, nitrogen system, metal-salt system, hydroxide metal system, inorganic system etc.Above-mentioned fire retardant both can use a kind of also can be used in combination two or more.
The addition of fire retardant is preferably 5～50 weight parts with respect to total 100 weight parts of Resins, epoxy and active ester compound (when containing polyarylate, Resins, epoxy and active ester compound and polyarylate add up to 100 weight parts).But, because polyarylate or dielectric ceramic powder 3 have the effect of flame retardant resistance, thus when they addition for a long time, can suitably reduce the addition of fire retardant according to this amount.In addition, the addition of fire retardant also can be according to suitably change of the requirement of the flame retardant resistance of UL94 (for example the grade of the 5V of UL94, V-0, V-1, V-2, HB etc. or be used to obtains the thickness of material of the identification of flame retardant resistance).
By flexible imparting agent being added in the hardening mixtures 19 that resin combination 18 contained, can improve the toughness of the cured article of hard and crisp resin combination 18.
As flexible imparting agent, can enumerate cycloaliphatic epoxy resin, epoxidized polybutadiene, polyhutadiene, hydrogenation polyhutadiene, rubber modified epoxy resin, styrene series thermoplastic elastomer of having been carried out modification etc. by dipolymer acid etc.The addition of flexible imparting agent is preferably 5～10 weight parts with respect to total 100 weight parts of Resins, epoxy and active ester compound.
By organic solvent being added in the hardening mixtures 19 that resin combination 18 contained to the viscosity or the flowability of adjustable tree oil/fat composition 18 or prepreg described later 6.As organic solvent, can enumerate tetrahydrofuran (THF), toluene, dimethylbenzene, butanone, pimelinketone, N,N-DIMETHYLACETAMIDE, dioxolane.The addition of organic solvent can suitably determine according to desired viscosity.
Then, cured resin of the present invention, laminar cured resin and layered product are described.
Figure 1B is the sectional view of first embodiment of expression laminar cured resin of the present invention.Laminar cured resin 1 shown in Figure 1B possesses, and makes hardening mixtures 19 solidified cured articles 2 Hes that are made of Resins, epoxy and active ester compound, dielectric ceramic powder 3, and dielectric ceramic powder 3 is dispersed in the cured article 2.
Fig. 1 C is the sectional view of first embodiment of expression layered product of the present invention.Layered product 5 shown in Fig. 1 C is made of above-mentioned laminar cured resin 1 and tinsel 4, and tinsel 4 is bonded on the one side of laminar cured resin 1.Here, as tinsel 4, can use the tinsel that constitutes by copper, nickel, chromium, gold and silver, tin, nickel-chromium etc., but, be preferably Copper Foil from cheap price, the viewpoint that obtains easily.In addition, the thickness of tinsel 4 is preferably 1～70 μ m, and the making method of tinsel 4 can be any mode of electrolysis, calendering, spraying plating, evaporation, can suitably select according to desired thickness or characteristic.
Resin combination of the present invention roughly is divided into, the curing reaction that makes Resins, epoxy and active ester compound partly finish and the cured resin that forms and, the curing reaction of Resins, epoxy and active ester compound is finished and the cured resin of formation.Here, so-called " curing reaction ends " be meant, not have to find to be accompanied by the absorption of heat of reaction or the state of emitting when using differential scanning calorimetry (DSC), such state by for example under solidification value the abundant resin combination that heats reach.On the other hand, so-called " curing reaction partly finishes " is meant, curing reaction has carried out a part, can observe the absorption of the heat that is accompanied by reaction or the state of emitting when using DSC, and such state is by for example reaching with solidification value short period of time heating resin combination.
The curing reaction that makes Resins, epoxy and active ester compound partly finishes and the cured resin that forms, for example, is configured as laminarly, can be used as laminar cured resin (semicure adhesive sheet).In addition, also can be used as prepreg, at this moment, under the heating and pressurizing condition, can make the shaping thing by laminated polylith prepreg is cured.Above-mentioned cured resin can also be bonded in tinsel on the one or both sides of laminar cured resin as layered product.Such layered product is by being heating and curing separately, can be used as the single layer substrate of the individual layer veneer sheet that printing distributing board uses, and by overlapping polylith and be heating and curing, also can be used as the multilager base plate of the multilayer layer pressing plate that printing distributing board uses.
On the other hand, the curing reaction of Resins, epoxy and active ester compound is finished and the cured resin of formation, for example, the laminar cured resin (thin slice cured article) that can be used as high-k, low-dielectric loss angle tangent, tinsel is bonded on the plate object on the one or both sides of laminar cured resin, the veneer sheet that can directly use as printing distributing board.
Above-mentioned any situation all can be used tinsel 4.
Laminar cured resin can be by mixing and be slurried into mashed prod in organic solvent (tetrahydrofuran (THF), toluene, dimethylbenzene, butanone, pimelinketone, N,N-DIMETHYLACETAMIDE, dioxolane etc.) with resin combination 18, is coated with this mashed prod and carries out drying and make.In addition, under solidification value, can access above-mentioned thin slice cured article, then can access cementability semicure thin slice at low temperature or process short period of time through adequate time.In addition, the mixing known devices such as ball mill or stirrer that use carry out.
As resin combination 18 coating processes that will become pulpous state, can adopt known method such as mode based on scraper control, spray regime, curtain formula coating method, rotary coating mode, screen printing mode, can supply with form (web-like, laminar etc.) according to needed thickness, precision, material and suitably select.The thickness of resin combination 18 of coating is 5～200 μ m after the preferred drying, is preferably the thickness more than 2 times of maximum particle diameter of the dielectric ceramic powder 3 of interpolation.
When 2 times of the maximum particle diameter of the discontented dielectric ceramic powder 3 of the thickness of resin combination 18, or during the discontented 5 μ m of dried thickness, have problems aspect the insulativity of the coating when coating, smoothness, cured article sometimes.On the other hand, when dried thickness surpasses 200 μ m, be difficult to remove remaining organic solvent.Therefore, when obtaining dry back thickness and surpassing the laminar cured resin of 200 μ m, can adopt on the resin of thin and thick the method for coating repeatedly.
Drying conditions can be according to the suitably decisions such as organic solvent of the composition of resin combination 18, thickness, use, but be preferably 50～150 ℃ dry 1～60 minute down.In addition, can carry out temperature is divided into the stage drying of several stages as required.In addition, coating can be carried out on based on film above-mentioned tinsel, that be made of PET, PI, PPS, LCP.In addition, when obtaining laminar cured resin, being preferably under high-temperature vacuum and pushing, is 1.5～6.0MPa as 150～250 ℃ of this condition optimizations, 0.5～20 hour, pressure.And, as required also can step curing or reduce pressure below the 30torr.
Then, prepreg of the present invention, laminar cured resin and layered product are described preferred embodiment.In addition, integrant identical with above-mentioned embodiment or that be equal to is used prosign, omit repeat specification.
Fig. 1 D is the sectional view of an embodiment of expression prepreg of the present invention.Prepreg 6 shown in Fig. 1 D comprises: to Resins, epoxy and, the compound that makes the compound with plural carboxyl and have a phenolic hydroxyl group reacts and hardening mixtures 19 that the active ester compound (being designated hereinafter simply as " active ester compound ") that obtains constitutes carries out the semicure thing 7 of semicure; Dielectric ceramic powder 3; With reinforcing fiber 8, dielectric ceramic powder 3 is dispersed in the semicure thing 7, reinforcing fiber 8 with the state configuration of reinforcing fiber fabric in semicure thing 7.Hardening mixtures 19 is used for constituting above-mentioned resin combination 18.
That is the structure of the prepreg shown in Fig. 1 D 6 resin layer that constitutes by semicure thing 7 that has and possess the reinforcing fiber fabric, on the two sides of this reinforcing fiber fabric, form.Here, the thickness of reinforcing fiber fabric is preferably 20～300 μ m, more preferably 20～200 μ m.When the thickness of reinforcing fiber fabric is discontented with 20 μ m, the tendency that has problems is arranged on intensity; When surpassing 300 μ m, there is the resin adhesion amount to reduce, be difficult to show the tendency of the feature of rerum natura.On the other hand, the thickness of the resin layer that is made of semicure thing 7 is preferably 5～100 μ m, more preferably 5～50 μ m.When the discontented 5 μ m of the thickness of resin layer, there is the ratio of resin to reduce, is difficult to show the tendency of rerum natura; When surpassing 100 μ m, the tendency that is difficult to adhere to is equably arranged.In addition, the reinforcing fiber fabric of Fig. 1 D is the fabric that the mode that multi beam reinforcing fiber 8 bundle reinforcing fiber bundle 9 is together reported to the leadship after accomplishing a task mutually as warp thread and weft yarn, with them is carried out weaving.In addition, semicure thing 7 also is present between the reinforcing fiber 8 of reinforcing fiber fabric.
In prepreg of the present invention, the hardening mixtures that is made of Resins, epoxy and active ester compound is the state of semicure.Here so-called " semicure " is meant, a part is only carried out in the reaction of Resins, epoxy and active ester compound, when using differential scanning calorimetry (DSC), can observe the absorption of the heat that is accompanied by above-mentioned reaction or the state of emitting, such state can pass through, for example, reach at heating prepreg of following short period of time of solidification value.On the other hand, can above-mentioned reaction be finished, at this moment, not observe the absorption of the heat that is accompanied by reaction or emit with DSC by prepreg is cured.
Then, the reinforcing fiber 8 that is configured in the prepreg 6 is described.Reinforcing fiber 8 is preferably at least a reinforcing fiber that is selected from E glass fibre, D glass fibre, NE glass fibre, H glass fibre, T glass fibre and tynex, wherein, be preferably NE glass fibre, the H glass fibre of high-k, the cost equilibrated E glass fibre of low-dielectric loss angle tangent.Reinforcing fiber 8 can be with the state configuration of filamentary state of reinforcing fiber or reinforcing fiber bundle in prepreg, but the state configuration that is preferably the marshalling thing (for example reinforcing fiber fabric, reinforcing fiber are compiled thing etc.) with the reinforcing fiber bundle is in prepreg 6.
When using reinforcing fiber fabric (reinforcing fiber cloth), its preferred thickness as mentioned above.The thickness of particularly preferred reinforcing fiber fabric is 20 μ m, 30 μ m, 50 μ m, 100 μ m or 200 μ m.The reinforcing fiber fabric both can be to have implemented to open the fabric that fibre, obturation etc. are handled as required, also can be to have carried out the surface-treated fabric for the surface treatment agent that improves with the binding property of hardening mixtures with coupler etc.
Then, illustrate with respect to must composition Resins, epoxy, the addition of any interpolation composition polyarylate of the solidified nature cured article 19 that contained of active ester compound and dielectric ceramic powder 3 and resin combination 18.
The addition of active ester compound is preferably the ester equivalent becomes the amount of 0.3～4.0 times of equivalent of the epoxy equivalent (weight) of Resins, epoxy (0.8～3.0 times of equivalent more preferably).When the discontented 0.3 times of equivalent of the ester equivalent of active ester compound, the curing of the Resins, epoxy inadequate tendency that becomes is arranged; When surpassing 4.0 times of equivalents, the specific inductivity of the resultant of reaction of Resins, epoxy and active ester compound has insufficient low tendency that becomes.
When adding polyarylate, the addition of polyarylate is preferably 5～70 weight parts with respect to total 100 weight parts of Resins, epoxy and active ester compound.When the addition of polyarylate was discontented with 5 weight parts, although added polyarylate, the viscosity of prepreg raw material (mashed prod described later) can fully not uprise yet, and goes wrong on coating sometimes.When the addition of polyarylate surpassed 70 weight parts, the mobile excessively reduction and the cementability etc. of prepreg raw material (mashed prod described later) were insufficient sometimes.
The addition of dielectric ceramic powder 3 is preferably 5～100 parts by volume with respect to total 100 parts by volume of Resins, epoxy and active ester compound (when containing polyarylate, Resins, epoxy, active ester compound and polyarylate add up to 100 parts by volume).
Then, laminar cured resin of the present invention and layered product are described.Fig. 1 E is the sectional view of second embodiment of expression laminar cured resin of the present invention.Laminar cured resin 15 shown in Fig. 1 E possesses makes the hardening mixtures 19 that is made of Resins, epoxy and active ester compound carry out solidified cured article 2, dielectric ceramic powder 3, reinforcing fiber 8, dielectric ceramic powder 3 is dispersed in the cured article 2, reinforcing fiber 8 with the state configuration of reinforcing fiber fabric in cured article 16.In addition, above-mentioned reinforcing fiber fabric be with multi beam reinforcing fiber 8 bundle reinforcing fiber bundle 9 together as warp thread and weft yarn, the fabric that the mode of reporting to the leadship after accomplishing a task mutually with them is carried out weaving.In addition, cured article 2 also is present between the reinforcing fiber 8 of reinforcing fiber fabric.
Fig. 1 F is the sectional view of second embodiment of expression layered product of the present invention.Layered product 17 shown in Fig. 1 F is the layered products that are made of above-mentioned laminar cured resin 15 and tinsel 4, and tinsel 4 is bonded on the one side of laminar cured resin 15.
The preferred manufacture method of prepreg of the present invention, laminar cured resin and layered product then, is described.
When making prepreg 6, laminar cured resin 15 and layered product 17, the mashed prod of making like that below preferred the use.Promptly, preferably use in the necessary composition that constitutes by Resins, epoxy, active ester compound and dielectric ceramic powder 3, add as required and add composition polyarylate, coupler, curing catalyst, fire retardant and flexible imparting agent, this resin combination and organic solvent is mixing, that pulp obtains mashed prod arbitrarily.Here employed organic solvent is the volatile solvent of tetrahydrofuran (THF), toluene, dimethylbenzene, butanone, pimelinketone, N,N-DIMETHYLACETAMIDE, dioxolane etc., can adjust the viscosity of mashed prod by changing addition.In addition, can use known devices such as ball mill or stirrer to carry out mixing.
As the representational manufacture method of prepreg of the present invention, laminar cured resin and layered product, can enumerate two kinds of following methods.
Method 1: by pickling process the mashed prod of pulp is coated on the reinforcing fiber fabric, and carried out drying and obtain prepreg.At this moment, the thickness of coating is preferably the thickness with respect to reinforcing fiber fabric one side 5～50 μ m.When being discontented with this thickness, be difficult to guarantee the flowability of prepreg; When surpassing this thickness, be easy to generate the sagging etc. of mashed prod, it is big that the deviation of thickness or adhesion weight etc. becomes.Drying conditions can suitably determine according to the solvent that uses or the thickness of coating, for example is decided to be 1～60 minute condition of drying under 50～150 ℃.In addition, as required, also can carry out with temperature be divided into several stages stage drying.Laminar cured resin 15 is preferably the prepreg 6 that obtains like this by the high-temperature vacuum press forming and makes.The high-temperature vacuum press forming be preferably under 150～250 ℃ the temperature, 0.5～20 hour, with the pressure of 1.5～6.0MPa, under the vacuum tightness below the 30torr, carry out.When making laminar cured resin 15, also can carry out step curing as required.When layered product 17 is high-temperature vacuum press formings when obtaining laminar cured resin 15, tinsel 4 is laminated to the surface of prepreg 6 and/or the inside and gets final product all carrying out heating and pressurizing.
Method 2: in method 2, at first, utilize known coating process to be coated on the above-mentioned mashed prod of pulp on the tinsel or the film of PET, PI, PPS, LCP etc. on.As coating process, for example can enumerate mode based on scraper control, spray regime, curtain formula coating method, rotary coating mode, screen printing mode etc., can supply with form (web-like, laminar etc.) according to needed thickness, precision, material and select suitable mode.After the preferred drying of thickness of coating is 5～100 μ m, more preferably the thickness more than 2 of the maximum particle diameter of dielectric ceramic powder 3 times.When 2 times of the maximum particle diameter of discontented 5 μ m of thickness or discontented dielectric ceramic powder 3, have problems on the insulativity of the coating when being coated with sometimes, smoothness, cured article; When thickness surpasses 100 μ m, be difficult to remove remaining organic solvent.Therefore, when carrying out the coating that thickness surpasses 100 μ m, should adopt behind the resin of making thin and thick thereon the method for coating repeatedly.
Above-mentioned drying conditions can for example can carry out drying under 1～60 minute the condition of drying down at 50～150 ℃ according to the suitably decisions such as organic solvent of material composition, thickness, use.In addition, can carry out temperature is divided into the stage drying of several stages as required.Clamp the reinforcing fiber fabric with the coating thing that obtains like this, for example, can remove the organic solvent that contains and obtain prepreg by carrying out vacuum press.In addition, with the above-mentioned the same thing that obtains being coated with, after clamping the reinforcing fiber fabric with the coating thing that obtains, for example, by 150～250 ℃ temperature, 0.5～20 hour, with the pressure of 1.5～6.0MPa, under the vacuum tightness below the 30torr, carry out the high-temperature vacuum press forming, can obtain laminar cured resin 15.Here, when being coated on mashed prod on the tinsel, obtain layered product 17.In addition, worry in the reinforcing fiber fabric soak stagnant, fillibility the time, can in advance the reinforcing fiber fabric be soaked and stagnate in the above-mentioned mashed prod of dilution solid ingredient concentration, and make it dry.
Then, electron device of the present invention and multilager base plate are described.
Electron device of the present invention possesses: contain organic insulation and at least one composite dielectric layer with dielectric ceramic powder of the specific inductivity bigger than organic insulation; Be arranged on the composite dielectric layer, constitute at least one conductive element portion of capacitor element or inductor element; Above-mentioned organic insulation is to make Resins, epoxy and active ester compound be cured reaction and the material of the cured resin that forms, and the compound that this active ester compound makes the compound with plural carboxyl and has a phenolic hydroxyl group reacts and forms.
This electron device is because dielectric ceramic powder has the relative permittivity bigger than the organic insulation that contains cured resin, organic insulation has low-dielectric loss angle tangent, even so in the high frequency field of gigabit Hz, composite dielectric layer also demonstrates high-k and low-dielectric loss angle tangent.Therefore, reduced the conveyance loss of electron device, made the miniaturization of electron device, lightweight become possibility.In addition, even under the high temperature more than 100 ℃, use for a long time, also can fully be reduced in relative permittivity in the above high frequency field of 100MHz through the time change.And this electron device so the operability of electron device is improved, can fully prevent the damaged and even distortion of electron device etc. because flexural strength becomes big.In addition, utilize electron device of the present invention, the dielectric characteristics in the time of also can improving the high temperature use.In other words, utilize electron device of the present invention, can fully improve its characteristic.
At first, above-mentioned composite dielectric layer is described.In addition, the integrant identical or equal with above-mentioned embodiment used prosign, omits repeat specification.
Composite dielectric layer comprises the organic insulation that contains cured resin, and cured resin is to make Resins, epoxy and active ester compound be cured reaction and the material of formation.Can be in other words, composite dielectric layer is by for example constituting with above-mentioned laminar cured resin 1 or laminar cured resin 15.Laminar cured resin 1 or laminar cured resin 15, as mentioned above, possess cured article 2 and dielectric ceramic powder 3 that hardening mixtures 19 that Resins, epoxy and active ester compound are constituted is cured, dielectric ceramic powder 3 is dispersed in the cured article 2.That is, the cured resin that above-mentioned organic insulation contained is made of cured article 2.
Addition with respect to the above-mentioned active ester compound of above-mentioned Resins, epoxy is preferably, and the ester equivalent becomes 0.3～4.0 times of normal amount of epoxy equivalent (weight) with respect to Resins, epoxy, more preferably becomes 0.8～3.0 times of normal amount.When the discontented 0.3 times of equivalent of ester equivalent, Resins, epoxy be solidified with inadequate tendency; When surpassing 4.0 times of equivalents, the tendency that is difficult to obtain the fully low cured resin of specific inductivity is arranged.
Cured article 2 also can be to make Resins, epoxy and active ester compound be cured reaction and the material of formation in the presence of additive.
Additive is at least a additive that is selected from curing catalyst, surface treatment agent, fire retardant and flexible imparting agent.
Above-mentioned curing catalyst as such curing catalyst, mainly can use employed common curing catalyst when cured epoxy resin so long as can promote Resins, epoxy and the material of the curing reaction of active ester compound just has no particular limits.
That is,, for example can enumerate the imidazolium compounds of glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2-undecyl imidazole etc. as this curing catalyst; Organic phosphine compound such as triphenylphosphine, tributylphosphine; Organophosphorous compounds such as trimethylammonium phosphide, triethyl phosphatization thing; Microcosmic salts such as Ethyltriphenylphosphonium brimide, tetraphenylphosphonium tetraphenyl borate salts; Trialkylamine such as triethylamine, Tributylamine; 1,8-diazacyclo (5.4.0)-undecylene-7 amine and DBU and terephthalic acid or 2 such as (being designated hereinafter simply as DBU), the salt of 6-naphthalene monocarboxylic acid; Quaternary ammonium salts such as etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, four hexyl brometo de amonios, benzyl trimethyl ammonium chloride; 3-phenyl-1,1-dimethyl urea, 3-(4-aminomethyl phenyl)-1,1-dimethyl urea, 3-(4-chloro-phenyl-)-1,1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-urea compounds such as dimethyl urea; Bases such as sodium hydroxide, potassium hydroxide; Crown ether salt such as (benzene) phenol potassium or Potassium ethanoate etc.They can use separately or use as two or more mixtures.
The addition of curing catalyst is preferably 0.005～10.0 weight part with respect to total 100 weight parts of Resins, epoxy and active ester compound.When being discontented with 0.005 weight part, curing reaction has slack-off tendency; When surpassing 10.0, there is storage stability to reduce and preferentially carry out the tendency of the self-polymerization of Resins, epoxy.
Above-mentioned fire retardant adds according to needed flame retardant resistance.Fire retardant roughly is divided into the reaction flame retardant and adds flame retardant two kinds.As the host of reaction flame retardant, can enumerate brominated bisphenol type Resins, epoxy, bromination phenolic resin, bromination phenol-phenol aldehyde type epoxy resin; As solidifying agent, can enumerate hexachloroendomethylene-tetrahvdrophthalic anhydride, tetrabromophthalic anhydride etc.In addition, as adding flame retardant, can enumerate halogenated flame retardants such as Firemaster 836, brominated epoxy resin; Phosphoric acid flame retardants such as phosphoric ester amides; The nitrogen flame retardant; The metal-salt flame retardant; Hydroxide metal flame retardant; Inorganic flame retardant such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminum hydride etc.Above-mentioned fire retardant both can use a kind of also can mix use two or more.
In addition, the addition of fire retardant is preferably in the scope of 5～50 weight parts with respect to resin combination 100 weight parts and adds.Polyarylate, dielectric ceramic powder self have flame retardant resistance or, be the material that shows flame retardant effect, when the addition of polyarylate, dielectric ceramic powder for a long time, the addition of fire retardant can lack; When the addition of polyarylate, dielectric ceramic powder after a little while, can increase the addition of fire retardant.In addition, addition can be according to needed flame retardant resistance (for example the 5V of UL94, V-0, V-1, V-2, HB grade and wanting obtain thickness) decision.
Above-mentioned flexible imparting agent can be given composite dielectric layer toughness, in addition, and when composite dielectric layer is when containing the prepreg of reinforcing fiber, to improve its operability.
As flexible imparting agent, for example can enumerate cycloaliphatic epoxy resin through dimer acid modified grade, epoxidized polybutadiene, polyhutadiene, hydrogenation polyhutadiene, rubber modified epoxy resin, styrene series thermoplastic elastomer etc., but flexible imparting agent is not limited thereto.
Above-mentioned surface treatment agent is can improve the binding property of dielectric ceramic powder and organic insulation and reduce absorptive material.
As this surface treatment agent, for example can enumerate chlorosilane and be coupler, alkoxyl silicone methane series coupler, organic functional silane is that coupler, silazane are silane coupling agent, and titanate is a coupler, and aluminium is coupler etc.The surface treatment agent that uses both can use separately also can mix according to needed characteristic and use more than two kinds.
In electron device, because the thermotolerance of the stream of will negating etc. is coupler, alkoxyl silicone methane series coupler so surface treatment agent is preferably organic functional silane.
The addition of surface treatment agent can suitably be selected in the scope of 0.1～5 weight part with respect to dielectric ceramic powder 100 weight parts.The selection of addition is according to the kind decision of the surface treatment agent of the particle diameter of employed dielectric ceramic powder, shape, interpolation.As surface treatment method, for example can enumerate drying process, damp process, gunite, whole hybrid system etc., can select as required.
In addition, organic insulation also preferably contains polyarylate except that above-mentioned cured article 2.At this moment, the flexible and bendability under B scalariform attitude rises, and operability is good.
Above-mentioned polyarylate is the material (X of this structure unit and the Y of structure unit of a plurality of existence both can be the same or different separately) that the repeating unit by being expressed as of constituting of X of structure unit and the Y of structure unit-X-Y-repeatedly forms repeatedly; the X of said structure unit is preferably the phthalyl with following formula (2) expression; isophthaloyl or paraphenylene terephthalamide are (with respect to this phthalyl; isophthaloyl and paraphenylene terephthalamide's total mole number; paraphenylene terephthalamide's mole number is discontented with 40 moles of %)
Figure C20038010777700401
The Y of said structure unit is preferably the divalent radical with following general formula (3) expression.
Figure C20038010777700402
(in the formula, R 11And R 12Alkyl, alkoxyl group or the halogen atom of representing carbonatoms 1～4 respectively independently, Z are represented singly-bound, ehter bond, thioether bond, sulfone key or carbonyl key, and p and q represent 0～4 integer respectively independently.But, in above-mentioned polyarylate, when there being a plurality of R 11, R 12And during Z, R 11, R 12And Z both can be the same or different separately.)
Polyarylate is compared with the polyarylate with said structure structure in addition by becoming said structure, can give prepreg toughness and operability and be improved.
In above-mentioned general formula (3), above-mentioned R 11And above-mentioned R 12Be preferably methyl, Z is preferably singly-bound.
At this moment, prepreg toughness can be given especially and operability is improved.
As the synthesis method of above-mentioned polyarylate, can preferably use interfacial polymerization, solution polymerization process, but owing to can obtain the low polyarylate of purity height and tangent of the dielectric loss angle at short notice, so preferably obtain by interfacial polymerization.
In interfacial polymerization, preferably make be selected from phthalic acid, m-phthalic acid, terephthalic acid more than one dicarboxylic acid halogenide and organic solvent solution and contact, produce surperficial polycondensation and obtain polyarylate with the phenolate ion of the binary oxybenzene compound of following general formula (3a) expression.In addition, the R in the general formula (3a) 11, R 12, Z, p and q and above-mentioned synonym.In addition, in above-mentioned reaction, the halid ratio of the terephthalic acid in the di-carboxylic acid halogenide is necessary for 40 moles below the %.
Figure C20038010777700403
Above-mentioned reaction more preferably makes di-carboxylic acid halogenide be dissolved in the organic solvents such as toluene or methylene dichloride, above-mentioned binary phenol is dissolved in the alkali-metal aqueous solution, by making this two kinds of solution contacts, make dicarboxylic acid halogenide and binary phenol carry out interfacial polymerization.
At this moment, preferably alternate moving catalyst is added in the organic solvent to promote reaction.As alternate moving catalyst, can enumerate the ammonium salt of methyl trioctylphosphine ammonium chloride, benzyltriethylammoinium chloride etc., the microcosmic salt of tetrabutyl phosphonium bromide phosphorus etc.
Preferably remove the oxygen in the employed water when carrying out interfacial polymerization in advance.Can suppress painted to the arylide that obtains by removing deoxidation.
In addition, also can add tensio-active agent in the reaction system.The polycondensation mode both can be that intermittent type also can be a continous way, and temperature of reaction is preferably the temperature of-5～100 ℃ the boiling point that is no more than organic solvent, is preferably 0～80 ℃ especially.
In addition, when organic insulating material contained above-mentioned arylide, the addition of polyarylate can be 5～70 weight parts with respect to total amount 100 weight parts of above-mentioned Resins, epoxy and active ester compound.When the addition of polyarylate is discontented with 5 weight parts, the tendency of the manufacturing efficient reduction of electron device is arranged; When surpassing 70% weight part, might the binding property of the conductive metal of composite dielectric layer be reduced, during through long-time the use, conductive metal strips down from composite dielectric layer, the performance change of electron device.
Composite dielectric layer used in the present invention contains the dielectric ceramic powder that is distributed in the above-mentioned organic insulation.As this dielectric ceramic powder, use have in the high frequency field more than 100MHz than big relative permittivity of organic insulation and Q value, for example dielectric ceramic powder 3.
The addition of dielectric ceramic powder is preferably the scope of 5～185 parts by volume with respect to organic insulation 100 parts by volume, in this scope, can select suitable amount according to needed specific inductivity and tangent of the dielectric loss angle.When the addition of dielectric ceramic powder is discontented with 5 parts by volume, utilize dielectric ceramic powder to be difficult to make specific inductivity to increase; When surpassing 185 parts by volume, might the binding property of the conductive metal of composite dielectric layer be reduced, during through long-time the use, conductive metal strips down from composite dielectric layer, the performance change of electron device.
In addition, composite dielectric layer used in the present invention also preferably contains the magnetic substance powder except that above-mentioned dielectric ceramic powder.Utilize this magnetic substance powder, can be to the additional magnetic properties of composite dielectric layer, reduction linear expansivity, the raising strength of materials.
With regard to above-mentioned magnetic substance powder, can enumerate the ferromagnetism metal of wustite such as Mn-MgZn, Ni-Zn, Mn-Mg, plane (planar) material or iron carbonyl, iron-Si system alloy, iron-aluminium-Si system alloy, iron-nickel system alloy, non-crystalline state system.They both can use separately more than use two kinds also capable of being combined.
The median size of above-mentioned magnetic substance powder is preferably in 0.01～100 scope, more preferably in 0.2～20 scope.When the median size of magnetic substance powder is discontented with 0.01 μ m, the mixing tendency that becomes difficulty of resin is arranged; When surpassing 100 μ m, have and homodispersely to be inclined to.
In addition, the addition of magnetic substance powder is preferably the scope of 5～185 parts by volume with respect to organic insulation 100 parts by volume, can select suitable amount in this scope.When being discontented with 5 parts by volume, the tendency that can not show the effect of adding powder is arranged; When surpassing 185 parts by volume, mobile variation.
In addition, above-mentioned composite dielectric layer also preferably contains the cloth that is made of reinforcing fiber.At this moment, utilize the cloth that constitutes by reinforcing fiber, strengthen the physical strength of composite dielectric layer, fully prevent the damaged or distortion of electron device etc.
The material of above-mentioned reinforcing fiber is preferably any that is selected from E glass fibre, D glass fibre, NE glass fibre, H glass fibre, T glass fibre and tynex.Wherein, the NE glass fibre has that low-dielectric loss angle tangent, H glass fibre have high-k, E glass can be obtained and the balance of cost.Therefore, can suitably separate use according to desired characteristic.
The thickness of cloth is preferably 20～300 μ m, can suitably separate use according to needed thickness, characteristic.
As the concrete example of cloth, can enumerate 101 (thickness 20 μ m), 106 (thickness 30 μ m), 1080 (thickness 50 μ m), 2116 (thickness 100 μ m), 7628 (thickness 200 μ m) etc.
In addition, the surface of cloth also can be implemented out processing such as fibre, obturation as required, also can implement the surface treatment carried out with coupler etc. to the cloth surface in order to improve with the bounding force of resin.
Electron device of the present invention has at least a conductive element portion that is arranged on the above-mentioned composite dielectric layer.Conductive element portion is the element that constitutes capacitor element or inductor element, and in composite dielectric layer, conductive element portion is not limited to one, can be for a plurality of.Be arranged on the composite dielectric layer by conductive element portion, can give electron device various performances a plurality of or multiple class.Specifically, electroconductibility electronics portion constitutes on tinsel 4 grades that form on the surface of composite dielectric layer.
In the present invention, in order to obtain becoming the prepreg on electron device basis, coating with the regulation mixed the resin combination that contains Resins, epoxy, active ester compound, polyarylate and dielectric ceramic powder, magnetic substance powder and solvent is mixing and the mashed prod of pulp, carry out drying its state that becomes semicure got final product.As the solvent that use this moment, can enumerate the volatile solvent of tetrahydrofuran (THF), toluene, dimethylbenzene, butanone, pimelinketone, N,N-DIMETHYLACETAMIDE, dioxolane etc.Such solvent is used for Resins, epoxy, active ester compound and aqueousization of polyarylate are used for adjusting the viscosity of mashed prod simultaneously.The mixing known method such as ball mill, stirrer of utilizing are carried out.
As making above-mentioned prepreg and making the prepreg completely solidified and the method for the laminar cured article (substrate) that constitutes, can enumerate two kinds of above-mentioned methods, i.e. method 1 and method 2.
In addition, layered product of the present invention has double-side pattern substrate or multilager base plate etc., and they can be made as described below.
Figure 72 is the figure of the manufacturing process of expression double-side pattern substrate, and Figure 73 is the process picture sheet that expression double-side pattern substrate forms example.Shown in Figure 72,73, copper (Cu) paper tinsel 2 of the prepreg of overlapping specific thickness (not having Copper Foil) 1 and specific thickness and pressurized, heated shaping (operation A).Then, form through hole (process B) by through hole (through-hole) boring.The through hole that forms is implemented copper facing (Cu), form plated film 23 (operation C).And, on the Copper Foil 2 on two sides, form pattern, form conductor pattern 211 (step D).Then, shown in Figure 72, implement to electroplate (operation E) in order to be connected with outside terminal etc.At this moment plating can be by carrying out in the method for plating Pd behind the plating Ni again, the method (electroplate and be metallide or electroless plating) of implementing plating Au behind plating Ni again, the method for using soft tin all to be coated with machine (solder leveller).
Figure 74 is the schema of multilager base plate Production Example, and Figure 75 is the manufacturing procedure picture of multilager base plate, the example of three layers of dielectric layer of expression lamination.Shown in Figure 74, Figure 75, copper (Cu) paper tinsel 2 of the prepreg 1 of overlapping specific thickness and specific thickness, pressurized, heated are shaped, and (operation a).Then, on the Copper Foil 2 on two sides, form pattern, form arrangement of conductors Figure 21 (operation b).In the two sides side of the double-side pattern substrate that obtains like this, the prepreg 1 of overlapping specific thickness and Copper Foil 2 carry out pressurized, heated and be shaped (operation c) simultaneously again.Then, form through hole (operation d) by through hole boring.The through hole that forms is implemented copper facing (Cu), form plated film 4 (operation e).And, on the Copper Foil 2 on two sides, form pattern, form arrangement of conductors Figure 21 (operation f).Then, shown in Figure 74, implement to electroplate (operation g) in order to be connected with outside terminal etc.At this moment plating can be by carrying out in the method for plating Pd behind the plating Ni again, the method (electroplate and be metallide or electroless plating) of implementing plating Au behind plating Ni again, the method for using soft tin all to be coated with machine (solder leveller).
The molding condition of above-mentioned heating and pressurizing is preferably 100～200 ℃ temperature, 9.8 * 10 5～7.84 * 10 6Pa (10～80kgf/cm 2) pressure under, 0.5～20 hour.
Electron device of the present invention is not limited to above-mentioned example, can use various substrate manufacturings.For example use substrate or band copper clad laminate (layered product) and prepreg, prepreg is carried out lamination as adhesive linkage, also can obtain multilager base plate as shaped material.
In addition, bonding prepreg or as the mode of the substrate and the Copper Foil of its shaped material, can with by mixing above-mentioned dielectric ceramic powder, magnetic substance powder, as required and high boiling solvent such as the fire retardant, Resins, epoxy, active ester compound and the diethylene glycol monobutyl ether acetic ester that add and mashed prod that the composite dielectric material that obtains constitutes, form on the substrate that has formed pattern with methods such as silk screen print methods, thus, can realize the raising of characteristic.
Electron device of the present invention can obtain with element formation pattern by making up aforesaid prepreg, band copper clad laminate, laminated substrate etc.
Electron device of the present invention except that aforesaid electrical condenser (capacitor), coil (inducer), wave filter etc., also can be combination they and except that the high-frequency circuit of the antenna of the Wiring pattern them, amplification element, functional element or RF assembly (RF amplification section), VCO (voltage controlled oscillator), power amplifier (electric power amplification section) etc., optical sensor employed overlapping elements such as (pick-up) etc.
Then, be described more specifically the embodiment of electron device of the present invention.
(the 1st embodiment)
Fig. 1 G is the perspective oblique drawing of inducer of the 1st embodiment of expression electron device of the present invention, and Fig. 2 is the sectional view of inducer of the 1st embodiment of expression electron device of the present invention.
In Fig. 1 G, Fig. 2, inducer 10 comprises: lamination constitute layer 10a～10e layered product, be arranged on the inner conductor 13a～13d that constitutes on layer 10b～10e, the through hole 14 that is used to be electrically connected this inner conductor 13a～13d.In addition, constitute coil pattern (conductive element portion) by inner conductor 13 and through hole 14.
Each constitutes layer 10a～10e and is made of above-mentioned composite dielectric layer.Through hole 14 can pass through formation such as drilling machine, laser processing, etching.
In addition, be respectively equipped with end electrode 12 on the two sides of the subtend of layered product, the both ends of coil pattern are connected respectively on each end electrode 12.In addition, the design of the two ends of end electrode 12 has land pattern (land pattern) 11.
End electrode 12 becomes the structure that the cylinder of communicating pores is divided into half.It is in order to form a plurality of elements on the set laminated substrate, when finally cutting into each element, to utilize the heart cutting from communicating pores such as stripping and slicing (dicing), V cutting that end electrode 12 becomes such structure.
When the chip inductor that uses inducer 10 to use as high frequency, need reduce distributed capacity, so each relative permittivity that constitutes layer 10a～10e is preferably 2.6～3.5 as far as possible.In addition, when inducer 10 is when constituting the inducer of resonant circuit, to utilize distributed capacity sometimes energetically, in such purposes, each relative permittivity that constitutes layer 10a～10e is preferably 5～40.
At this inducer 10, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of inducer 10 uprises.And inducer 10 uses the big composite dielectric layer of flexural strengths to constitute a layer 10a～10e as each, so the damaged and even distortion can fully prevent operating induction device 10 time etc.In addition, can realize electron device miniaturization, can omit capacity cell is installed on the circuit.In addition, in these inducers, the loss of material need be suppressed as far as possible,, the inducer that loss is few, the Q value is high of material can be obtained so the tangent of the dielectric loss angle (tan δ) of formation layer 10a～10e is 0.0025～0.0075 by making respectively.In addition, each formation layer 10a～10e both can be the same or different, and selected optimal combination to get final product.
In addition, the equivalent electrical circuit of the electron device of Fig. 1 G is shown in Figure 10 (a).Shown in Figure 10 (a), inducer 10 is expressed as in equivalent electrical circuit, as the electron device with coil 31 (inducer).
(the 2nd embodiment)
Fig. 3 is the perspective oblique drawing of inducer of the 2nd embodiment of expression electron device of the present invention, and Fig. 4 is the sectional view of inducer of the 2nd embodiment of expression electron device.
The electron device of present embodiment, coil pattern along laterally, promptly, on this point of the direction rollback of the relative end electrode 12 of connection, different with the electron device of first embodiment.
Other integrant is identical with the 1st embodiment, in Fig. 3, Fig. 4, to same integrant mark prosign, omits explanation.
(the 3rd embodiment)
Fig. 5 is the perspective oblique drawing of inducer of the 3rd embodiment of expression electron device of the present invention, and Fig. 6 is the sectional view of inducer of the 3rd embodiment of expression electron device of the present invention.
The electron device of present embodiment forms respectively on this point of spiral helicine inner conductor 13 by through hole 14 connections in top and bottom, and is different with the electron device of first embodiment.
Other integrant is identical with the 1st embodiment, in Fig. 5, Fig. 6, to same integrant mark prosign, omits explanation.
(the 4th embodiment)
Fig. 7 is the perspective oblique drawing of inducer of the 4th embodiment of expression electron device of the present invention, and Fig. 8 is the sectional view of inducer of the 4th embodiment of expression electron device of the present invention.
The electron device of present embodiment, the pattern form of inner conductor 13 that is arranged on the end electrode 12 of layered product both sides in connection is on this point of bending (meander), and is different with the electron device of first embodiment.
Other integrant is identical with the 1st embodiment, in Fig. 7, Fig. 8, to same integrant mark prosign, omits explanation.
(the 5th embodiment)
Fig. 9 is the perspective oblique drawing of inducer of the 5th embodiment of expression electron device of the present invention.
The electron device of present embodiment is on this point that 4 coil pattern is connected with at layered product, and is different with the electron device of first embodiment that is provided with 1 coil pattern.By becoming such structure, when being configured in electron device on the circuit substrate etc., compare with using four situations with electron device of a coil pattern, can realize saving the space.
In addition, Figure 10 (b) is the equivalent-circuit diagram of the inducer of expression present embodiment.Shown in Figure 10 (b), the inducer of present embodiment is expressed as the mode that coil 31a～31d installs four continuously in equivalent electrical circuit.
(the 6th embodiment)
Figure 11 is the perspective oblique drawing of electrical condenser (condenser) of the 6th embodiment of expression electron device of the present invention, and Figure 12 is the sectional view of electrical condenser of the 6th embodiment of expression electron device of the present invention.
In Figure 11, Figure 12, electrical condenser 20 possesses: lamination constitute layer 20a～20g layered product, constituting the inner conductor 23 that is formed with on layer 20b～20g, the end electrode 22 that is respectively equipped with in the layered product both sides.And the inner conductor 23 of adjacency is connected on the different end electrode 22.In addition, the design of the two ends of end electrode 22 has land pattern 21.Constitute conductive element portion by the inner conductor 23 that on layered product, is provided with.In addition, each formation layer 20a～20g is made of above-mentioned composite dielectric layer.
In addition, from the diversity of the electric capacity that obtains or the viewpoint of precision, each constitutes layer 20a～20g preferably has 2.6～40 relative permittivity, has 0.0025～0.0075 tangent of the dielectric loss angle (tan δ).Even because the relative permittivity of this electrical condenser 20 is also high in the high frequency field, thus the area of inner conductor 23 is diminished, and then make the miniaturization of electrical condenser 20 become possibility.In addition, though under hot conditions, use electrical condenser 20 also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of electrical condenser 20 uprises.And electrical condenser 20 uses the big composite dielectric layer of flexural strengths as constituting a layer 20a～20g, so the damaged and even distortion can fully prevent operation of capacitor device 20 time etc.In addition, be 0.0075～0.025 by making tangent of the dielectric loss angle (tan δ), can obtain the few electrical condenser of material unaccounted-for (MUF).Each formation layer 20a～20g both can be the same or different, and selected optimal combination to get final product.
The equivalent-circuit diagram of Figure 14 (a) expression electrical condenser 20.Shown in Figure 14 (a), in equivalent electrical circuit, be shown with electron device (electrical condenser) with electrical condenser 32.
(the 7th embodiment)
Figure 13 is the perspective oblique drawing of electrical condenser of the 7th embodiment of expression electron device of the present invention.
The electron device of present embodiment, being provided with on this point of four conductive element portions that constitute capacitor element to arrange (array) shape on the layered product, different with the electrical condenser of the 6th embodiment that on layered product, is provided with a conductive element portion that constitutes capacitor element.In addition, the number according to capacitor element is provided with end electrode 12 and land pattern 11.And, when forming electrical condenser, form various electric capacity with good accuracy sometimes to arrange shape.Therefore, scope that we can say above-mentioned specific inductivity, tangent of the dielectric loss angle is preferred.
Other integrant is identical with the 6th embodiment, in Figure 13, to same integrant mark prosign, omits explanation.
Figure 14 (b) is the equivalent-circuit diagram of the electrical condenser of present embodiment.Shown in Figure 14 (b), the company of being expressed as adorns the electron device (electrical condenser) of four electrical condenser 32a～32d in equivalent electrical circuit.
(the 8th embodiment)
Figure 15～Figure 18 represents the balanced-to-unbalanced transformer of the 8th embodiment of electron device of the present invention.Here, Figure 15 is the perspective oblique drawing, and Figure 16 is a sectional view, and Figure 17 is the stratified decomposition view of each structure, and Figure 18 is an equivalent-circuit diagram.
In Figure 15～Figure 17, balanced-to-unbalanced transformer 40 comprises: lamination constitute the layered product of layer 40a～40o, be configured in layered product up and down and the inner GND conductor 45 of intermediary, and the inner conductor 43 that between this inside GND conductor 45, forms.This inner conductor 43 is the long helical conductors 43 of λ g/4, in the joint line 53a～53d mode shown in the equivalent-circuit diagram that constitutes Figure 18, with through hole 44 connections such as grade.
The relative permittivity of the formation layer 40a～40o of this balanced-to-unbalanced transformer 40 is preferably 2.6～40, and tangent of the dielectric loss angle (tan δ) is preferably 0.0075～0.025, constitutes layer 40a～40o as each, can use above-mentioned composite dielectric layer.In addition, each formation layer both can be the same or different, and selected optimal combination to get final product.
As long as utilize this balanced-to-unbalanced transformer 40, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, can improve reliability under the hot environment of balanced-to-unbalanced transformer 40.And, in the balanced-to-unbalanced transformer 40, use the big composite dielectric layer of flexural strength as constituting a layer 40a～40o, so the damaged and even distortion can fully prevent to operate balanced-to-unbalanced transformer 40 time etc.
(the 9th embodiment)
Figure 19～Figure 22 represents the laminated filter of the 9th embodiment of electron device of the present invention.Here, Figure 19 is an oblique drawing, and Figure 20 is an exploded perspective view, and Figure 21 is an equivalent-circuit diagram, and Figure 22 is for passing on performance chart.
The laminated filter of present embodiment constitutes in the mode of reception and registration characteristic with two electrode types.Shown in Figure 19～21, laminated filter 60 possesses and has carried out laminated layered product to constituting a layer 60a～60e.Here, constituting layer 60b is that top constitutes layer group, and constituting layer 60d is that the bottom constitutes layer group.On the formation layer 60c of the approximately central authorities of layered product, be formed with a pair of strip line 68, constitute on the layer group 60d in the bottom of adjacency therewith and be formed with a pair of electrical condenser conductor 67.Be formed with GND conductor 65 respectively on the surface of formation layer 60b, 60e, clamp strip line 68 and electrical condenser 67 by these GND conductors 65.Strip line 68, electrical condenser conductor 67 and GND conductor 65 are connected on the tip electrodes that forms on the end face of layered product (outside terminal) 62.In addition, be formed with GND pattern 66 in the both sides of tip electrodes 62, GDN pattern 66 is connected on the GND conductor 65.
Strip line 68 is strip line 74a, the 74b with long or its following length of the λ g/4 shown in the equivalent-circuit diagram of Figure 21, and electrical condenser 67 constitutes input and output coupling capacity Ci.In addition, between strip line 74a, the 74b, by coupling capacity Cm and percentage coupling M combination.Laminated filter 60 is owing to constituting in the mode that forms such equivalent electrical circuit, so have the reception and registration characteristic of 2 electrode types shown in Figure 22.
The formation layer 60a～60e of this laminated filter 60 is 2.6～40 by making relative permittivity, in the band territory of hundreds of MHz～number GHz, can obtain desired reception and registration characteristic.In addition, expectation suppresses the material unaccounted-for (MUF) of stripline syntonizer as far as possible, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.Formation layer 60a～60e as such can use above-mentioned composite dielectric layer.In addition, each formation layer both can be the same or different, and selected optimal combination to get final product.
As long as utilize this laminated filter 60, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of laminated filter 60 uprises.And laminated filter 60 uses the big composite dielectric layer of flexural strengths as constituting a layer 60a～60e, so the damaged and even distortion can fully prevent to operate laminated filter 60 time etc.
(the 10th embodiment)
Figure 23～Figure 26 represents the laminated filter of the 10th embodiment of electron device of the present invention.Here, Figure 23 is an oblique drawing, and Figure 24 is an exploded perspective view, and Figure 25 is an equivalent-circuit diagram, and Figure 26 is for passing on performance chart.
The laminated filter of present embodiment constitutes in the mode of reception and registration characteristic with 4 electrode types.Shown in Figure 23～25, laminated filter 60 is on this point that constitutes 4 strip line 68 of formation on the layer 60c, with different at the laminated filter that constitutes the 9th embodiment that forms two strip line 68 on the layer 60c.
In the laminated filter of present embodiment, strip line 68 is strip line 74c, 74d, 74e, the 74f with long or its following length of the λ g/4 shown in the equivalent-circuit diagram of Figure 25, in addition, between strip line 74c, the 74d, between strip line 74d, the 74e and between strip line 74e, the 74f respectively by coupling capacity Cm and percentage coupling M combination.Laminated filter 60 constitutes in the mode that forms such equivalent electrical circuit, so have the reception and registration characteristic of 4 electrode types shown in Figure 26.
Other integrant is identical with the 9th embodiment, in Figure 23, Figure 24, to same integrant mark prosign, omits explanation.
(the 11st embodiment)
Figure 27～Figure 32 is the stop filter (block filter) of the 11st embodiment of expression electron device of the present invention.Here, Figure 27 is the perspective oblique drawing, and Figure 28 is a front cross-sectional view, and Figure 29 is a side cross-sectional views, and Figure 30 is a plan cross-sectional view, and Figure 31 is an equivalent-circuit diagram, and Figure 32 is the perspective side figure of the structure of expression metal die.
The stop filter of present embodiment constitutes in the mode of reception and registration characteristic with 2 electrode types.As Figure 27～shown in Figure 32, stop filter 80 has component parts 80a, be arranged on a pair of coaxial conductor 81 in the component parts 80a and be connected electrical condenser coaxial conductor 82 on the coaxial conductor 81.Coaxial conductor 81 and electrical condenser coaxial conductor 82 constitute in order to the conductor that the mode of digging through component parts 80a forms hollow form.In addition, around component parts 80a, be formed with surperficial GND conductor 87 in the mode that covers it.And, on the position relative, be formed with electrical condenser conductor 83 with the electrical condenser coaxial conductor 82 of component parts 80a.In addition, electrical condenser conductor 83 and surperficial GND conductor 87 also are used as input and output terminal respectively and portion's product are fixedly used terminal.In addition, the internal surface at coaxial conductor 81 and electrical condenser coaxial conductor 82 is attached with electro-conductive material with methods such as electroless plating, evaporations, has formed transmission route thus.
Coaxial conductor 81 is coaxial line 94a, the 94b with long or its following length of the λ g/4 shown in the equivalent-circuit diagram of Figure 31, forms GND conductor 87 in the mode of surrounding them.In addition, electrical condenser coaxial conductor 82 and electrical condenser conductor 83 constitute input and output coupling capacity Ci.And, pass through coupling capacity Cm and percentage coupling M combination between the coaxial conductor 81.Stop filter 80 constitutes in the mode that forms equivalent electrical circuit shown in Figure 31, so have the reception and registration characteristic of 2 electrode types.
Figure 32 is the fragmentary cross sectional view of metal die that expression is used to form the component parts 80a of stop filter 80.In Figure 32, metal die is to be formed with resin inlet 104 and filling orifice 106 on the metab 103 of iron etc., is formed with the parts formation 105a of portion, 105b with this filling orifice 106 with communicating.The composite resin material that is used to form component parts 80a injects from resin inlet 104 with the state of liquid, arrives the parts formation 105a of portion, 105b by filling orifice 106.Then, fill in the inside of this metal die under the state of compound resin, cool off or heat treated cured composite resin and from metal die, taking out, be breaking at the part that solidified is not wanted in waiting in the inlet 104.Like this, just form Figure 27～component parts 80a shown in Figure 30.
When processing such as the component parts 80a to such formation electroplates, etching, printing, injection, evaporation, form surperficial GND conductor 87, coaxial conductor 81 and the electrical condenser coaxial conductor 82 etc. that form by copper, gold, palladium, platinum, aluminium etc.
The component parts 80a of stop filter 80 is 2.6～40 by making relative permittivity, in the band territory from hundreds of MHz to number GHz, can obtain desired reception and registration characteristic.In addition, expectation suppresses the material unaccounted-for (MUF) of coaxial resonator as far as possible, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.Component parts 80a as such can use above-mentioned composite dielectric layer.
As long as utilize this stop filter 80, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of stop filter 80 uprises.And stop filter 80 uses the big composite dielectric layer of flexural strengths as component parts 80a, so the damaged and even distortion can fully prevent to operate stop filter 80 time etc.
(the 12nd embodiment)
Figure 33～Figure 37 is the unitor of the 12nd embodiment of expression electron device of the present invention.Here, Figure 33 is the perspective oblique drawing, and Figure 34 is a sectional view, and Figure 35 is the stratified decomposition view of each structure, and Figure 36 is a cut-away view, and Figure 37 is an equivalent-circuit diagram.
In Figure 33～Figure 37, unitor 110 has: lamination constitute the layered product of layer 110a～110c, the inside GND conductor 115 that on the top and bottom of the formation layer 110b of layered product, forms, and two coil pattern that between this inside GND conductor 115, form, constitute transformer.Each coil pattern is made of with the through hole 114 that is connected these inner conductors 113 a plurality of inner conductors 113, becomes spirrillum.In addition, each overhang of formation and inner GND conductor 115 as shown in figure 36, are connected to respectively on the end electrode 112 that forms on the side of layered product.In addition, be formed with land pattern 111 at the both ends of end electrode 112.
Like this, shown in the equivalent-circuit diagram of Figure 37, unitor 110 becomes the device that combines two coil 125a, 125b.
In the time will realizing the wideband territory, the relative permittivity of the formation layer 110a～110c of unitor 110 is preferably an as far as possible little side.On the other hand, when considering miniaturization, require relative permittivity high as far as possible.Therefore, as the material that constitutes layer 110a～110c,, use material to get final product with its corresponding relative permittivity according to purposes, desired performance, mode etc.Usually be 2.6～40 by making the relative permittivity that constitutes layer 110a～110c, in band territory, can obtain desired reception and registration characteristic from hundreds of MHz to number GHz.In addition, in order to improve the Q value of internal electrical sensor, tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.Thus, the inducer that material unaccounted-for (MUF) is few, the Q value is high can be formed, high performance unitor can be obtained.As above-mentioned formation layer 110a～110c, can use above-mentioned composite dielectric layer.In addition, each formation layer both can be the same or different, and selected optimal combination to get final product.
As long as utilize this unitor 110, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of unitor 110 uprises.And unitor 110 uses the big composite dielectric layer of flexural strengths as constituting a layer 110a～110c, so the damaged and even distortion can fully prevent to operate unitor 110 time etc.
(the 13rd embodiment)
Figure 38～Figure 40 is the figure of antenna of the 13rd embodiment of expression electron device of the present invention, and Figure 38 is the perspective oblique drawing, and Figure 39 (a) is an orthographic plan, (b) is side cross-sectional views, (c) is front cross-sectional view, and Figure 40 is the stratified exploded perspective view of each structure.
As Figure 38～shown in Figure 40, antenna 130 has: lamination constitute the layered product of the long chi shape of layer 130a～130c, this constitute layer 130b and constitute the inner conductor 133 that forms respectively on the layer 130c and two ends at the layered product of long chi shape on the end electrode 132 of setting respectively.
Inner conductor 133 constitutes antenna pattern (antenna pattern).In the present embodiment, inner conductor 133 constitutes into the reactive element of the about λ g/4 of length with respect to frequency of utilization, and antenna pattern forms bending.
In addition, the both ends of inner conductor 133 are connected respectively on each end electrode 132.In the formation layer 130a～130c of this antenna 130, in the time will realizing the wideband territory, relative permittivity is preferably an as far as possible little side.On the other hand, when considering miniaturization, require relative permittivity high as far as possible.Therefore, as the material that constitutes layer 130a～130c,, use material to get final product with its corresponding relative permittivity according to purposes or desired performance, mode etc.Usually the relative permittivity that constitutes layer 130a～130c is preferably 2.6～40, and tangent of the dielectric loss angle is preferably 0.0075～0.025, as constituting layer 130a～130c, can use above-mentioned composite dielectric layer.Thus, the scope of frequency is wide, can form high precision.In addition, need suppress the loss of material as far as possible.Therefore, be 0.0025～0.0075 by making tangent of the dielectric loss angle (tan δ), can form the few antenna of material unaccounted-for (MUF).In addition, each formation layer both can be the same or different, and selected optimal combination to get final product.
As long as utilize this antenna 130, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of antenna 130 uprises.And antenna 130 uses the big composite dielectric layer of flexural strengths as constituting a layer 130a～130c, so the damaged and even distortion can fully prevent operational antennas 130 time etc.
(the 14th embodiment)
Figure 41 is the perspective oblique drawing of antenna of the 14th embodiment of expression electron device of the present invention, and Figure 42 is the exploded perspective view of antenna of the 14th embodiment of expression electron device of the present invention.
In Figure 41,42, antenna 140 has: lamination constitute the layered product of layer 140a～140c, at this formations layer 140b and constitute on the layer 140c inner conductor 143a of formation respectively.And inner conductor 143a up and down connects with through hole 144, becomes spiral helicine antenna pattern (inductance element).In addition, identical with the 13rd embodiment, be respectively equipped with end electrode at the two ends of layered product, the both ends of antenna pattern are connected with each end electrode respectively.
(the 15th embodiment)
Figure 43 is the perspective oblique drawing of patch antenna (patchantenna) of the 15th embodiment of expression electron device of the present invention, and Figure 44 is the sectional view of patch antenna of the 15th embodiment of expression electron device of the present invention.
Shown in Figure 43,44, the patch antenna 150 of present embodiment has: constitute a layer 150a, the tabular wire conductors 159 that is formed with on the surface of this formations layer 150a, constituting the GND conductor 155 that forms on the bottom surface of layer 150a in the mode relative with this wire conductors 159.Here, wire conductors 159 constitutes antenna pattern.In addition, on wire conductors 159 with perforation conductor 154 connections of will give electric usefulness for electric portion 153, this perforation conductor 154 with and GND conductor 155 unconnected modes and GND conductor 155 between be provided with gap 156.Therefore, become: from the bottom of GND conductor 155 by connect conductor 154 carry out to.
In the formation layer 150a of this patch antenna 150, in the time will realizing the wideband territory, relative permittivity is preferably an as far as possible little side.On the other hand, when considering miniaturization, require relative permittivity high as far as possible.Therefore, as constituting layer 150a,, use material to get final product with its corresponding relative permittivity according to purposes or desired performance, mode etc.Usually the relative permittivity that constitutes layer 150a is preferably 2.6～40, and tangent of the dielectric loss angle is preferably 0.0075～0.025, as constituting layer 150a, can use above-mentioned composite dielectric layer.Thus, the scope of frequency is wide, can form high precision.In addition, be 0.0025～0.0075 by making tangent of the dielectric loss angle (tan δ), can form the high antenna of the few emission efficiency of material unaccounted-for (MUF).
In addition, in the frequency band territory below hundreds of MHz, magnet also obtains the wavelength decreases effect same with dielectric medium, and, can improve the inductance value of emissive element.In addition, by the frequency peak of combination Q, even in lower frequency, also can obtain high Q.Therefore, when using patch antenna 150 in the purposes of the radio equipment of tens of～hundreds of MHz, permeability is preferably 3～20, constitutes a layer 150a and preferably uses the composite magnetic body layer that contains the magnetic substance powder.Thus, in the frequency band territory below hundreds of MHz, can realize high characterization, miniaturization.In addition, each formation layer both can be the same or different, and selected optimal combination to get final product.
As long as utilize this patch antenna 150, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of patch antenna 150 uprises.And patch antenna 150 uses the big composite dielectric layer of flexural strengths as constituting a layer 150a, so the damaged and even distortion can fully prevent to operate patch antenna 150 time etc.
(the 16th embodiment)
Figure 45 is the perspective oblique drawing of patch antenna of the 16th embodiment of expression electron device of the present invention, and Figure 46 is the sectional view of patch antenna of the 16th embodiment of expression electron device of the present invention.
Shown in Figure 45,46, patch antenna 160 have constitute a layer 160a, the wire conductors (antenna pattern) 169 that on the surface of this formations layer 160a, forms and, the GND conductor 165 that on the bottom surface of formation layer 160a, forms in the mode relative with this wire conductors 169.In addition, near the side that constitutes layer 160a, wire conductors 169, with discontiguous mode therewith dispose to electric usefulness give electric conductor 161, become from give electric terminal 162 to give electric conductor 161 carry out to.Constitute for electric terminal 162 by copper, gold, palladium, platinum, aluminium etc., can use factures such as plating, termination (terminate), printing, injection, evaporation to form.Other integrant is identical with the 15th embodiment, to same integrant mark prosign, omits explanation.
(the 17th embodiment)
Figure 47 is the perspective oblique drawing of multi-layered type patch antenna of the 17th embodiment of expression electron device of the present invention, and Figure 48 is the sectional view of multi-layered type patch antenna of the 17th embodiment of expression electron device of the present invention.
As shown in figure 47, the patch antenna 170 of present embodiment has: lamination the layered product that constitutes layer 150a and constitute layer 150b; Constitute wire conductors 159a, the 159e that forms respectively on the surface of layer 150a, 150b at this; The GND conductor 155 that on the bottom surface that constitutes layer 150b, forms in the mode relative with this wire conductors 159a, 159e.In addition, on wire conductors 159a, use and to connect for the electric 153a of portion to the perforation conductor 154 of electric usefulness, this connect conductor 154 with GND conductor 155 and the unconnected mode of wire conductors 159e, and GND conductor 155 and wire conductors 159e between, be provided with gap 156.Therefore, from the bottom of GND conductor 155 by connect conductor 154 butted line conductor 159a carry out to.At this moment, by by with the condenser coupling of wire conductors 159a and the electric capacity that forms with the gap that connects conductor 154, butted line conductor 159e to.Other integrant is identical with the 15th embodiment, to same integrant mark prosign, omits explanation.
(the 18th embodiment)
Figure 49 is the perspective oblique drawing that connects the type patch antenna of the 18th embodiment of expression electron device of the present invention more, and Figure 50 is the sectional view that connects the type patch antenna of the 18th embodiment of expression electron device of the present invention more.
The patch antenna 180 of present embodiment, being provided with on the layered product on four conductive element portion this point of cancellate formation antenna, different with the patch antenna of the 17th embodiment that on layered product, only is provided with a conductive element portion.That is, as Figure 49, shown in Figure 50, patch antenna 180 has: lamination constitute the layered product of layer 150a, 150b; Constituting wire conductors 159a, 159b, 159c, the 159d that forms on the layer 150a; Constituting wire conductors 159e, 159f, 159g, the 159h that forms on the layer 150b; The GND conductor 155 that on the bottom surface that constitutes layer 150b, forms in the mode relative with these wire conductors 159a, 159e.Other integrant is identical with the 17th embodiment, to same integrant mark prosign, omits explanation.
Like this, make it become reticulation, can realize the miniaturization of patch antenna and the reduction that element is counted by on a layered product, setting a plurality of conductive element portion.
(the 19th embodiment)
Figure 51～Figure 53 is the VCO (voltage controlled oscillator) of the 19th embodiment of expression electron device of the present invention.Here, Figure 51 is the perspective oblique drawing, and Figure 52 is a sectional view, and Figure 53 is an equivalent-circuit diagram.
In Figure 51～Figure 53, VCO210 has: lamination constitute the layered product of layer 210a～210g; Electrical elements 261 such as the electrical condenser that on layered product, forms, disposes, inducer, semiconductor element, resistor; Constituting the conductor pattern that forms on layer 210a～210d; And constituting the conductor pattern 262,263,264 that forms respectively on layer 210e～210g.VCO210 constitutes in the mode that forms the equivalent electrical circuit shown in Figure 53, and conductor pattern 263 becomes stripline (strip line).In addition, VCO210 also has electrical condenser, signal wire, semiconductor element, supply lead etc. except that stripline.Therefore, materials with function formation is effective with adapting to separately to constitute layer.
More specifically, on the surface of above-mentioned formation layer 210g, form inner conductor stripline 263, inside go up and form GND conductor 262 and terminal conductor 266.In addition, on the surface that constitutes layer 210e, form electrical condenser conductor 264, on the surface that constitutes layer 210b, form wired electric sensor conductor 265.In addition, constitute the inner conductor that forms on the layer at each and connect, carry the electron device 261 that has been assembled from the teeth outwards, form the VCO of the equivalent electrical circuit that shows Figure 53 by through hole 214.
For example, in the VCO210 of present embodiment, the preferred tangent of the dielectric loss angle of using is 0.0025～0.0075 composite dielectric layer in constituting formation layer 210f, the 210g of syntonizer, uses preferably at the formation layer 210c～210e that constitutes electrical condenser that tangent of the dielectric loss angle is 0.0075～0.025, relative permittivity is 5～40 composite dielectric layer.Formation layer 210a, the 210b that constitutes distribution and inducer uses preferably that tangent of the dielectric loss angle is 0.0025～0.0075, relative permittivity is 2.6～3.5 composite dielectric layer.
Adapt to relative permittivity, Q, the tangent of the dielectric loss angle of function separately by becoming such structure, can becoming, make high performance, miniaturization, slimming become possibility.As long as utilize this VCO210, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of VCO210 uprises.And VCO210 uses the big composite dielectric layer of flexural strength as constituting a layer 210a～210g, so the damaged and even distortion can fully prevent to operate VCO210 time the etc.
(the 20th embodiment)
Figure 54～Figure 56 is the power amplifier (power amplifier) of the 20th embodiment of expression electron device of the present invention.Here, Figure 54 is the stratified decomposition view of each structure, and Figure 55 is a sectional view, and Figure 56 is an equivalent-circuit diagram.
In Figure 54～Figure 56, power amplifier 300 has: lamination constitute the layered product of layer 300a～300e; Electrical elements 361 such as the electrical condenser that on layered product, disposes, inducer, semiconductor element, resistor; In this formation layer 300a～300e with and top and bottom on the conductor pattern 313,315 that forms.This power amplifier becomes the equivalent electrical circuit shown in Figure 56, so have stripline L11～L17, electrical condenser C11～C20, signal wire, to semi-conductive supply lead etc.Therefore, materials with function formation formation layer is effective with adapting to separately.
More specifically, on the surface of these formation layers 300a～300e, be formed with inner conductor 313, GND conductor 315 etc.In addition, each inner conductor connects by through hole 314, the power amplifier shown in the equivalent electrical circuit of electron device 361 formation Figure 56 that lift-launch has been assembled on the surface of layered product.
In the power amplifier 300 of present embodiment, preferably in constituting formation layer 300d, the 300e of stripline use that tangent of the dielectric loss angle is 0.0075～0.025, relative permittivity is 2.6～40 composite dielectric layer.The formation layer 300a～300c that constitutes electrical condenser uses preferably that tangent of the dielectric loss angle is 0.0075～0.025, relative permittivity is 5～40 composite dielectric layer.
Be suitable for relative permittivity, Q, the tangent of the dielectric loss angle of function separately by forming such structure, can becoming, make high performance, small-sized, slimming become possibility.As long as utilize this power amplifier 300, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of power amplifier 300 uprises.And power amplifier 300 uses the big composite dielectric layer of flexural strengths as constituting a layer 300a～300e, so the damaged and even distortion can fully prevent operand power amplifier 300 time etc.
(the 21st embodiment)
Figure 57～Figure 59 is the overlapping element that is used in optical sensor etc. of the 21st embodiment of expression electron device of the present invention.Here, Figure 57 is the stratified decomposition view of each structure, and Figure 58 is a sectional view, and Figure 59 is an equivalent-circuit diagram.
In Figure 57～Figure 59, overlapping element 400 has: lamination constitute the layered product of layer 400a～400k; Electrical elements 461 such as the electrical condenser that on layered product, forms, disposes, inducer, semiconductor element, resistor; In this formation layer 400a～400k with and top and bottom on the conductor pattern 413,415 that forms etc.This overlapping element 400 constitutes the equivalent electrical circuit shown in Figure 59, so have inducer L21, L23, electrical condenser C21～C27, signal wire, to semi-conductive supply lead etc.Therefore, materials with function formation formation layer is effective with being suitable for separately.
More specifically, on the surface of these formation layers 400a～400k, be formed with inner conductor 413, GND conductor 415 etc.In addition, each inner conductor connects up and down by through hole 414, carries the overlapping element shown in the equivalent electrical circuit of the electron device 461 formation Figure 59 that have been assembled from the teeth outwards.
In the overlapping element 400 of present embodiment, preferably in constituting the formation layer 400d～400h of electrical condenser use that tangent of the dielectric loss angle is 0.0075～0.025, relative permittivity is 10～40 composite dielectric layer.Formation layer 400a～400c, the 400j～400k that constitutes inducer uses preferably that tangent of the dielectric loss angle is 0.0025～0.0075, relative permittivity is 2.6～3.5 composite dielectric layer.
Adapt to relative permittivity, Q, the tangent of the dielectric loss angle of function separately by becoming such structure, can becoming, make high performance, small-sized, slimming become possibility.As long as utilize this overlapping element 400, though under hot conditions, use also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of overlapping element 400 uprises.And overlapping element 400 uses the big composite dielectric layer of flexural strengths as constituting a layer 400a～400k, so the damaged and even distortion can fully prevent operation overlap assembly 400 time etc.
(the 22nd embodiment)
Figure 60～Figure 63 is the RF assembly of the 22nd embodiment of expression electron device of the present invention.Here, Figure 60 is an oblique drawing, and Figure 61 is the oblique drawing that takes off the state of externally mounted part material, and Figure 62 is the stratified exploded perspective view of each structure, and Figure 63 is a sectional view.
In Figure 60～Figure 63, FR assembly 500 has: lamination constitute the layered product of layer 500a～500i; Electrical elements 561 such as the electrical condenser that on layered product, disposes, inducer, semi-conductor, resistor; In this formation layer 500a～500i with and top and bottom on the conductor pattern 513,515,572 that forms etc.; Antenna pattern 573.This FR assembly 500 has inducer, electrical condenser, signal wire as described above, to semi-conductive supply lead etc.Therefore, materials with function formation formation layer is effective with being suitable for separately.
In the FR of present embodiment assembly, antenna configuration, stripline structure and wiring layer 500a～500d, 500g use preferably that tangent of the dielectric loss angle is 0.0025～0.0075, relative permittivity is 2.6～3.5 composite dielectric layer.The formation layer 500e～500f of electrical condenser uses preferably that tangent of the dielectric loss angle is 0.0075～0.025, relative permittivity is 10～40 composite dielectric layer.It is 3～20 that supply lead layer 500h～500i preferably uses permeability, contain the composite magnetic body layer of magnetic substance powder.
And, on the surface of these formation layers 500a～500i, be formed with inner conductor 513, GND conductor 515, antenna conductor 573 etc.In addition, each inner conductor connects up and down by through hole 514, carries the electronic component 561 that has been assembled and form the RF assembly on the surface of layered product.
Adapt to relative permittivity, Q, the tangent of the dielectric loss angle of function separately by becoming such structure, can becoming, make high performance, small-sized, slimming become possibility.As long as utilize this FR assembly 500, though under hot conditions, use FR assembly 500 also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of FR assembly 500 uprises.And FR assembly 500 uses the big composite dielectric layer of flexural strengths as constituting a layer 500a～500i, so the damaged and even distortion can fully prevent to operate FR assembly 500 time etc.
(the 23rd embodiment)
Figure 64, Figure 65 represent the syntonizer of the 23rd embodiment of electron device of the present invention.Here, Figure 64 is the perspective oblique drawing, and Figure 65 is a sectional view.
In Figure 64,65, syntonizer 600 possesses base material 610 and connects the tubular coaxial conductor 641 of base material 610.
The manufacture method of syntonizer 600 is identical with the stop filter of the 11st embodiment.Promptly, at first, on the surface of the base material 610 that utilizes metal die to be configured as to have formed cylindric communicating pores, utilize factures such as plating, etching, printing, injection, evaporation, form surperficial GND conductor 647 and end conductor 682, to connect the mode of this surface GND conductor 647 and end conductor 682, on the inner-wall surface of base material 610, form coaxial conductor 641, to form syntonizer HOT terminal 681 etc. with coaxial conductor 641 ways of connecting.Surface GND conductor 647, end conductor 682, coaxial conductor 641, syntonizer are formed by copper, gold, palladium, platinum, aluminium etc. with HOT terminal 681.Here, coaxial conductor 641 is the coaxial-type circuits with certain natural impedance, to surround the mode of coaxial conductor 641, forms surperficial GND conductor 647 on base material 610.
The base material 610 of this syntonizer is 2.6～40 by making relative permittivity, in the band territory from hundreds of MHz to number GHz, can obtain desired resonance characteristic.In addition, wish to suppress as far as possible the material unaccounted-for (MUF) of syntonizer, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.As such base material 610, can use above-mentioned composite dielectric layer.As long as utilize this syntonizer 600, though under hot conditions, use syntonizer 600 also can fully suppress relative permittivity through the time change.Therefore, the reliability under the hot environment of syntonizer 600 uprises.And syntonizer 600 uses the big composite dielectric layer of flexural strengths as base material 610, so the damaged and even distortion can fully prevent to operate syntonizer 600 time etc.
(the 24th embodiment)
Figure 66, Figure 67 represent the banded syntonizer of the 24th embodiment of electron device of the present invention.Here, Figure 66 is the perspective oblique drawing, and Figure 67 is a sectional view.
Shown in Figure 66,67, banded syntonizer 700 has: lamination constitutes layer 710a～710d and the layered product that forms; Constituting the rectangular tape conductor 784 that forms on the layer 710c; At the rectangular-shaped GND conductor 783 that constitutes a layer 710b, constitutes on the layer 710d, forms in the mode of clamping tape conductor 784.In addition, syntonizer HOT terminal 781 and GND terminal 782 are set respectively in the both sides of layered product, the two ends of tape conductor 784 are connected syntonizer respectively with on HOT terminal 781 and the GND terminal 782.Can make banded syntonizer 700 in the same manner with the inducer of the 1st embodiment.
The formation layer 710a～710d of syntonizer is 2.6～40 by making relative permittivity, in the band territory from hundreds of MHz to number GHz, can obtain desired resonance characteristic.In addition, wish to suppress as far as possible the material unaccounted-for (MUF) of syntonizer, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.Formation layer 710a～710d as such can use above-mentioned composite dielectric layer.
(the 25th embodiment)
Figure 68 is the perspective oblique drawing of syntonizer of the 25th embodiment of expression electron device of the present invention.
Shown in Figure 68, syntonizer 800 possesses: base material 810, the coaxial-type electrical conductor 842 that connects the coaxial-type electrical conductor 841 cylindraceous of base material 810, is provided with abreast with the coaxial-type electrical conductor 841 that connects base material 810.In base material 810, on an end of coaxial-type electrical conductor 842, form tip electrodes 882, on the other end, form to connect and use electrode 885.In addition, an end of coaxial-type electrical conductor 841 is connected with coaxial-type electrical conductor 841 by connecting with electrode 885, is formed with syntonizer HOT terminal 881 on the other end.Here, tip electrodes 882 is electrical isolations with syntonizer with HOT terminal 881.Then, to surround the mode of base material 810, be formed with surperficial GND conductor 847.Surface GND conductor 847 is connected with tip electrodes 882, but with syntonizer usefulness HOT terminal 881 electrical isolations.Therefore, coaxial conductor 841,842 is being brought into play as having the function of the coaxial-type circuit of certain natural impedance.
The base material 810 of this syntonizer is 2.6～40 by making relative permittivity, in the band territory from hundreds of MHz to number GHz, can obtain desired resonance characteristic.In addition, wish to suppress as far as possible the material unaccounted-for (MUF) of syntonizer, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.As such base material 810, can use above-mentioned composite dielectric layer.
(the 26th embodiment)
Figure 69 is the perspective oblique drawing of banded syntonizer of the 26th embodiment of expression electron device of the present invention.
In Figure 69, banded syntonizer 850 has: laminated multilayer constitutes layer 810 and the layered product of formation; At the tape conductor 884 that constitutes the U word shape that forms on the layer 810; By constituting the rectangular-shaped GND conductor 883 that layer 810 disposes in the mode that sandwiches tape conductor 884 up and down.In addition, be set up in parallel syntonizer HOT terminal 881 and GND terminal 882 respectively in the both sides of layered product, the both ends of tape conductor 884 are connected syntonizer respectively with on HOT terminal 881 and the GND terminal 882.The manufacture method of banded syntonizer 850 is identical with the inducer of the 1st embodiment.
The material of the formation layer 810 of this syntonizer 850 is 2.6～40 by making relative permittivity, in the band territory from hundreds of MHz to number GHz, can obtain desired resonance characteristic.In addition, wish to suppress as far as possible the material unaccounted-for (MUF) of syntonizer, so tangent of the dielectric loss angle (tan δ) is preferably 0.0025～0.0075.Formation layer 810 as such preferably uses above-mentioned composite dielectric layer.
Figure 70 represents the equivalent-circuit diagram of the syntonizer of above-mentioned the 23rd～26 embodiment.In Figure 70, syntonizer is connected on the end of the syntonizer 984,941 that is made of coaxial road or stripline with HOT terminal 981, and is connected with GND terminal 982 on the other end.
(the 27th embodiment)
Figure 71 is the square pie graph of the 27th embodiment of expression electron device of the present invention, is illustrated in the example that uses electron device of the present invention on the mobile terminal machine.
In the mobile terminal machine 1000 shown in Figure 71, the transmission signal of being sent by Base Band Unit 1010 mixes with RF signal from hybrid circuit 1021 by frequency mixer 1001.Be connected with voltage control oscillating circuit (VCO) 1020 on this hybrid circuit 1021, constitute combiner circuit, to supply with the RF signal of assigned frequency with phase locking circuit 1019.
Utilize frequency mixer 1001 to carry out the synthetic transmission signal of RF through bandpass filter (BPF) 1002, by power amplifier 1003 amplification.The coupled device of the part of the output of this power amplifier 1,003 1004 takes out, adjust to the level of regulation with losser 1005 after, be transported to once more in the power amplifier 1003, the gain that is adjusted into power amplifier keeps necessarily.The transmission signal process of being sent by unitor 1004 prevents that shield retaining (isolater) 1006, low-pass filter 1007 that adverse current is used are imported into duplexer (duplexer) 1008, launches from the antenna 1009 that connects therewith.
On the other hand, the received signal that is transported to antenna 1009 is transported to the amplifier 1011 from duplexer 1008, by the level of amplification to regulation.Be transported to the frequency mixer 1013 through bandpass filter 1012 from the received signal of amplifier 1011 outputs.In this frequency mixer 1013, through bandpass filter (BPF) 1022 input rf signals, remove the RF signal content, carry out demodulation from hybrid circuit 1021.Through SAW wave filter 1014, after amplifier 1015 is by amplification, be imported into frequency mixer 1016 from the received signal of frequency mixer 1013 output.The local letter signal of assigned frequency is imported into frequency mixer 1016 from local transmitting circuit 1018, and above-mentioned received signal is transformed into the frequency of regulation, in amplifier 1017 by amplification to the regulation level after, be sent to Base Band Unit.
Above-mentioned mobile terminal device 1000, as the antenna front end that comprises antenna 1009, duplexer 1008, low-pass filter 1007 (front end) assembly (with reference to the dotted line of Figure 71) 1200, or comprise shield retaining 1006, unitor 1004, with shield retaining power amplifier component (aisolater power amplifier module) (with reference to the dotted line of Figure 71) 1100 of losser 1005, power amplifier 1003, above-mentioned antenna or power amplifier can be used, electric hybrid module (hybrid module) can be constituted thus.In addition, will as the RF unit, can constitute the device that contains integrant in addition method as the 22nd embodiment shown in like that, the BPF of Figure 71, VCO etc. also can use the VCO shown in the 9th～12 embodiment and the 19th embodiment etc.
When on the mobile terminal machine, carrying the electron device of present embodiment as described above, utilize the miniaturization of electron device can make 1000 miniaturizations of mobile terminal machine.In addition, the flexural strength of the electron device of present embodiment is good, thus when electron device is installed, can fully prevent electron device damaged and even distortion etc.And, even the electron device of present embodiment at high temperature use also can fully prevent capacitance characteristic through the time change, so, also can keep its performance for a long time even at high temperature use mobile terminal machine 1000.
(the 28th embodiment)
Then, explain the 28th embodiment of the present invention.
Figure 76 is the partial cross section figure of the 28th embodiment of expression electron device of the present invention.
In Figure 76,, represented to possess multilager base plate 1110 and the power magnification 1100 of the electrical element 1120a, the 1120b that on multilager base plate 1110, are provided with as electron device.
Multilager base plate 1110 has the two-layer formation of outermost layer layer (the 1st dielectric layer) 1110a, 1100g, between two-layer outermost layer 1110a, 1100g, dispose resiniferous multilayer (being 3 layers in the present embodiment) and constitute layer (the 2nd a dielectric layer) 1110b～1110f.In addition, multilager base plate 1110 on the surface that constitutes layer 1110a, constitute layer 1110a and constitute between the layer 1110b, constitute layer 1110b and constitute between the layer 1110c, constitute layer 1110c and constitute between the layer 1110d, constitute layer 1110d and constitute between the layer 1110e, constitute layer 1110e and constitute between the layer 1110f, constitute between layer 1110f and the formation layer 1110g and constitute layer and have conductor layer 1130a～1130h respectively on the surface of 1110g.Constituting layer 1110a～1110g, conductor layer 1130a～1130h is constituted by lamination.
In above-mentioned multilager base plate 1110, the limit amount of deflection that constitutes layer 1110a, 1110g is to constitute more than 1.3 times of 1110b～1110f of layer, and the tangent of the dielectric loss angle tan δ that constitutes layer 1110b～1110f is below 0.01.
That is, multilager base plate 1110 comprises formation layer 1110a, 1110g that physical strength is good and the formation layer 1110b～1110f of good electric performance.Therefore, after goodsization,, when also can keep electrical characteristic well, can prevent the damaged generation in the multilager base plate 1110 in the power amplifier 1100 fully even power amplifier 1100 is applied excessive load.In other words, as long as utilize power magnification 1100, just can improve its characteristic fully.
In addition, usually under the situation of crooked multilager base plate, how disrumpent feelings from the top layer part, the ratio that the intensity of multilager base plate depends on outermost intensity is very big, but in multilager base plate 1110, constitute the outermost layer that a layer 1110a, 1110g become multilager base plate 1110 by what the big material of physical strength constituted, so can prevent the disrumpent feelings of multilager base plate 1110 more fully.
In addition, when the limit amount of deflection that constitutes layer 1110a, 1110g is discontented with 1.3 times that constitute layer 1110b～1110f, be difficult to link together the damaged generation of the multilager base plate 1110 in the time of can not preventing to apply excessive loads fully with the intensity rising of multilager base plate 1110.In addition, when the tangent of the dielectric loss angle tan δ that constitutes layer 1110b～1110f surpasses 0.01, be that situation below 0.01 is compared with tan δ, the Q value of power amplifier 1100 reduces significantly, can not keep good electrical characteristic.
Constitute the limit amount of deflection of layer 1110a, 1110b,, be preferably more than 1.5 times of 1110b～1110f of formation layer, but also be preferably below 20 times from the viewpoint that the physical strength that makes power amplifier 1100 increases.When limit amount of deflection surpassed 20 times, it is difficult that the operation on operation becomes.In addition, the tangent of the dielectric loss angle tan δ of formation layer 1110b～1110f is preferably below 0.005.At this moment, compare above 0.005 situation with tan δ, it is better that electrical characteristic can become.
Constituting the layer resin that 1110b～1110f contained is not particularly limited.As this resin, for example can enumerate tetrafluoroethylene, aromatic liquid-crystal polyester, polyphenylene sulphite, polyvinyl benzylic ether compound, Vinylstyrene, fumarate, polyphenylene oxide (ether), cyanate ester, Bismaleimide Triazine, polyether-ether-ketone, polyimide etc.In addition, as above-mentioned resin, can use Resins, epoxy and mixture with active ester cured resin of high Q value.
But, except that above-mentioned resin, constitute a layer 1110b～1110f and also can contain and compare the big ceramic powder of specific inductivity with this resin.At this moment, even under the situation of using the little resin of specific inductivity, in constituting layer 1110b～1110f, also can make tangent of the dielectric loss angle tan δ is below 0.01.
Such ceramic powder can be divided into dielectric ceramic powder and magnetic substance powder.
Above-mentioned dielectric ceramic powder is the metal oxide powder that contains at least a metal that is selected from magnesium, silicon, aluminium, titanium, zinc, calcium, strontium, zirconium, barium, tin, neodymium, bismuth, lithium, samarium and tantalum, be preferably specific inductivity and be 3.7～300, the Q value is 500～100,000 metal oxide powder.
When the relative permittivity of metal oxide powder is discontented with 3.7, the relative permittivity that can not improve composite dielectric layer, the miniaturization that is difficult to realize electron device, light-weighted tendency are arranged.When the relative permittivity of metal oxide powder surpasses 300, Q value is discontented 500 the time, when electron device 1100 excessive heating are arranged in use, the tendency of conveyance loss reduction.In addition, above-mentioned dielectric ceramic powder constitutes with single crystal or many crystallizations usually.
Concrete example as above-mentioned dielectric ceramic powder, except that as the concrete example of the dielectric ceramic powder that above-mentioned composite dielectric layer contained and enumerate, also can enumerate the material with insulativity of silicon-dioxide, glass, oxyhydroxide (aluminium hydroxide, magnesium hydroxide etc.) etc.The shape of dielectric ceramic powder can be spherical, broken shape, flakey, acicular any shape.
As above-mentioned dielectric ceramic powder, be preferably with TiO 2, CaTiO 3, SrTiO 3, BaO-Nd 2O 3-TiO 2, BaO-CaO-Nd 2O 3-TiO 2, BaO-SrO-Nd 2O 3-TiO 2, BaO-Sm 2O 3-TiO 2, BaTi 4O 9, Ba 2Ti 9O 20, Ba 2(Ti, Sn) 9O 20, MgO-TiO 2, ZnO-TiO 2, MgO-SiO 2, Al 2O 3Composition be the material of major ingredient, identical with the dielectric ceramic powder that is contained in the above-mentioned composite dielectric layer.With above-mentioned composition is that the dielectric ceramic powder of major ingredient both can use separately also and can be used in combination more than two kinds.
The median size of above-mentioned dielectric ceramic powder, from above-mentioned composite dielectric layer the identical reason of dielectric ceramic powder that contained, be preferably in the scope of 0.01～100 μ m, more preferably in the scope of 0.2～20 μ m.
In addition, the addition of above-mentioned dielectric ceramic powder, from with above-mentioned composite dielectric layer the identical reason of dielectric ceramic powder that contained, with respect to organic insulation 100 parts by volume, be preferably the scope of 5～185 parts by volume, in this scope, specific inductivity as required and tangent of the dielectric loss angle select suitable amount to get final product.
On the other hand, the magnetic substance powder can be given magnetic properties to constituting layer 1110b～1110f, reduces linear expansivity, improve the strength of materials.
As the concrete example of above-mentioned magnetic substance powder, can enumerate with above-mentioned composite dielectric layer in the identical material of magnetic substance powder that contained.They both can use separately more than use two kinds also capable of being combined.
The median size of above-mentioned magnetic substance powder, from above-mentioned composite dielectric layer the same reason of magnetic substance powder that contained, be preferably in the scope of 0.01～100 μ m, more preferably in the scope of 0.2～20 μ m.
In addition, from above-mentioned composite dielectric layer the identical reason of magnetic substance powder that contained, the addition of magnetic substance powder is preferably the scope of 5～185 parts by volume with respect to organic insulation 100 parts by volume, selects suitable amount to get final product in this scope.
As constituting the layer resin that 1110a, 1110g contained, except that constituting the layer resin that 1110b～1110f contained, can enumerate Resins, epoxy or phenolic resin etc., except that above-mentioned resin, also can contain the ceramic powder bigger than this resin specific inductivity but constitute layer 1110a, 1110g.But as a formation layer 1110a, when 1110g contains a large amount of ceramic powder, the limit amount of deflection that constitutes layer 1110a, 1110g is difficult to become formation layer more than 1.3 times of 1110b～1110f.On the other hand, when constituting layer 1110a, when 1110g contains a large amount of ceramic powder, further improving electrical characteristic.Therefore, be preferably and suitably add ceramic powder, specifically,, preferably add ceramic powder 100～200 parts by volume with respect to resin 100 parts by volume.
In addition, as constituting the layer resin that 1110b～1110f contained, when using benzyl ether compound, compare with benzyl ether compound that flexural strength is big, crooked elastic rate is low, be heat-curing resin, from compare the closer reason of solidification value with other resin, preferably use Resins, epoxy as constituting the layer resin that 1110a, 1110g contained.
In above-mentioned multilager base plate 1110, the stripping strength that constitutes layer 1110a, 1110g is preferably more than 1.5 times of stripping strength that constitute layer 1110b～1110f.At this moment, after the goodsization, even power amplifier 1100 is applied excessive load, when also can keep electrical characteristic well, what can prevent from fully in the multilager base plate 1110 to take place is damaged, in addition, compare with discontented 1.5 times situation, or further improve the constant intensity and the stripping strength of being moved of real dress-active element ( electrical element 1120a, 1120b), or further improve multilager base plate 1110 and as the intensity as the conductor layer 1130h of electrode of the power amplifier 1100 of electron device.
The stripping strength that constitutes layer 1110a, 1110g more preferably constitutes more than 2 times of stripping strength of layer 1110b～1110f.But the stripping strength that constitutes layer 1110a, 1110g is preferably below 20 times of stripping strength that constitute layer 1110b～1110f.When the stripping strength that constitutes layer 1110a, 1110g surpassed 20 times of the stripping strength that constitutes layer 1110b～1110f, conductor layer (for example Copper Foil) must become quite thick, and the high frequency characteristic of power magnification 1100 is produced baneful influence.
The stripping strength that constitutes layer 1110a, 1110g is preferably more than the 8N/cm particularly, more preferably more than the 10N/cm.At this moment, compare with the situation of the discontented 8N/cm of stripping strength that constitutes layer 1110a, 1110g, obtain following advantage: more be difficult to cause damaged because of as the stress of electrical element 1120a, the 1120b of real dress parts, or as problems such as peeling off of the conductor layer 1130h of terminal.
The stripping strength that constitutes layer 1110a, 1110g is preferably below the 100N/cm.When the stripping strength that constitutes layer 1110a, 1110g surpassed 100N/cm, conductor layer (for example Copper Foil) must become quite thick, to the high frequency characteristic generation baneful influence of power magnification 1100.
In addition, in Figure 76, constitute layer 1110d and have the cloth 1131 that constitutes by reinforcing fiber, constitute central substrate.The material of this cloth 1131 and thickness are as mentioned above.
Constitute the material of above-mentioned conductor layer 1130a～1130h so long as electro-conductive material just is not particularly limited,, can enumerate Cu, Ni, Al, Au, Ag etc. as such electro-conductive material.Cu more preferably wherein.This be because the internal resistance of Cu little, be difficult to cause migration (migration).In addition, as electrical element 1120a, 1120b, for example use electrical condenser, inducer, semi-conductor, resistor etc.
Above-mentioned multilager base plate 1110 can use the modus operandi manufacturing of common printed base plate such as combination (build up) modus operandi, a lamination modus operandi.
(the 29th embodiment)
Figure 77 is the perspective oblique drawing of electrical condenser of the 29th embodiment of expression electron device of the present invention, and Figure 78 is the partial cross section figure of electrical condenser of the 29th embodiment of expression electron device of the present invention.
In Figure 77, Figure 78, electrical condenser 1200 possesses: lamination constitute layer 1200a～1200g and the layered product that forms; Constituting the conductor layer 23 that forms on layer 1200b～1200g; The end electrode 22 that on the both sides of layered product, is provided with respectively.And contiguous inner conductor 23 is connected respectively on the different end electrode 22.In addition, be provided with land pattern 21 at the two ends of end electrode 22.In addition, constitute layer 1200a, 1200g and be made of the same material of a layer 1100a, 1100b that constitutes with above-mentioned the 27th embodiment, each constitutes layer 1200b～1200f and is made of the same material of layer 1110b～1110f that constitutes with the 27th embodiment.That is, the limit amount of deflection that constitutes layer 1200a, 1200g is to constitute more than 1.3 times of 1200b～1200f of layer, and the tangent of the dielectric loss angle tan δ that constitutes layer 1200b～1200f is below 0.01.Therefore, as long as utilize this electrical condenser 1200, even after goodsization electrical condenser 1200 is applied excessive load, when also can keep electrical characteristic well, it is damaged to prevent fully that electrical condenser 1200 from taking place.
In order to make electrical condenser 1200 high capacities, each constitutes the specific inductivity that layer 1200a～1200g needs to improve as far as possible the material that constitutes layer 1200b～1200f, therefore, with respect to constituting the resin that is contained among layer 1200b～1200f, preferred compound ceramic powder with specific inductivity higher than this resin.In addition, when electrical condenser 1200 is used in the purposes that applies the high frequency electromagnetic field, the Q of electrical condenser 1200 is also many to the situation that electrical characteristic impact, so under these circumstances, it is as far as possible little to be preferably tan δ, for this reason, and as the resin that constitutes layer 1200b～1200f, select the little resin of tan δ of resin self, but the compound low ceramic powder of tan δ of comparing with resin gets final product.As such resin or ceramic powder, can use the resin or the ceramic powder of the 27th embodiment.Each constitute layer 1200a, 1200g both can be identical also can be different, select optimal combination to get final product.In addition, each constitute layer 1200b～1200f both can be identical also can be different, select optimal combination to get final product.
In addition, to the integrant mark same-sign identical or equal, omit repeat specification with above-mentioned embodiment.
(the 30th embodiment)
Figure 79 is the perspective oblique drawing of inducer of the 30th embodiment of expression electron device of the present invention, and Figure 80 is the partial cross section figure of inducer of the 30th embodiment of expression electron device of the present invention.
In Figure 79, Figure 80, inducer 1300 possesses: lamination constitute layer 1300a～1300e and the layered product that forms; Constituting inner conductor 13a～13 (conductor layer) d that is provided with on layer 1300b～1300e; Be used to be electrically connected the through hole 14 of this inner conductor 13a～13d.In addition, constitute coil pattern (conductive element portion) by inner conductor 13 and through hole 14.
Constitute layer 1300a, the 1300e material formation same with formation layer 1110a, the 1110g of above-mentioned the 28th embodiment, each constitutes layer 1300b～1300d material formation same with the formation layer 1110b～1110f of the 28th embodiment.That is, the limit amount of deflection that constitutes layer 1300a, 1300g is to constitute more than 1.3 times of 1300b～1300d of layer, and the tangent of the dielectric loss angle tan δ that constitutes layer 1300b～1300d is below 0.01.Therefore, as long as utilize this inducer 1300, even after goodsization inducer 1300 is applied excessive load, when also can keep electrical characteristic well, it is damaged to prevent fully that inducer 1300 from taking place.
In addition, be respectively arranged with end electrode 12 in the relative two sides of layered product, the both ends of coil pattern are connected respectively on each end electrode 12.In addition, be provided with land pattern 11 at the two ends of end electrode 12.
In addition, each constitute layer 1300a, 1300e both can be identical also can be different, select optimal combination to get final product.In addition, each constitutes a layer 1300b～1300d and also is, both can be identical also can be different, select optimal combination to get final product.In addition, to the integrant mark same-sign identical or equal, omit repeat specification with above-mentioned embodiment.
In addition, inner conductor 13a～13d constitutes spirrillum with through hole 14, but removes through hole 14, with inner conductor 13a～13d accumulate one, to constitute bending also passable.Such structure also can be brought into play the function as inducer.
The present invention is not limited to above-mentioned embodiment.Electron device for example of the present invention also can be a magnetic bobbin core except that the electron device that above-mentioned the 1st～the 27th embodiment is put down in writing, toroidal core, disk condenser, feedthrough capacitor, clamping filter (clamp filter), common mode filter filter (common mode filter), the EMC wave filter, the power supply wave filter, pulse transformer, deflection coil, choke coil, the DC-DC transmodulator, retarding line, the electric wave absorbing sheet, slim wave absorber, electromagnetic shielding, diplex machine (diplexer), duplexer (duplexer), the duplexer assembly, antenna front end assemblies (antenna front end module), shield retaining-power amplifier component, the PLL assembly, front end assemblies (front end module), tuner components, directional coupler, double balanced mixer (DBM), power combiner, power divider, toner sensor (toner sensor), current sensor, setter (actuator), sounder (voltage-type sound generator), microphone, receiving apparatus, hummer, the PTC thermistor, Thermal Cutoffs, wustite magnet etc.
In addition, in above-mentioned the 28th～the 30th embodiment, use power amplifier 1100, electrical condenser 1200, inducer 1300 as electron device, but electron device of the present invention is except that above-mentioned power amplifier, electrical condenser, inducer, also applicable VCO, duplexer assembly, front end (front end) assembly, PLL assembly, RF tuner pack, RF unit, overlapping element, TCXO etc.
In addition, in above-mentioned the 28th～the 30th embodiment, outermost limit amount of deflection is that the structure that is disposed between them is stratified more than 1.3 times, if but that outermost stripping strength is the structure that is disposed between them is stratified more than 1.5 times, it is stratified more than 1.3 times that outermost limit amount of deflection may not become the structure that is disposed between them.At this moment also be, even after goodsization, electron device is applied excessive load, when also can keep electrical characteristic well, to prevent fully that electron device from taking place damaged.In addition, to be preferably the structure that is disposed between them stratified below 20 times for outermost stripping strength.When outermost stripping strength surpassed stratified 20 times of the structure be disposed between them, conductor layer (for example Copper Foil) must become quite thick, and the high frequency characteristic of electron device is produced baneful influence.
In addition, in above-mentioned the 28th～the 30th embodiment, two-layer outermost layer all has the stratified limit amount of deflection more than 1.3 times of the structure that is disposed between them, but as long as either party's outermost limit amount of deflection is that above-mentioned structure is stratified more than 1.3 times.At this moment also be, even after goodsization, electron device is applied excessive load, when also can keep electrical characteristic well, to prevent fully that electron device from taking place damaged.
Below, illustrate in greater detail suitable embodiment of the present invention, but the present invention is not limited to these embodiment.
(Production Example A: active ester compound synthetic)
In possessing the 2L split flask (separable flask) of nitrogen ingress pipe, pack into 0.5833 mole in distilled water 900mL and sodium hydroxide (23.33g) utilize the nitrogen ingress pipe that nitrogen is fully bubbled and remove in the distilled water and the interior oxygen of reaction system.Chien shih naphthyl alcohol 0.54 mole (77.85g) is dissolved in wherein when spending 1 hour, obtains naphthyl alcohol solution.Different therewith, 600mL toluene is encased in another flask that is warmed up to 60 ℃ dissolving m-phthalic acid muriate (Tokyo HuaCheng Industry Co., Ltd's system) 0.27 mole (54.82g).
This m-phthalic acid chloride soln is warmed up to 60 ℃, spent 10 seconds and drip to, kept 4 hours, make it reaction with such rotation number with in the above-mentioned naphthyl alcohol solution of paddle blade (paddle blade) with the stirring of 300 revolutions.Reaction is left standstill separatory after finishing, and takes out water.After washing clean 30 minutes toluene phases, leave standstill separatory and repeat 3 times with 0.5% carbonated soda, clean 30 minutes, leave standstill separatory and repeat 3 times with deionized water.Then, intensification with 15 seconds heptane 600mL that drip, separates out two (Alpha-Naphthyl) isophthalic ester after removing and concentrating about toluene 400mL.Filter this precipitate, at room temperature use the methanol cleaning 30 minutes of 300mL,, obtain active ester compound two (Alpha-Naphthyl) isophthalic ester 106g by filtration-drying.Esterification yield is 99.8%.Be " IAAN " to call two (Alpha-Naphthyl) isophthalic ester that obtains in the following text.
(Production Example B: polyarylate synthetic)
The solution that will constitute by the toluene of the methyl trioctylphosphine ammonium chloride of the terephthalyl chloride of terephthalyl chloride, 0.258kg between 1.031kg, 0.057kg and 27.3kg, with by 3 of 1.540kg, 3 '-5, the solution that the sodium hydroxide of 5 '-tetramethyl-bis-phenol, 0.648kg and the de-oxygenised water of 19.2kg constitute mixed under 11 ℃ 30 minutes in the 100L still, made it contact.
Behind the standing separation Generation Liquid, remove water, follow water three clean toluene phases repeatedly.Then the speed of dividing with 10L/ branch, 100L/ respectively in mutually to the toluene that obtains is supplied with weak solvent (badsolvent) methyl alcohol, carries out precipitation operation (separating out of polyarylate) by continous way shears (the high speed dispersor FM-25 of Pacific Ocean machine worker system, blade speed 15m/ second) continuously.Then, collect the polyarylate obtain on filter material, with 80 ℃ warm water cleaning 30 minutes, filter repeatedly three times in still, drying obtains polyarylate then.(0.1g/dL) is 1.5dL/g with the logarithmic specific concentration viscosity of the polyarylate of Ubbelohde viscometer decision under 30 ℃ in chloroform.Below the polyarylate that obtains is called " polyarylate 1 ".
(embodiment A 1)
With BaNd 2TiO 4Be that dielectric ceramic powder (dielectric property of median size 1.6 μ m, gigabit Hz band: ε 90/Q1700, TDK (strain)) 177 weight parts, organic solvent tetrahydrofuran 620 weight parts, coupler KBM573 (SHIN-ETSU HANTOTAI's chemical industry (strain)) 0.9 weight part are encased in 5 liters of beakers, use stirrer to carry out 4 hours stir process.Then, add epoxy resin ICLON HP7200H (big Japanese ink chemical industry (strain)) 174 weight parts, active ester Compound I AAN158 weight part, fire retardant EPICLON152 (big Japanese oily ink chemistry industry (strain)) 48 weight parts, curing catalyst CUREZOL2E4MZ (four countries change into industry (strain)) 1.1 weight parts, stir up to dissolving fully, disperseing, obtain mashed prod (mashed prod A).
On the other hand, 67 weight parts of polyarylate 1 and tetrahydrofuran (THF) 840 weight parts of organic solvent are encased in 2 liters of beakers, stir up to polyarylate and dissolve fully, disperse, obtain mashed prod (mashed prod B).
Then, above-mentioned mashed prod B is encased in the beaker of mashed prod A, is stirred to fully and disperses, obtain mashed prod (mashed prod C).
Use scraping blade (doctor blade) that this mashed prod C is coated on 18 μ m electrolytic copper foils (CF-T9, FUKUDA METAL's paper tinsel industry (strain)) or the 50 μ mPET films, carry out 50 ℃/10 minutes+120 ℃/10 minutes drying treatment.The thickness of the resin combination that obtains is 50 μ m.12 these resin combinations are overlapping, suppress under the condition of " after being warmed up to after 150 ℃ from 30 ℃ with 2 ℃/minute speed, keeping 60 minutes, be warmed up to 190 ℃, keep 60 minutes temperature curve with 3 ℃/minute speed, the pressure of 3MPa, the following vacuum tightness of 30torr " by high-temperature vacuum pressing make-up machine (KVHC type, Beichuan smart machine (strain)).The thickness of the cured article of the resin combination that obtains after the compacting is 500 μ m.
(embodiment A 2～A11)
The material of being put down in writing except that use table 1 (weight of carrying with souvenir), other is identical with embodiment A 1, obtains containing BaNd 2TiO 4It is the cured article of dielectric ceramic powder.
(Embodiment B 1～B8)
The material of being put down in writing except that use table 2 (weight of carrying with souvenir), other is identical with embodiment A 1, obtains containing Ba 2Ti 9O 20It is the cured article of dielectric ceramic powder (dielectric property of median size 1.7 μ m, gigabit Hz band: ε 39/Q9000, TDK (strain)).
(Embodiment C 1～C8)
The material of being put down in writing except that use table 3 (weight of carrying with souvenir), other is identical with embodiment A 1, obtains containing A1 2O 3It is the cured article of dielectric ceramic powder (dielectric property of median size 2.2 μ m, gigabit Hz band: ε 9.8/Q40000, TDK (strain)).
(comparative example 1)
The material of being put down in writing except that use table 2 (weight of carrying with souvenir), other is identical with Embodiment B 5, obtains replacing Resins, epoxy and active ester compound and contains the cured article of the polyvinyl benzylic ether of 332g.
The cured article that use obtains in embodiment A 1～A11, B1～B8 and C1～C8 utilizes following method, tries to achieve specific inductivity, tangent of the dielectric loss angle, second-order transition temperature and water-intake rate.
(specific inductivity and tangent of the dielectric loss angle)
With the bar-shaped sample of cured article, with frequency measurement specific inductivity and the tangent of the dielectric loss angle of empty syntonizer perturbation method (using high frequency dielectric property determinator, Hewlett-Packard (strain) system 83620A and the 8757D of TDK (strain) exploitation), usefulness 2GHz as length 100mm, wide 1.5mm, thick 0.5mm.
(second-order transition temperature)
Measuring method according to JIS C6481, use DSC-50 (Shimadzu Seisakusho Ltd.'s system), with 10 ℃/minute intensifications, in 30 ℃～200 ℃ temperature range, measure, calculate the beginning (onset) of heat release, endothermic curve and the neutral temperature that finishes (endset), try to achieve second-order transition temperature.
(water-intake rate)
With the tabular sample of cured article as length 50mm, wide 50mm, thick 0.5mm, carry out 120 ℃/hour drying under reduced pressure (decompression degree 5torr is following), after the constant temperature that keeps 25 ℃/60%RH decide to place 1 hour in the wet sump, with accurate Libra (ER-182A, grind Seiko already (strain)) mensuration initial stage weight.Then, in the hot and humid groove of 85 ℃/85%RH, place 24 hours, from this groove, take out, decide in the wet sump placement after 1 hour, at the constant temperature that keeps 25 ℃/60%RH with weight behind the above-mentioned accurate Libra determination test.Water-intake rate is calculated according to following formula.
Water-intake rate (%)=(test back weight-initial stage weight)/initial stage weight * 100
In addition, use the mashed prod C in embodiment A 1～A11, B1～B8 and C1～C8, obtain (or be equivalent to mashed prod C material), carry out fluidity test by following method.
(flowability)
On the electrolytic copper foil of 18 μ m, be coated with mashed prod C (or be equivalent to mashed prod C material), carry out 50 ℃/10 minutes+120 ℃/10 minutes drying treatment, make subsidiary resin Copper Foil in the mode of length 100mm, wide 100mm, thick 0.5mm.(the thickness: 2mm) and cushioning material of overlapping successively separating slices (release film), Die and mould plate on the surface of this subsidiary resin Copper Foil and the inside, with high-temperature vacuum pressing make-up machine (KVHC type, the smart machine (strain) of Beichuan), under the condition of " being warmed up to 60 minutes temperature curve of maintenance, the pressure of 3MPa, the vacuum tightness below the 30torr after 150 ℃ with 2 ℃/minute speed from 30 ℃ ", suppress, measure the dimensional change after suppressing, calculate flowability according to following formula.
Area * 100 before mobile (%)=(area before compacting back area-compacting)/compacting
The result of above-mentioned test with the composition of resin combination shown in following table 1～table 3.In addition, as long as the value of the specific inductivity of measuring with above-mentioned condition is 3.0 or more, just can be described as high-k, need only tangent of the dielectric loss angle and be below 0.0045, just can be described as low-dielectric loss angle tangent.In addition, as long as second-order transition temperature is more than 130 ℃, just can claims that this temperature is a high temperature, the value that needs only water-intake rate is below 0.20%, it is low just to can be described as water-intake rate.The hurdle of the flowability of table 1～table 3 records zero and △, and zero means that flowability is more than 101%, and △ means that flowability is more than 100.1% discontented 101%.
Table 1
Embodiment A 1 Embodiment A 2 Embodiment A 3 Embodiment A 4 Embodiment A 5 Embodiment A 6 Embodiment A 7 Embodiment A 8 Embodiment A 9 Embodiment A 10 Embodiment A 11
Resins, epoxy EPICLON-HP7200H 174 174 174 174 174 174 174 174 174 177 174
YX-4000 - - - - - - - - - 75 -
The active ester compound IAAN 158 158 158 158 158 158 158 158 158 240 158
Polyarylate Polyarylate 1 67 67 67 67 67 67 67 67 67 93 67
Fire retardant EPICLON152 48 48 48 48 48 48 48 48 48 36 48
Curing catalyst CUREZOL2E4MZ 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 - - 1.1
DMAP - - - - - - - - 1.1 1.1 -
Organic solvent THF 1460 1460 1460 1460 1460 1460 1460 1460 1460 1460 1460
Dielectric ceramic powder BaNd 2Ti 4O 12System 177 354 708 1062 1415 1769 2123 2300 1415 1971 -
Ba 2Ti 9O 20System - - - - - - - - - - -
Al 2O 3 - - - - - - - - - - -
Surface treatment agent KBM573 0.9 1.8 3.5 5.3 7.1 8.9 10.6 11.5 7.1 9.9 -
Dielectric ceramic powder addition (parts by volume) 5 10 20 30 40 50 60 65 40 40 0
Specific inductivity (2GHz) Perturbation method (empty syntonizer method) 3.2 3.8 5.5 7.9 11.3 15.9 22.0 24.0 11.2 11.2 2.8
Tangent of the dielectric loss angle (2GHz) Perturbation method (empty syntonizer method) 0.0043 0.0042 0.0038 0.0036 0.0033 0.0031 0.0029 0.0027 0.0034 0.0030 0.0048
Mobile ○ ○ ○ ○ ○ ○ ○ △ ○ ○ ○
Second-order transition temperature The DSC method (℃) 132 133 133 133 133 134 134 133 136 134 132
Water-intake rate 85 ℃ of 85%RH * 24 hour (%) 0.19 0.16 0.13 0.09 0.07 0.05 0.04 0.04 0.07 0.07 0.21
EPICLON-HP7200H (dicyclopentadiene-type epoxy resin, epoxy equivalent (weight): 280, big Japanese ink chemical industry society), YX-4000 (bisphenol-type epoxy resin, epoxy equivalent (weight): 186, oiling シ ェ Le ェ Port キ シ society), EPICLON152 (brominated bisphenol a type epoxy resin, epoxy equivalent (weight): 360, bromine containing ratio 45%, big Japanese ink chemical industry society), CUREZOL2EMZ (2-ethyl-4-methylimidazole, four countries change into industrial society), DMAP (dimethyl aminopyridine, Tokyo changes into industrial society), KBM573 (N-phenyl-γ-An Bingjisanyiyangjiguiwan, chemical industry society of SHIN-ETSU HANTOTAI)
Table 2
Embodiment B 1 Embodiment B 2 Embodiment B 3 Embodiment B 4 Embodiment B 5 Embodiment B 6 Embodiment B 7 Embodiment B 8 Comparative example 1
Resins, epoxy EPICLON-HP7200H 174 174 174 174 174 174 174 174 -
YX-4000 - - - - - - - - -
The active ester compound IAAN 158 158 158 158 158 158 158 158 -
The polyvinyl benzylic ether - - - - - - - - 332
Polyarylate Polyarylate 1 67 67 67 67 67 67 67 67 67
Fire retardant EPICLON152 48 48 48 48 48 48 48 48 48
Curing catalyst CUREZOL2E4MZ 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
DMAP - - - - - - - - -
Organic solvent THF 1460 1460 1460 1460 1460 1460 1460 1460 1460
Dielectric ceramic powder BaNd 2Ti 4O 12System - - - - - - - - -
Ba 2Ti 9O 20System 177 354 708 1062 1415 1769 2123 2300 1415
Al 2O 3 - - - - - - - - -
Surface treatment agent KBM573 0.9 1.8 3.5 5.3 7.1 8.9 10.6 11.5 7.1
Dielectric ceramic powder addition (parts by volume) 5 10 20 30 40 50 60 65 40
Specific inductivity (2GHz) Perturbation method (empty syntonizer method) 3.1 3.6 5.0 6.9 9.2 12.1 15.7 17.2 -
Tangent of the dielectric loss angle (2GHz) Perturbation method (empty syntonizer method) 0.0042 0.0041 0.0036 0.0035 0.0034 0.0030 0.0028 0.0027 -
Mobile ○ ○ ○ ○ ○ ○ ○ △ -
Second-order transition temperature The DSC method (℃) 131 133 133 134 134 133 135 134 -
Water-intake rate 85 ℃ of 85%RH * 24 hour (%) 0.2 0.17 0.14 0.1 0.00 0.06 0.05 0.04 -
EPICLON-HP7200H (dicyclopentadiene-type epoxy resin, epoxy equivalent (weight): 280, big Japanese ink chemical industry society), YX-4000 (bisphenol-type epoxy resin, epoxy equivalent (weight): 186, oiling シ ェ Le ェ Port キ シ society), EPICLON152 (brominated bisphenol a type epoxy resin, epoxy equivalent (weight): 360, bromine containing ratio 45%, big Japanese ink chemical industry society), CUREZOL2EMZ (2-ethyl-4-methylimidazole, four countries change into industrial society), DMAP (dimethyl aminopyridine, Tokyo changes into industrial society), KBM573 (N-phenyl-γ-An Bingjisanyiyangjiguiwan, chemical industry society of SHIN-ETSU HANTOTAI)
Table 3
Embodiment C 1 Embodiment C 2 Embodiment C 3 Embodiment C 4 Embodiment C 5 Embodiment C 6 Embodiment C 7 Embodiment C 8
Resins, epoxy EPICLON-HP7200H 174 174 174 174 174 174 174 174
YX-4000 - - - - - - - -
The active ester compound IAAN 158 158 158 158 158 158 158 158
Polyarylate Polyarylate 1 67 67 67 67 67 67 67 67
Fire retardant EPICLON152 48 48 48 48 48 48 48 48
Curing catalyst CUREZOL2E4MZ 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
DMAP - - - - - - - -
Organic solvent THF 1460 1460 1460 1460 1460 1460 1460 1460
Dielectric ceramic powder BaNd 2Ti 4O 12System - - - - - - - -
Ba 2Ti 9O 20System - - - - - - - -
Al 2O 3 177 354 708 1062 1415 1769 2123 2300
Surface treatment agent KBM573 0.9 1.8 3.5 5.3 7.1 8.9 10.6 11.5
Dielectric ceramic powder addition (parts by volume) 5 10 20 30 40 50 60 65
Specific inductivity (2GHz) Perturbation method (empty syntonizer method) 3.0 3.2 3.8 4.4 5.1 5.8 6.5 7.0
Tangent of the dielectric loss angle (2GHz) Perturbation method (empty syntonizer method) 0.004 0.004 0.004 0.003 0.003 0.003 0.003 0.003
Mobile ○ ○ ○ ○ ○ ○ ○ △
Second-order transition temperature The DSC method (℃) 131 132 132 133 132 133 133 134
Water-intake rate 85 ℃ of 85%RH * 24 hour (%) 0.2 0.17 0.13 0.1 0.07 0.06 0.05 0.04
EPICLON-HP7200H (dicyclopentadiene-type epoxy resin, epoxy equivalent (weight): 280, big Japanese ink chemical industry society), YX-4000 (bisphenol-type epoxy resin, epoxy equivalent (weight): 186, oiling シ ェ Le ェ Port キ シ society), EPICLON152 (brominated bisphenol a type epoxy resin, epoxy equivalent (weight): 360, bromine containing ratio 45%, big Japanese ink chemical industry society), CUREZOL2EMZ (2-ethyl-4-methylimidazole, four countries change into industrial society), DMAP (dimethyl aminopyridine, Tokyo changes into industrial society), KBM573 (N-phenyl-γ-An Bingjisanyiyangjiguiwan, chemical industry society of SHIN-ETSU HANTOTAI)
For Embodiment B 5 and comparative example 1, measure flexural strength (according to JISC6481), crooked elastic rate (according to JISC6481) and Copper Foil stripping strength (according to JISC6481).The result who obtains is shown in above table 4.In addition, for Embodiment B 5, the bar-shaped sample of measuring the size of specific inductivity heated 1000 hours down at 125 ℃, with above-mentioned same condition under measure from the heating beginning after 240 hours, after 500 hours and the specific inductivity after 1000 hours, try to achieve poor with the specific inductivity that does not add heat determination.The result who obtains is shown in Figure 81.Shown in Figure 81, about the cured article of Embodiment B 5, the rising of the specific inductivity when at high temperature keeping for a long time is very little.
Table 4
Embodiment B 5 Comparative example 1
Flexural strength (MPa) 125 85
Crooked elastic rate (GPa) 9.0 11.0
Copper Foil stripping strength (N/cm) 10.0 6.0
(embodiment 1)
With BaNd 2TiO 4Be that dielectric ceramic powder (dielectric property of median size 1.6 μ m, gigabit Hz band: ε 90/Q1700, TDK (strain)) 177 weight parts, organic solvent tetrahydrofuran 620 weight parts, coupler KBM573 (SHIN-ETSU HANTOTAI's chemical industry (strain)) 0.9 weight part are encased in 5 liters of beakers, use stirrer to carry out 4 hours stir process.Then, add epoxy resin ICLON HP7200H (big Japanese ink chemical industry (strain)) 174 weight parts, active ester Compound I AAN158 weight part, fire retardant EPICLON152 (big Japanese ink chemical industry (strain)) 48 weight parts, curing catalyst CUREZOL2E4MZ (four countries change into industry (strain)) 1.1 weight parts, stir up to dissolving fully, disperseing, obtain mashed prod (mashed prod D).
On the other hand, 67 weight parts of polyarylate 1 and tetrahydrofuran (THF) 840 weight parts of organic solvent are encased in 2 liters of beakers, stir up to polyarylate and dissolve fully, disperse, obtain mashed prod (mashed prod E).
Then, above-mentioned mashed prod E is encased in the beaker of mashed prod D, stirs, obtain mashed prod (mashed prod F) up to disperseing fully.
This mashed prod F is coated on the 2116 type woven fiber glass (NEA2116, thickness: 100 μ m, day east weaving (strain)), carries out 50 ℃/10 minutes+120 ℃/10 minutes drying treatment, obtain prepreg (prepreg).The thickness of the prepreg that obtains is 170 μ m.3 these prepregs are overlapping, with high-temperature vacuum pressing make-up machine (KVHC type, the smart machine (strain) of Beichuan), under the condition of " after being warmed up to after 150 ℃ with 2 ℃/minute speed from 30 ℃, keeping 60 minutes, be warmed up to after 190 ℃, keep 60 minutes temperature curve; the pressure of 3MPa, the following vacuum tightness of 30torr ", suppress, obtain laminar cured resin with 3 ℃/minute speed.The thickness of the laminar cured resin that obtains is 500 μ m.
(embodiment 2～9)
The material of being put down in writing except that use table 5 (weight of carrying with souvenir), other is identical with embodiment 1, obtains containing BaNd 2TiO 4Be the prepreg and the laminar cured resin of dielectric ceramic powder.
(embodiment 10)
The material of being put down in writing except that use table 5 (weight of carrying with souvenir), other is identical with embodiment 1, obtains containing Ba 2Ti 9O 20Be the prepreg and the laminar cured resin of dielectric ceramic powder (dielectric property of median size 1.7 μ m, gigabit Hz band: ε 39/Q9000, TDK (strain)).
(embodiment 11)
The material of being put down in writing except that use table 5 (weight of carrying with souvenir), other is identical with embodiment 1, obtains containing Al 2O 3Be the prepreg and the laminar cured resin of dielectric ceramic powder (dielectric property of median size 2.2 μ m, gigabit Hz band: ε 9.8/Q40000, TDK (strain)).
The laminar cured resin that use obtains in embodiment 1～11 utilizes the method identical with embodiment A 1, tries to achieve specific inductivity, tangent of the dielectric loss angle, second-order transition temperature and water-intake rate.
In addition, use the mashed prod F in embodiment 1～9, obtain (or be equivalent to mashed prod F material), carry out the test of fillibility-cementability by following method.
(fillibility-cementability)
With mashed prod F is that the mode of 0.17mm is coated on the 2116 type woven fiber glass (NEA2116, thickness: 100 μ m, day east weaving (strain)) with thickness, carries out 50 ℃/10 minutes+120 ℃/10 minutes drying treatment, makes prepreg.(the thickness: 2mm) and cushioning material of the electrolytic copper foil (CF-T9, FUKUDA METAL's industry (strain)) of overlapping successively thickness 18 μ m, Die and mould plate on the surface of this prepreg and the inside, with high-temperature vacuum pressing make-up machine (KVHC type, the smart machine (strain) of Beichuan), under the condition of " being warmed up to after 150 ℃, keeping 60 minutes temperature curve, the pressure of 3MPa, the following vacuum tightness of 30torr from 30 ℃ ", suppress with 2 ℃/minute speed.Like this, the making layer pressing plate substrate of tinsel (two sides subsidiary) is observed inner fillibility with SEM, by stripping metal paper tinsel in the scope of 100mm * 100mm, the cementability of tinsel is estimated.
The result of above-mentioned test is shown in the following table 5 with forming.In addition, as long as the value of the specific inductivity of measuring with above-mentioned condition is 3.6 or more, just can be described as high-k, need only tangent of the dielectric loss angle and be below 0.05, just can be described as low-dielectric loss angle tangent.In addition, as long as second-order transition temperature is more than 120 ℃, just can claims that this temperature is a high temperature, the value that needs only water-intake rate is below 0.1%, it is low just to can be described as water-intake rate.The hurdle of the fillibility-cementability of table 5 record zero and △, zero mean be filled very close to each otherly and prepreg between bonding good; △ means and finds bonding and incomplete between part gap, prepreg.
Table 5
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
Resins, epoxy EPICLON-HP7200H 174 174 174 174 174 174 174 174 177 174 174
YX-4000 - - - - - - - - 75 - -
The active ester compound IAAN 158 158 158 158 158 158 158 158 240 158 158
Polyarylate Polyarylate 1 67 67 67 67 67 67 67 67 93 67 67
Fire retardant EPICLON152 48 48 48 48 48 48 48 48 38 48 48
Curing catalyst CUREZOL2E4MZ 1.1 1.1 1.1 1.1 1.1 1.1 1.1 - - 1.1 1.1
DMAP - - - - - - - 1.1 1.1 - -
Organic solvent THF 1460 1460 1460 1460 1460 1460 1460 1460 1460 1460 1460
Dielectric ceramic powder BaNd 2Ti 4O 12System 177 354 708 1062 1415 1769 1730 1415 1971 - -
Ba 2Ti 9O 20System - - - - - - - - - 1415 -
Al 2O 3 - - - - - - - - - - 1415
Surface treatment agent KBM573 0.9 1.8 3.5 5.3 7.1 8.9 8.7 7.1 9.9 7.1 7.1
Dielectric ceramic powder addition (parts by volume) 5 10 20 30 40 50 55 40 40 40 40
Specific inductivity (2GHz) Perturbation method (empty syntonizer method) 3.6 4 4.8 6.8 9.7 12.3 13.1 10.2 10.1 8.1 4.7
Tangent of the dielectric loss angle (2GHz) Perturbation method (empty syntonizer method) 0.0031 0.0033 0.0036 0.0038 0.0038 0.0040 0.0042 0.0038 0.0030 0.0033 0.003
Fillibility-cementability ○ ○ ○ ○ ○ ○ △ ○ ○ - -
Second-order transition temperature The DSC method (℃) 133 134 133 133 134 133 132 133 135 134 132
Water-intake rate 85 ℃ of 85%RH * 24 hour (%) 0.08 0.07 0.06 0.05 0.04 0.04 0.04 0.04 0.04 0.05 0.04
EPICLON-HP7200H (dicyclopentadiene-type epoxy resin, epoxy equivalent (weight): 280, big Japanese ink chemical industry society), YX-4000 (bisphenol-type epoxy resin, epoxy equivalent (weight): 186, oiling シ ェ Le ェ Port キ シ society), EPICLON152 (brominated bisphenol a type epoxy resin, epoxy equivalent (weight): 360, bromine containing ratio 45%, big Japanese ink chemical industry society), CUREZOL2EMZ (2-ethyl-4-methylimidazole, four countries change into industrial society), DMAP (dimethyl aminopyridine, Tokyo changes into industrial society), KBM573 (N-phenyl-γ-An Bingjisanyiyangjiguiwan, chemical industry society of SHIN-ETSU HANTOTAI)
(embodiment 12)
With Ba 2Ti 9O 20Be that dielectric ceramic powder (dielectric property of median size 1.7 μ m, gigabit Hz band: ε 39/Q9000, TDK (strain)) 1415 weight parts, organic solvent tetrahydrofuran 620 weight parts, coupler KBM573 (SHIN-ETSU HANTOTAI's chemical industry (strain)) 7.1 weight parts are encased in 5 liters of beakers, use stirrer to carry out 4 hours stir process.Then, add epoxy resin ICLON HP7200H (big Japanese ink chemical industry (strain)) 174 weight parts, active ester Compound I AAN158 weight part, fire retardant EPICLON152 (big Japanese ink chemical industry (strain)) 48 weight parts, curing catalyst CUREZOL2E4MZ (four countries change into industry (strain)) 1.1 weight parts, stir up to dissolving fully, disperseing, obtain mashed prod (mashed prod G).
On the other hand, 67 weight parts of polyarylate 1 and tetrahydrofuran (THF) 840 weight parts of organic solvent are encased in 2 liters of beakers, stir up to polyarylate and dissolve fully, disperse, obtain mashed prod (mashed prod H).
Then, above-mentioned mashed prod H is encased in the beaker of mashed prod G, stirs, obtain mashed prod (mashed prod I) up to disperseing fully.
Use scraping blade that this mashed prod I is coated on 18 μ m electrolytic copper foils (CF-T9, FUKUDA METAL's paper tinsel industry (strain)) or the 50 μ mPET films, carry out 50 ℃/10 minutes+120 ℃/10 minutes drying treatment.The thickness of the film that obtains is 50 μ m.With 12 these film overlaies, with high-temperature vacuum pressing make-up machine (KVHC type, the smart machine (strain) of Beichuan), under the condition of " after being warmed up to after 150 ℃ with 2 ℃/minute speed from 30 ℃, keeping 60 minutes, be warmed up to after 190 ℃, keep 60 minutes temperature curve, the pressure of 3MPa, the following vacuum tightness of 30torr ", suppress with 3 ℃/minute speed.The thickness of the laminar cured article that obtains after the compacting is 500 μ m.
(comparative example 2)
The material of being put down in writing except that use table 6 (weight of carrying with souvenir), other is identical with embodiment 12, obtains replacing Resins, epoxy and active ester compound and contains the cured article of the polyvinyl benzylic ether of 332g.In addition, in table 6, be the material (society of Asahi Chemical Industry system) of the hydrogenation of styrene-butadiene-styrene triblock copolymer as the flexible TuftecH1043 that gives the material use, SAYTEX, BT93 are the two tetrabromo phthalimides (ALBEMARLE society system) of ethene.
The laminar cured article that use obtains in embodiment A 12 utilizes the method identical with the foregoing description A1, tries to achieve specific inductivity, tangent of the dielectric loss angle, second-order transition temperature and water-intake rate.
In addition, the flexural strength of thin slice cured article (MPa) is measured according to JIS C6481.
The result of above-mentioned test is shown in the following table 6 with the composition of resin combination.In addition, as long as the value of the specific inductivity of measuring with above-mentioned condition is 3.6 or more, just can be described as high-k, need only tangent of the dielectric loss angle and be below 0.05, just can be described as low-dielectric loss angle tangent.In addition, as long as second-order transition temperature is more than 120 ℃, just can claims that this temperature is a high temperature, the value that needs only water-intake rate is below 0.1%, it is low just to can be described as water-intake rate.
Table 6
Embodiment 12 Comparative example 2
Resins, epoxy - 174 -
The active ester compound - 158 -
The polyvinyl benzylic ether - - 344
The flexible material of giving Polyarylate 67 -
Tuftec H1043 - 86
Fire retardant EPICLON152 48 -
SAYTEX BT93 - 122
Curing catalyst CUREZOL2E4MZ 1.1 -
Dicumyl peroxide - 5.2
Organic solvent THF 1390 -
Toluene - 1967
Dielectric ceramic powder Ba 2Ti 9O 20System 1415 1415
Surface treatment agent KBM573 7.1 7.1
The dielectric ceramic powder amount Volume % 40 40
Specific inductivity (2GHz) Perturbation method (empty resonant method) 9.2 8.8
Tangent of the dielectric loss angle (2GHz) Perturbation method (empty resonant method) 0.0034 0.0029
Second-order transition temperature (℃) The DSC method 134 192
Water-intake rate (%) 85 ℃ 85%RH24 hour 0.08 0.05
Flexural strength (MPa) - 125 98
As shown in table 6, the flexural strength of the thin slice cured article of embodiment 12 is big, and the flexural strength of the thin slice cured article of comparative example 2 is little.Think thus: be difficult to cause distortion or damaged etc. during electron device that operation is made of the thin slice cured article of embodiment 12.
(embodiment 13)
As described below, making is as the power amplifier component of the electron device shown in Figure 82.In addition, in Figure 82, the integrant mark same-sign identical or equal with Figure 76.
At first, will be with following constitutional formula (I)
Figure C20038010777700811
(in the above-mentioned formula (I), R 1Be methyl, R 2Be benzyl, R 3Be vinyl benzyl, n is 3) vinyl benzyl resin (polyvinyl benzylic ether compound (VB)) and the Tuftec H1043 of molecular weight about 6000 of expression put into toluene, stir up to dissolving fully.Then, wherein put into SATYEXBT93, dicumyl peroxide, BaNd 2Ti 4O 12The zirconia ball 200g of (median size 0.2 μ m, relative permittivity 93), KBM573 and 20mm φ mixed 4 hours with ball mill.
Obtain mashed prod (hereinafter referred to as " mashed prod J ") thus.At this moment, the containing ratio of the ceramic powder among the mashed prod J is about 40 volume %.Then, mashed prod J is coated on the 12 μ m electrolytic copper foils (JTM, day ore deposit マ テ リ ア Le ズ (strain)),, obtains the thin slice that thickness is 50 μ m (hereinafter referred to as " thin slice A ") 120 ℃ of drying treatment of carrying out 5 minutes with scraping blade.As described above, prepare 4 identical thin slice A.In addition, the specific inductivity of mashed prod J is about 10, tan δ is about 0.0025.In addition, measure flexural strength, crooked elastic rate and the stripping strength of thin slice A, its flexural strength is 80MPa, and crooked elastic rate is 8GPa.Stripping strength is counted 4.2N/cm with 12 μ m Copper Foils.In addition, measure the limit amount of deflection of thin slice A, its limit amount of deflection is 3.6mm.In addition, flexural strength is according to measuring with above-mentioned same method, and crooked elastic rate is measured according to JIS K6911.
On the other hand, Resins, epoxy obtains mashed prod (hereinafter referred to as " mashed prod K ") with compound by dissolving the ceramic powder that silicon-dioxide constitutes (electrochemical industry FB-3SX).At this moment, the containing ratio of the ceramic powder among the mashed prod K is about 15 volume %.Then, mashed prod K is coated on the 12 μ m electrolytic copper foils (JTM, day ore deposit MATERIARUZU (strain)),, obtains the thin slice that thickness is 50 μ m (hereinafter referred to as " thin slice B ") 110 ℃ of drying treatment of carrying out 5 minutes with scraping blade.Prepare 2 thin slice B as described above.The specific inductivity of mashed prod K is about 3.2, tan δ is about 0.011.In addition, measure flexural strength, crooked elastic rate and the stripping strength of thin slice B, its flexural strength is that 140Mpa, crooked elastic rate are 5GPa.Stripping strength is counted 11N/cm with 12 μ m Copper Foils, is 2.2 times of stripping strength of thin slice A.In addition, the limit amount of deflection of thin slice B is 5.7mm, is 2.3 times of thin slice A.In addition, flexural strength, crooked elastic rate and stripping strength are according to measuring with above-mentioned same method.
Then, between 2 thin slice B, configuration is about core (core) substrate of the thickness 150 μ m that the woven fiber glass 1131 of 95 μ m constitutes by mashed prod D and thickness, disposes 2 thin slice A between 2 thin slice B and core substrate respectively.Then, overlapping thin slice A, core substrate and thin slice B, use high-temperature vacuum pressing make-up machine (KVHC type, the smart machine (strain) of Beichuan), in condition: when keeping pressing pressure 4Mpa, with 3 ℃/minute speed heat up the back, 150 ℃ keep down 40 minutes, with 4 ℃/minute speed heat up the back, keep down suppressing under 180 minutes at 200 ℃.Obtain thus by constituting the multilager base plate 1110 that layer 1110a～1110g and conductor layer 1130a～1130h constitute.
Then, on multilager base plate 1110, as semi-conductive hollow sheet (bare chip) 1120a of electrical element with built-in amplification circuit, after terminal conjunction method (wirebonding) installation, with this hollow sheet of resin combination 1140 mold pressings (mold) 1120a of Resins, epoxy and silicon-dioxide formation.And, will be installed on the multilager base plate as the chip capacitor 1120b of electrical element.Obtain the power amplifier component 1100 shown in Figure 82 thus.
(comparative example 3)
Except that all replace thin slice A with thin slice B, other is identical with embodiment 13, obtains power amplifier component.Therefore, the outermost limit amount of deflection of this power amplifier component is 1 times of its la m, and outermost stripping strength is 1 times of its la m.
(electrical characteristic and mechanical characteristic test)
To the embodiment 13 that obtains by aforesaid method and the power amplifier component of comparative example 3, carry out the test of electrical characteristic and mechanical characteristics in accordance with the following methods.
That is, testers such as signal generator, power meter, frequency spectrum analyser are used in the test of electrical characteristic, measure output level, efficient, distortion etc.On the other hand, horizontal pressure degree, pliability test, adhesion test, the stripping test of installation parts chip capacitor 1120b all measured in the test of mechanical characteristics according to JIS C7210.
Its result is as can be known: the power amplifier component of embodiment 13 and comparative example 3 is all kept good electrical characteristic.With respect to this as can be known: the power amplifier component of embodiment 13 is compared with the power amplifier component of comparative example 3, can prevent damaged generation fully.
Utilizability on the industry
As mentioned above, as long as according to resin combination of the present invention, cured resin, laminar cured resin, layered product, prepreg, electronic device and multilager base plate, just can fully improve the characteristic of electronic device.

Claims (10)

1. multilager base plate is characterized in that:
Lamination contain resin the 1st dielectric layer of one deck at least, contain the 2nd dielectric layer of one deck at least of resin and one deck conductor layer and constituting at least,
The tangent of the dielectric loss angle tan δ of described the 2nd dielectric layer is below 0.01,
The limit amount of deflection of described the 1st dielectric layer is more than 1.3 times of described the 2nd dielectric layer.
2. multilager base plate as claimed in claim 1 is characterized in that:
Described the 2nd dielectric layer also contains compares the big ceramic powder of relative permittivity with described resin.
3. multilager base plate as claimed in claim 1 or 2 is characterized in that:
Have two-layer outermost layer, described two-layer outermost one deck at least constitutes with described the 1st dielectric layer, disposes described the 2nd dielectric layer of one deck at least between described two-layer outermost layer.
4. multilager base plate as claimed in claim 1 or 2 is characterized in that:
The stripping strength of described the 1st dielectric layer is more than 1.5 times of stripping strength of described the 2nd dielectric layer.
5. electron device is characterized in that:
Lamination contain resin the 1st dielectric layer of one deck at least, contain the 2nd dielectric layer of one deck at least of resin and one deck conductor layer and constituting at least,
The tangent of the dielectric loss angle tan δ of described the 2nd dielectric layer is below 0.01,
The limit amount of deflection of described the 1st dielectric layer is more than 1.3 times of described the 2nd dielectric layer.
6. electron device as claimed in claim 5 is characterized in that:
Described the 2nd dielectric layer also contains compares the big ceramic powder of relative permittivity with described resin.
7. as claim 5 or 6 described electron devices, it is characterized in that:
Have two-layer outermost layer, described two-layer outermost one deck at least is made of described the 1st dielectric layer, disposes described the 2nd dielectric layer of one deck at least between described two-layer outermost layer.
8. as claim 5 or 6 described electron devices, it is characterized in that:
The stripping strength of described the 1st dielectric layer is more than 1.5 times of stripping strength of described the 2nd dielectric layer.
9. electron device as claimed in claim 8 is characterized in that:
The stripping strength of described the 1st dielectric layer is more than the 8N/cm.
10. electron device is characterized in that possessing:
The described multilager base plate of each of claim 1～4;
Be arranged on the electrical element on the described multilager base plate.
CNB2003801077778A 2002-12-27 2003-12-26 Resin composition, cured resin, sheet-like cured resin, laminated body, prepreg, electronic parts and multilayer boards Expired - Fee Related CN100348661C (en)

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