CN1665966A - Method of forming polymide coating containing dielectric filler on surface of metallic material process for producing copper clad laminate for formation of capacitor layer for printed wiring board and - Google Patents
Method of forming polymide coating containing dielectric filler on surface of metallic material process for producing copper clad laminate for formation of capacitor layer for printed wiring board and Download PDFInfo
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- CN1665966A CN1665966A CN038152487A CN03815248A CN1665966A CN 1665966 A CN1665966 A CN 1665966A CN 038152487 A CN038152487 A CN 038152487A CN 03815248 A CN03815248 A CN 03815248A CN 1665966 A CN1665966 A CN 1665966A
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- polyimide
- copper foil
- mulch film
- dielectric
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/0929—Conductive planes
- H05K2201/09309—Core having two or more power planes; Capacitive laminate of two power planes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
- H05K2203/1333—Deposition techniques, e.g. coating
- H05K2203/135—Electrophoretic deposition of insulating material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Electroplating Methods And Accessories (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
A method of forming a dielectric layer containing dielectric filler, which is excellent in film thickness uniformity, from a polyimide electrodeposition liquid containing dielectric filler. In particular, a method of forming a polyimide coating containing dielectric filler on a surface of metallic material according to the electrodeposition coating technique, characterized in that as the dielectric filler, use is made of dielectric powder of perovskite structure in approximately spherical form which has an average particle diameter (D1A) of 0.05 to 1.0 mum and a weight cumulative particle diameter (D50), measured in accordance with the laser diffraction scattering type particle size distribution measuring method, of 0.1 to 2.0 mum and further exhibits an aggregation degree, in terms of D50/D1A wherein D50 and D1A represent a weight cumulative particle diameter and an average particle diameter obtained by image analysis, respectively, of 4.5 or less.
Description
Technical field
The present invention relates to form the formation method of the polyimide mulch film contain dielectric filler and capacitor layer that printing distributing board is used and form the manufacture method of copper-clad laminate of usefulness and the copper-clad laminate that makes by this manufacture method at metal material surfaces such as copper.
Background technology
In recent years, generally, use copper-clad laminate, adopt the method identical to form capacitor arrangement, used as built-in electrical condenser with forming circuitry shapes at the interior layer segment of printing distributing board, particularly multi-layer printed circuit board.Form capacitor arrangement by interior layer segment at multi-layer printed circuit board, just can save the electrical condenser that is configured in outer layer surface, realize miniaturization, the densification of outer circuit, the surface mount component number is reduced, be easy to make printing distributing board with close interval circuit.
The method that forms capacitor arrangement with copper-clad laminate is, use so-called two-sided copper-clad laminate, this copper-clad laminate is made of the copper foil layer and the dielectric layer between this two copper foil layer on two sides, the copper foil layer corrosion processing on its two sides is become the electrode for capacitors of desired shape, form the capacitor arrangement of state that dielectric layer is clipped in the capacitor electrode interpolar on two sides in the target location.
As the most basic specification of quality, require electrical condenser to have big as far as possible electric capacity.Capacitor volume (C) can be by formula C=ε ε
0(A/d) (ε
0Specific inductivity for vacuum) calculates.Therefore, increase, can 1. increase the surface-area (A) of electrode for capacitors in order to make condenser capacity.2. reduce dielectric layer thickness (d).3. increase the relative permittivity (ε) of dielectric layer.Can adopt any method wherein.
But, with regard to 1. surface-area (A), the trend along with nearest electronics, compactization of electric installation also has same requirement to printing distributing board, therefore will be in certain printing distributing board area, the area that a sizable part is used as electrode for capacitors almost is impossible.And for 2. reducing dielectric layer thickness (d), so long as dielectric layer contains framework materials such as glass fabric, as epoxy resin impregnated frit etc., thin layerization will be restricted because of the influence of framework material.And if only use dielectric layer constituent material in the past and save framework material, then when utilizing corrosion to make electrode for capacitors, can produce following unfavorable condition, promptly the dielectric layer of having removed on the position of copper foil layer in corrosion is destroyed because of the injection pressure that is subjected to etching solution.Owing to there are above-mentioned these problems, 3. therefore general consideration increases the relative permittivity (ε) of dielectric layer.
Promptly, in the formation of dielectric layer, with framework materials such as glass fabrics as must composition, utilize the realization thin layerizations such as nonwovenization of framework material, reduce the thickness of dielectric layer integral body, and make dielectric filler disperse to be included in the constituent material of dielectric layer formed resin etc. by employing, realize the increase of condenser capactiance.
But, along with the further high capacity of the electric capacity of built-in electrical condenser, it is thin and thickness and precision is high that dielectric layer thickness is established in expectation, and have the manufacture method that flexible capacitor layer that the injection of the etching solution in the time of bearing corrosion processing presses forms the copper-clad laminate of usefulness.
In order to make the copper-clad laminate that the capacitor layer that can satisfy these conditions forms usefulness, worked out as the disclosed method of Japanese Patent Te Open 2001-15883 communique.This method is: use the polyimide electroplate liquid that contains dielectric filler to be formed on the dielectric layer that contains dielectric filler in the polyimide resin by the electro dipping method in the one side of Copper Foil, the Copper Foil of fitting on this dielectric layer again, the aforementioned polyimide electroplate liquid that contains dielectric filler is included in the polyimide electroplate liquid dielectric filler and forms.
But, directly use the polyimide electroplate liquid to utilize the electro dipping method to form the polyimide mulch film on the surface of copper, though compare with coating method, the thickness this respect is highly beneficial reducing, but still quite difficult in actual applications, polyimide plating itself just is difficult to stably operate.And, electroplate by the dielectric filler powder is included in the polyimide electroplate liquid, make the powder of dielectric filler powder be evenly dispersed in the polyimide mulch film then difficulty more, in actual production, can't realize mass.
From the above problem, wish to find and a kind ofly when manufacturing is used to form the dielectric medium of copper-clad laminate of capacitor layer, use the polyimide electroplate liquid that contains dielectric filler, form the technology of the good dielectric layer of thickness and precision.
Summary of the invention
The present inventor is through further investigation, found as follows form the formation method of the polyimide mulch film that contains dielectric filler and printing distributing board at metal material surfaces such as copper and form the manufacture method of the copper-clad laminate of usefulness, unexistent in the past copper-clad laminate can be provided with capacitor layer by adopting.
Record in the claims: " form the method for the polyimide mulch film that contains dielectric filler at metal material surface; it is to use the polyimide electroplate liquid that contains dielectric filler; form the method for the polyimide mulch film that contains dielectric filler at metal material surface by the electro dipping method; it is characterized in that the aforementioned polyimide electroplate liquid that contains dielectric filler is contained in the polyimide electroplate liquid dielectric filler and forms; Dielectric filler adopts and is the dielectric medium powder that approximate globular has perovskite structure, the median size D of this dielectric medium powder
IAThe weight build-up particle diameter D that is 0.05～1.0 μ m, records by laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and adopt weight build-up particle diameter D
50With the median size D that obtains by image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5 ".
That the electro dipping method of polyimide resin is believed on metal to form homogeneous and do not have the mulch film of defective such as pin hole, also can be used in and form complex-shaped homogeneous mulch film.Polyimide in the past is dissolved in solvent hardly, therefore with the state of its presoma polyamic acid, carries out electro dipping, utilizes heat to carry out cyclodehydration, forms polyimide film.But, polyamic acid instability, easily decomposition.Therefore in the present invention, better adopt the anion electroplating application of having used the many blocks polyimide that dissolves in the solvent that contains side carboxyl to carry out with the polyimide electroplate liquid of composition etc.Therefore, this polyimide electroplate liquid can be joined in market, and the polyimide electroplate liquid of Chu Shouing also has very excellent performance on the market.
When using this polyimide electroplate liquid on metal, to form the polyimide mulch film, because of the different plating property of kind of metal different.Therefore, must be according to the lining body that will form the polyimide mulch film, promptly the kind of metallic substance is prepared the polyimide electroplate liquid.Particularly on as the copper product of metallic substance when the electro dipping method forms the polyimide mulch film, if the particle diameter of the colloidal particle of many blocks polyimide is thinless in the polyimide electroplate liquid, then can not forms homogeneous and not have the good mulch film of pin hole.Therefore, must consider to electroplate the kind of polyimide, wait the miniaturization that realizes colloidal particle by increasing quantity of solvent according to this.But the particle diameter of the colloidal particle in the polyimide electroplate liquid is also relevant with the thickness of formed polyimide mulch film, therefore must be formulated in the suitable scope, with the equilibrium of polyimide mulch film thickness that keeps the ultimate aim product and plating property.
In addition in the present invention, also should consider the dispersiveness of the dielectric filler of dispersing and mixing in this polyimide electrolytic solution, determine the solution proterties of polyimide electrolytic solution.But with present state of the art, can form homogeneous on metallic substance and not have the kind of the polyimide electroplate liquid that contains many blocks polyimide of good polyimide mulch film of pin hole limited, the modulation range of its composition is also limited.
Therefore, present inventor's decision is guaranteed the good dispersiveness of dielectric filler powder in the polyimide electroplate liquid by the powder properties that improves dielectric filler.The used dielectric filler of the present invention is the dielectric filler that disperses to be present in the polyimide mulch film that contains dielectric filler, is used for bringing into play finally the function as the dielectric layer of electrical condenser, increases the electric capacity of the electrical condenser when being processed into the electrical condenser shape.This dielectric filler uses BaTiO
3, SrTiO
3, Pb (Zr-Ti) O
3(common name PZT), PbLaTiO
3PbLaZrO (common name PLZT), SrBi
2Ta
2O
9(common name SBT) etc. has the dielectric medium powder of the composite oxides of perovskite structure.
The powder characteristics of this dielectric filler at first must be the scope of particle diameter at 0.05～1.0 μ m.Here so-called particle diameter, owing to formed certain 2 times certain state of aggregations between powder, use is from the low precision of the particle diameter of the indirect measurement gained of the measured value supposition median size of laser diffraction and scattering formula particle size distribution method or BET method etc., thereby can't use, so refer to this SEM picture be carried out the median size of image analysis gained with scanning electron microscope (SEM) direct viewing dielectric filler.In this specification sheets, with particle diameter D at this moment
IAExpression.In addition, the image analysis of the dielectric filler powder that gets with scanning electron microscope (SEM) observation post in this manual is: with the IP-1000PC of Asahi Engineering Co., Ltd.'s system, carry out the round particle analysis with circularity threshold value 10, degree of overlapping 20, in the hope of median size D
IA
In addition, requirement is to be the dielectric medium powder that approximate globular has perovskite structure, the weight build-up particle diameter D that this dielectric medium powder is recorded by laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and adopt weight build-up particle diameter D
50With the median size D that obtains by image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
The weight build-up particle diameter D that records by laser diffraction and scattering formula particle size distribution method
50Be meant use that laser diffraction and scattering formula particle size distribution method records reach 50% o'clock particle diameter in weight build-up, this weight build-up particle diameter D
50Value more little, then the shared ratio of fine powder is just many more in the size distribution of dielectric filler powder.In the present invention, requiring this value is 0.1 μ m～2.0 μ m.That is weight build-up particle diameter D,
50Value during less than 0.1 μ m, be all tangible cohesion can take place, and can't become the dielectric filler powder that satisfies following condensation degree with the dielectric filler powder which kind of manufacture method makes.On the other hand, weight build-up particle diameter D
50Value when surpassing 2.0 μ m, then can not be, can realize the dielectric filler of target of the present invention as the built-in capacitor layer usefulness that forms printing distributing board.It is thick that the dielectric layer that promptly is used to form the two-sided copper-clad laminate of built-in capacitor layer is generally 10 μ m～25 μ m, and 2.0 μ m are upper limits to make dielectric filler be dispersed in wherein then equably.
Weight build-up particle diameter D among the present invention
50Mensuration be that dielectric filler powder blending dispersion in methyl ethyl ketone, is dropped into this solution laser diffraction and scattering formula particle size distribution device Micro Trac HRA 9320-X100 type (Ri Machine dress Co., Ltd. system then) circulator, measure.
Used this notion of condensation degree here, it is described to introduce the reasons are as follows of this notion.That is, adopt the weight build-up particle diameter D of laser diffraction and scattering formula particle size distribution method gained
50Value be not the value that diameter obtained of every powder of real direct viewing.The powder that constitutes the dielectric medium powder is not the isolating fully so-called single branch loose powder of each particle basically, but the state that is in a plurality of powder cohesions, gathers together.In laser diffraction and scattering formula particle size distribution method, powder agglomerated together is captured as a particle (aggregated particle), calculate the weight build-up particle diameter.
In contrast, look like to carry out the median size D that picture processing obtained by observation to the dielectric medium powder that gets with scanning electron microscope observation post
IADirectly try to achieve owing to observe picture, therefore can capture primary particle exactly, but from another point of view, not reflect the state of aggregation that has powder fully from SEM.
Comprehensive above each point considers that the present inventor determines to adopt the weight build-up particle diameter D of laser diffraction and scattering formula particle size distribution method
50With median size D by the image analysis gained
IA, with by D
50/ D
IAThe value that calculates is as condensation degree.That is, supposing can be with identical precision determination D in a collection of copper powder
50And D
IAValue, consider according to above-mentioned theory, then can think, in measured value, reflect the D that has state of aggregation
50Value be greater than D
IAValue (, also can obtain same result) even in practical measurement.
At this moment, if the state of aggregation completely dissolve of the powder of dielectric filler powder, then D
50Value be infinitely close to D
IAValue, condensation degree D
50/ D
IAValue near 1.Reach for 1 stage at condensation degree, can be described as single branch loose powder of the state of aggregation that does not have powder fully.But in fact condensation degree also can demonstrate the value less than 1 sometimes.Theoretically, can be for less than 1 value under the situation of ball, but actually, because powder is not a spheroidal, therefore can access value less than 1 condensation degree.
In the present invention, require the condensation degree of this dielectric filler powder below 4.5.If this condensation degree surpasses 4.5, then the cohesion degree between the dielectric filler medium silt is too high, is difficult to mix with above-mentioned polyimide electroplate liquid homogeneous.
As the manufacture method of dielectric filler powder, no matter adopt which kind of method such as alkoxide process, hydrothermal synthesis method, barkite method, owing to all will form certain state of aggregation inevitably, therefore can produce the dielectric filler powder that can not satisfy above-mentioned condensation degree.When particularly adopting the hydrothermal synthesis method of damp process, easily form state of aggregation.Therefore by carrying out the powder of this state of aggregation is separated into the decomposed particles processing of one one powder, can make the state of aggregation of dielectric filler powder be in above-mentioned condensation degree scope.
Iff being in order to carry out the decomposed particles operation, then can adopt various devices such as high energy ball mill, high speed conductor impact type airflow pulverizer, collision type pulverizer, standard grinding machine (gauge mill), medium stirring-type pulverizer, high hydraulic type shredding unit as the means that can carry out decomposed particles.But,, should consider to reduce the viscosity of the polyimide electroplate liquid that contains dielectric filler of the following stated in order to ensure the Combination and the dispersiveness of dielectric filler powder and polyimide electroplate liquid.On the basis of the viscosity of seeking to reduce the polyimide electroplate liquid that contains dielectric filler, also require the specific surface area of powder of dielectric filler little, and smooth.Therefore, though but can not adopt decomposed particles, when decomposed particles, can damage the powder surface, the decomposed particles device that its specific surface area is increased.
Based on this understanding, the present inventor is through research back discovery in depth, and two kinds of methods are effective.The something in common of these two kinds of methods be by with the touch controls of parts such as the inwall of the powder of dielectric filler powder and device, agitating vane, crushing medium in inferior limit, make the powder collision mutually to each other of cohesion, thus decomposed particles fully.That is, partly contact the surface that can damage powder with the inwall that installs, agitating vane, crushing medium etc., surfaceness is increased, therefore the degree of sphericity deterioration will prevent this situation.Can adopt by making powder collision fully take place between mutually, separately be in the powder of state of aggregation, the collision of powder between mutually simultaneously can make the method for powder surface smoothing.
The first is utilized jet mill that the dielectric filler powder that is in state of aggregation is carried out decomposed particles and is handled.Here said " jet mill " is meant the high velocity air that uses air, and the dielectric filler powder is imported in this air-flow, and powder is run foul of each other in this high velocity air, carries out the decomposed particles operation.
Be in addition, adopt the fluid pulverizer that utilizes centrifugal force, can not destroy formed slurry in its stoichiometric solvent, carry out decomposed particles and handle being dispersed in by the dielectric filler powder that is in state of aggregation.Said here by adopting " utilizing the fluid mill of centrifugal force " makes this slurry flow at high speed, just like the circular orbit that draws, utilizes the centrifugal force that is at this moment produced to make the powder collision mutually in solvent to each other of cohesion, carries out the decomposed particles operation.To finish slurry cleaning, filtration, the drying of above-mentioned decomposed particles operation, just can obtain to finish the dielectric filler powder that decomposed particles is handled.Adopt above-described method, can realize the smoothing of the powder surface of the adjustment of condensation degree and dielectric filler powder.
Mix above-described polyimide electroplate liquid and dielectric filler, form the polyimide electroplate liquid that contains dielectric filler.At this moment the polyimide electroplate liquid and the blending ratio of dielectric filler as claimed in claim, the content that contains the dielectric filler in the polyimide electroplate liquid of dielectric filler is preferably 50g/L～350g/L.
Under the situation of content less than 50g/L of dielectric filler, specific inductivity when forming electrical condenser is low excessively, can not satisfy desired in the market relative permittivity 20, if and the content of dielectric filler surpasses 350g/L, the containing ratio of the polyimide resin in the then formed polyimide mulch film that contains dielectric filler became low, adaptation between influence and the applying Copper Foil thereon is difficult to form electrical condenser.
In present stage, if consider from the manufacturing accuracy as powder, this dielectric filler better adopts the barium titanate in the composite oxides with perovskite structure.At this moment dielectric filler can use burnt barium titanate or without in the incinerating barium titanate any one.When going for high-k, better use burnt barium titanate, can select to use according to the design requirements of electrical condenser.
In addition, the barium titanate dielectric filler preferably has the crystalline structure of cube crystalline substance.The crystalline structure that barium titanate had has cube crystalline substance and regular crystal, use has the barium titanate dielectric filler of cube crystal structure and compares the value stabilization of the specific inductivity of the final dielectric layer that obtains with the situation of using the barium titanate dielectric filler that only has square crystal structure.Therefore, we can say and to use the barium titanate powder that has cube crystalline substance and two kinds of crystalline structure of regular crystal at least simultaneously.
By adopting the polyimide electroplate liquid that contains dielectric filler of above explanation, utilize the electro dipping method to form the polyimide mulch film that contains dielectric filler on the surface of copper product, even so surface of copper product, contain at this that dielectric filler is not concentrated in a place but homodisperse yet in polyimide mulch film of dielectric filler, and the polyimide mulch film self that contains dielectric filler also has the thickness of slick surface and homogeneous, zero defect.
In addition, as claimed in claim, " form the method for the polyimide mulch film contain dielectric filler at metal material surface; it is to use the polyimide electroplate liquid that contains dielectric filler; form the method for the polyimide mulch film that contains dielectric filler by the electro dipping method at metal material surface, the aforementioned polyimide electroplate liquid that contains dielectric filler is included in the polyimide electroplate liquid dielectric filler and forms; It is characterized in that, form the nickel of copper product or the metal seed layer of cobalt, on this metal seed layer, use contains the polyimide electroplate liquid of dielectric filler, utilize the electro dipping method to form the polyimide mulch film that contains dielectric filler at metal material surface, the aforementioned polyimide electroplate liquid that contains dielectric filler contain as being of dielectric filler approximate globular have the dielectric medium powder of perovskite structure, the median size D of this dielectric medium powder
IAThe weight build-up particle diameter D that is 0.05～1.0 μ m, records by laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and adopt weight build-up particle diameter D
50With the median size D that obtains by image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5 ".By adopting aforesaid method, can make the thickness homogeneity of the polyimide mulch film that contains dielectric filler on the metallic substance better.
This difference that contains the formation method of the formation method of polyimide mulch film of dielectric filler and preceding a kind of polyimide mulch film that contains dielectric filler is: form the metal seed layer of nickel or cobalt in advance on the surface of metallic substance, and then form the polyimide mulch film that contains dielectric filler.Since all identical in others, therefore to the no longer repeat specification of identical part, describe and only difference is promptly formed metal seed layer.Adopt under the situation of electro dipping method, the good nickel of the plating of extremely thin polyimide mulch film or the metal level of cobalt are set on metallic substance.In this manual, this metal level is called metal seed layer.Form metal seed layer at metal material surface and can adopt the whole bag of tricks such as drying process such as electrolytic process, sputter vapour deposition method, there is no particular limitation.
By setting in advance this metal seed layer,, also can form very good polyimide mulch film even be considered to be difficult to form the copper product surface of polyimide mulch film with the plating finishing.The possibility that adopts the final polyimide mulch film that contains dielectric filler that forms of the present invention to produce defective is extremely low, and the thickness homogeneity is significantly improved.
By adopting the aforesaid formation method that on metallic substance, forms the polyimide mulch film, dielectric filler is not concentrated in a place but homodisperse in containing the polyimide mulch film of dielectric filler, can reduce the fluctuation because of the caused specific inductivity in position in working area (work size) plane thus.And, because the polyimide mulch film that contains dielectric filler self has the thickness of slick surface and homogeneous, therefore when forming electrical condenser, acquisition is fitted in the adhesivity of the homogeneous of the electrode materialss such as Copper Foil on the polyimide mulch film that contains dielectric filler easily, thereby obtains not having the product of manufacturing defect.By adopting this formation method that on metallic substance, forms the polyimide mulch film, can also make thickness as the polyimide mulch film that contains dielectric filler of dielectric layer is thickness arbitrarily, thereby can make the product that has good electric capacity and have the high capacitance quality.
The capacitor layer that the above-described technological thought that forms the formation method of polyimide mulch film on metallic substance can be applied to printing distributing board forms in the manufacture method of copper-clad laminate of usefulness.Promptly, described in the claim: " capacitor layer used of printing distributing board forms the manufacture method of the copper-clad laminate of usefulness; it is to have the manufacture method that capacitor layer that the printing distributing board of layer structure of polyimide dielectric layer/the 2nd Copper Foil of the 1st Copper Foil/contain dielectric filler uses forms the copper-clad laminate of usefulness; it is characterized in that; use the Copper Foil with the polyimide mulch film that contains dielectric filler; form the Copper Foil with Kapton of Kapton with the side surface at the 2nd Copper Foil, the polyimide mulch film face that contains dielectric filler of aforementioned Copper Foil with the polyimide mulch film that contains dielectric filler and the aforementioned Kapton face of having the Copper Foil of Kapton is joined carry out overlapping lamination; Aforementioned is the polyimide electroplate liquid that contains dielectric filler by use with the Copper Foil of polyimide mulch film that contains dielectric filler, forms on the surface of the 1st Copper Foil through the electro dipping method to contain the polyimide mulch film of dielectric filler and form; Above-mentioned electroplate liquid be by the polyimide electroplate liquid and as being of dielectric filler the dielectric medium powder of approximate globular with perovskite structure mix; The median size D of above-mentioned dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and operating weight accumulation particle diameter D
50Median size D with the image analysis gained
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5 ".
The mode chart of the flow process of this manufacture method is seen Fig. 1.In addition, clear understandable for the explanation that makes manufacture method, accompanying drawing extremely illustrates to medelling with the form of section.What here will declare in advance especially a bit is that thickness, size etc. is not the value that verily reflects the material object in the actually operating.Because basic thinking and the above-mentioned formation method that forms the polyimide mulch film that contains dielectric filler on metallic substance are identical, therefore only describe with regard to the manufacturing sequence of copper-clad laminate.
With reference to Fig. 1, following this manufacture method is described.Surface at the 1st Copper Foil CF1 forms the polyimide mulch film 2 that contains dielectric filler, as the Copper Foil 3 with the polyimide mulch film that contains dielectric filler.At this moment form the polyimide mulch film 2 used polyimide electroplate liquids that contain dielectric filler contain dielectric filler and be in the polyimide electroplate liquid, add as being of dielectric filler the dielectric medium powder uniform mixing of approximate globular with perovskite structure form the median size D of this dielectric medium powder
IAThe weight build-up particle diameter D that is 0.05～1.0 μ m, records by laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and adopt weight build-up particle diameter D
50With the median size D that obtains by image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
Adopt this polyimide electroplate liquid that contains dielectric filler, utilize the electro dipping method to form the polyimide mulch film 2 that contains dielectric filler, obtain Copper Foil 3 with the polyimide mulch film that contains dielectric filler.
On the other hand, side surface at the 2nd Copper Foil CF2, finally want the thick Kapton 4 of residual 1～3 μ m, but solvent is removed and resin flows (resin flow) when considering drying and during pressurization, makes 2～3 times the Copper Foil 5 with Kapton that thickness is about target thickness.At this moment,, adopt the polyimide electroplate liquid that does not contain the aforementioned electric medium filler, utilize the electrolysis finishing, form 2～3 times the Kapton 4 that thickness is about final thickness in the one side of the 2nd Copper Foil CF2.When this Kapton 4 is fitted at polyimide mulch film 2 following and that contain dielectric filler, play the effect of tackiness agent.Here, if the final Kapton 4 after the pressurization processing is less than 1 μ m, then be difficult to cover fully the concavo-convex bonding plane of having of Copper Foil, if and Kapton 4 is more than 3 μ m, then because Kapton 4 self does not contain dielectric filler, therefore the specific inductivity of the final dielectric layer that constitutes significantly reduces.
By with above make like this with the Copper Foil 3 of the polyimide mulch film that contains dielectric filler and with the Copper Foil 5 of Kapton by making the state that joins with the polyimide mulch film 2 that contains dielectric filler of the Copper Foil 3 of the polyimide mulch film that contains dielectric filler with the Kapton 4 of the Copper Foil 5 of Kapton opposed, overlapping lamination makes and has the 1st Copper Foil CF1/ and contain the copper-clad laminate that capacitor layer that the printing distributing board of layer structure of polyimide dielectric layer 6/ the 2nd Copper Foil CF2 of dielectric filler uses forms usefulness.
In addition, claim item at other is also being put down in writing: " capacitor layer used of printing distributing board forms the manufacture method of the copper-clad laminate of usefulness; it is to have the manufacture method that capacitor layer that the printing distributing board of layer structure of polyimide dielectric layer/the 2nd Copper Foil of the 1st Copper Foil/contain dielectric filler uses forms the copper-clad laminate of usefulness; it is characterized in that; use the Copper Foil with the polyimide mulch film that contains dielectric filler; form the Copper Foil with Kapton of Kapton with the side surface at the 2nd Copper Foil, the polyimide mulch film face that contains dielectric filler of above-mentioned Copper Foil with the polyimide mulch film that contains dielectric filler and the above-mentioned Kapton face of having the Copper Foil of Kapton is joined carry out overlapping lamination; Above-mentioned Copper Foil with the polyimide mulch film that contains dielectric filler is by form the metal seed layer of nickel or cobalt on the surface of the 1st Copper Foil, on the face that has formed this metal seed layer, use contains the polyimide electroplate liquid of dielectric filler, forms through the electro dipping method to contain the polyimide mulch film of dielectric filler and form; Above-mentioned electroplate liquid be by the polyimide electroplate liquid with as being of dielectric filler the dielectric medium powder of approximate globular with perovskite structure mix; The median size D of this dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and operating weight accumulation particle diameter D
50Median size D with the image analysis gained
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5 ".The mode chart of the flow process of this manufacture method is seen Fig. 2.
The manufacture method of the copper-clad laminate of the manufacture method of the copper-clad laminate of the capacitor layer formation usefulness of this printing distributing board and the capacitor layer formation usefulness of previous described printing distributing board is basic identical, only different on following this aspect.Aspect the 1st Copper Foil CF1, contain in formation before the polyimide mulch film 2 of dielectric filler, form metal seed layer S on the surface of the 1st Copper Foil CF1 in advance.Equally, aspect the 2nd Copper Foil CF2, before forming Kapton 4, form metal seed layer S on the surface of the 2nd Copper Foil CF2 in advance.Because the formation method of this metal seed layer S is identical with the above-mentioned formation method that forms the polyimide mulch film on metallic substance, therefore for fear of repeat specification, no longer explains here.
The junction surface of employed the 1st Copper Foil CF1 and the 2nd Copper Foil CF2 is to be used for the face that engages with dielectric layer 6 in the above manufacture method, has concavo-convexly usually, and this concavo-convex effect is to submerge in the dielectric layer 6, plays fixed effect.The state that adheres to for fine shot copper shown in the figure, in order to keep the homogeneous of dielectric layer thickness, the employed Copper Foil of copper-clad laminate that constitutes capacitor layer better adopts the smooth as far as possible goods of alligatoring face of Copper Foil.Therefore, better use ultralow rugosity (VLP, very low profile) Copper Foil, rolled copper foil etc.That stain is represented in the drawings is dielectric filler F.
Though in fact by use 2 above-mentioned with the Copper Foils of polyimide mulch film that contain dielectric filler, separately the polyimide mulch film that contains dielectric filler is overlaped to each other, pressurize, also can make copper-clad laminate.But, adopt the manufacture method of above-described copper-clad laminate, can produce the dielectric layer that contains dielectric filler can be the goods of any thickness and thickness homogeneous, can form dielectric layer as thin as a wafer.The dielectric layer of the copper-clad laminate that the present invention relates in addition is owing to be the Kapton that is dispersed with dielectric filler, thereby the feature that fully possesses polyimide resin is high strength and flexibility, the embrittlement phenomenon can not take place in dielectric layer like this, sprays the caused damage of etching solution in the time of can preventing to form capacitor circuit.
Description of drawings
Fig. 1 is the cross section mode chart of the manufacturing process of the capacitor layer of the printing distributing board copper-clad laminate that forms usefulness.
Fig. 2 is the cross section mode chart of the manufacturing process of the capacitor layer of the printing distributing board copper-clad laminate that forms usefulness.
Fig. 3 is the observation by light microscope picture that the capacitor layer of printing distributing board forms the copper-clad laminate of usefulness.
Embodiment
Below, form the copper-clad laminate of usefulness by the capacitor layer of making printing distributing board, the present invention is described.
Embodiment 1
In the present embodiment, made the copper-clad laminate 1 of the capacitor layer formation usefulness of printing distributing board according to manufacturing process shown in Figure 1.In the present embodiment, the 1st Copper Foil CF1 employing nominal thickness is ultralow rugosity (VLP) Copper Foil of 35 μ m.
At first, the surface of the 1st Copper Foil CF1 form contain the polyimide mulch film 2 of dielectric filler before, promptly in the stage of Fig. 1 (a-1), carried out making the cleanup acid treatment and the electrolytic degreasing of the cleaning surfacesization of the 1st Copper Foil CF1 to handle.The method of carrying out cleanup acid treatment is that the 1st Copper Foil CF1 was flooded 1 minute in the sulphuric acid soln of 25 ℃ of liquid temperature, 1M concentration.After cleanup acid treatment, wash.
Then, the alkaline degreasing aqueous solution of the yellow soda ash of use 20g/L, the tertiary sodium phosphate of 5g/L, the liquid temperature that makes this aqueous solution is 50 ℃, with Faradaic current 5A/dm
2Carry out 1 minute skimming treatment, carried out washing, drying then.
Then, the preparation to the polyimide electroplate liquid that contains dielectric filler describes.In the present embodiment,, can be used on the pimelinketone that adds 25wt% among the made polyimide electroplate liquid Q-ED-22-10 of the ピ of Co., Ltd.-ア イ technical study, adjusted the electroplate liquid of colloidal particle size gained as the polyimide electroplate liquid.
In this polyimide electroplate liquid, blending dispersion has the barium titanate powder as dielectric filler F of powder characteristics shown below.Blending ratio is, barium titanate is the 80wt% of the polyimide solids component in the above-mentioned polyimide electroplate liquid that contains dielectric filler.
The powder characteristics of dielectric filler
Median size (D
IA) 0.25 μ m
Weight build-up particle diameter (D
50) 0.5 μ m
Condensation degree (D
50/ D
IA) 2.0
Use the polyimide electroplate liquid that contains dielectric filler that makes as mentioned above, utilize the electro dipping method to form the polyimide mulch film 2 that contains dielectric filler on the junction surface of aforementioned the 1st Copper Foil CF1.At this moment electro dipping condition is that to make the liquid temperature of the polyimide electroplate liquid that contains dielectric filler be that 25 ℃, the 1st Copper Foil CF1 are that anode, stainless steel plate are negative electrode, apply the volts DS of 5V, electrolysis 6 minutes, polyimide resin and dielectric filler F are electroplated simultaneously at copper foil surface, form the thick polyimide mulch film 2 that contains dielectric filler of about 8 μ m, wash then.
Then carry out final drying treatment, promptly in 120 ℃ temperature atmosphere, kept 30 minutes, again this atmosphere temperature is risen to 180 ℃, kept 30 minutes.So just made the Copper Foil 3 shown in Fig. 1 (a-2) with the polyimide mulch film that contains dielectric filler.
On the other hand, the 2nd Copper Foil CF2 adopts the Copper Foil identical with the 1st Copper Foil CF1 and above-mentioned same, carries out cleanup acid treatment, skimming treatment in the stage of Fig. 1 (b-1), makes its drying after the washing.Thereafter, the polyimide electroplate liquid with not containing above-mentioned dielectric filler has formed the thick Kapton 4 of 10 μ m on the surface, junction surface, and the final thickness of this Kapton is 2～3 μ m.Then carry out final drying treatment and above-mentioned same in 120 ℃ temperature atmosphere, kept 30 minutes, again this atmosphere temperature is risen to 180 ℃, kept 30 minutes.So just made the Copper Foil 5 shown in Fig. 1 (b-2) with Kapton.
Shown in Fig. 1 (c) like that will more than make with the polyimide mulch film 2 that contains dielectric filler of the Copper Foil 3 of the polyimide mulch film that contains dielectric filler with Kapton 4 subtends of the Copper Foil 5 of Kapton, lamination, the capacitor layer that has made printing distributing board forms the copper-clad laminate 1 of usefulness.At this moment stacked condition is press pressure 5kg/cm
2, pressed temperature is initially 250 ℃ of heating 30 minutes, keeps 30 minutes after being warming up to 300 ℃ then.
Form with the capacitor layer of the printing distributing board that makes more than the observation by light microscope usefulness copper-clad laminate 1 the cross section the results are shown in Figure 3.At this moment contain the fit together thickness average out to 10 μ m of the dielectric layer 6 that forms of the polyimide mulch film 2 of dielectric filler and Kapton 4, as shown in Figure 3, have the very thickness of homogeneous.
Two sides the 1st copper foil layer CF1 and the 2nd copper foil layer CF2 of the above-mentioned copper-clad laminate that makes 1 are carried out whole,, formed resist layer at its two sides applying dry film.Then, with the capacitor circuit exposure imaging, formed etched pattern at the resist layer on this two sides., with cupric chloride etching solution carry out circuit etching, peel off resist layer then, made capacitor circuit thereafter.When this etching, etching solution sprays presses the destruction that can not cause dielectric layer 6, can access the fine printing distributing board.
Relative permittivity to the dielectric layer 6 that constitutes this capacitor circuit is measured, and the result demonstrates very good value ε=24.7, shows thus to have obtained the high electrical condenser of electric capacity.
Embodiment 2
In this embodiment, made the copper-clad laminate 1 ' of the capacitor layer formation usefulness of printing distributing board according to manufacturing flow chart shown in Figure 2.In the present embodiment, identical with embodiment 1, it is ultralow rugosity (VLP) Copper Foil of 35 μ m that the 1st Copper Foil CF1 adopts nominal thickness.
At first, to carry out the cleanup acid treatment of the 1st Copper Foil CF1 in the stage of Fig. 2 (a-1), operation till the skimming treatment is all identical with embodiment 1, after skimming treatment finishes, the metal seed layer S of nickel is set shown in Fig. 2 (a-2), thereafter the surface as Fig. 2 (a-3) the 1st Copper Foil CF1 that is shown in forms the polyimide mulch film 2 that contains dielectric filler, has made the Copper Foil 3 ' with the polyimide mulch film that contains dielectric filler.At this moment, metal seed layer being set, to contain the formation of polyimide mulch film 2 of dielectric filler later on also identical with embodiment 1.
Therefore, only the formation method of the metal seed layer S of nickel is described.The forming process of metal seed layer S in the present embodiment is: use the nickel chloride hexahydrate of the nickel sulfate hexahydrate compound contain 240g/L, 45g/L, the nickel watt that contains the boric acid of 30g/L to bathe, at pH5,55 ℃ of liquid temperature, current density 2A/dm
2Condition under 1 second kind of electrolysis, form nickel dam as about 100 of metal seed layer S.
On the other hand, the 2nd Copper Foil CF2 adopts the Copper Foil identical with the 1st Copper Foil CF1 and above-mentioned same, carries out cleanup acid treatment, skimming treatment in the stage of Fig. 2 (b-1), makes its drying after the washing.Thereafter, the polyimide electroplate liquid with not containing above-mentioned dielectric filler has formed the thick Kapton 4 of 10 μ m on the surface, junction surface, and the final thickness of this Kapton is 2～3 μ m.Then carry out final drying treatment and above-mentioned same in 120 ℃ temperature atmosphere, kept 30 minutes, again this atmosphere temperature is risen to 180 ℃, kept 30 minutes.So just made the Copper Foil 5 ' shown in Fig. 2 (b-3) with Kapton.
Shown in Fig. 2 (c), with above make with the polyimide mulch film 2 that contains dielectric filler of the Copper Foil 3 ' of the polyimide mulch film that contains dielectric filler with Kapton 4 subtends of the Copper Foil 5 ' of Kapton, lamination, the capacitor layer that has made printing distributing board forms the copper-clad laminate 1 ' of usefulness.At this moment lamination is identical with embodiment 1, therefore for fear of repeat specification, omits the explanation of this part.
Form the cross section of the copper-clad laminate 1 ' of usefulness with the capacitor layer of the printing distributing board that makes more than the observation by light microscope, then, therefore can observe and identical state shown in Figure 3 because metal seed layer S is extremely thin can't observe.Thereby omit to use the explanation of the cross-section state of this copper-clad laminate 1 ' that observation by light microscope arrives.Hence one can see that, in the present embodiment, contains the fit together thickness average out to 9.5 μ m of the dielectric layer 6 that forms of the polyimide mulch film 2 of dielectric filler and Kapton 4, very smooth, and have the very thickness of homogeneous.
Two sides the 1st copper foil layer CF1 and the 2nd copper foil layer CF2 of the above-mentioned copper-clad laminate 1 ' that makes are carried out whole,, formed resist layer at its two sides applying dry film.Then, at the resist layer on this two sides capacitor circuit exposure imaging, formed etched pattern with 1cm * 1cm size., with cupric chloride etching solution carry out circuit etching, peel off resist layer then, made capacitor circuit thereafter.When this corroded, etching solution sprays pressed the destruction that can not cause dielectric layer 6, can access the fine printing distributing board.
Relative permittivity to the dielectric layer 6 that constitutes this capacitor circuit is measured, and the result demonstrates very good value ε=33.6, shows thus to have obtained the high electrical condenser of electric capacity.
Utilize feasibility on the industry
Use the electro dipping method of utilizing of the present invention to form the coated polyimide that contains dielectric filler at metal material surface The method of epiphragma can form thin and homogeneous, the smooth polyimides coverlay that contains dielectric filler. This layer is used When making the dielectric layer of capacitor, high-k can be reached, thereby the carrying of static capacity of capacitor can be realized Height, and defective is few, and quality stability is significantly improved. In addition, by using same technological thought, make Dielectric layer adopts the copper-clad laminate of the polyimides coverlay that contains dielectric filler, and high-quality conduct can be provided The copper-clad laminate of the constituent material of the capacitor layer of printing distributing board.
Claims (11)
1. form the method for the polyimide mulch film that contains dielectric filler at metal material surface, it is with the polyimide electroplate liquid that contains dielectric filler, form the method for the polyimide mulch film contain dielectric filler by the electro dipping method at metal material surface, wherein above-mentioned electroplate liquid is to contain dielectric filler and form in the polyimide electroplate liquid; It is characterized in that dielectric filler adopts and is the dielectric medium powder that approximate globular has perovskite structure, the median size D of this dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and adopt weight build-up particle diameter D
50With the resulting median size D of image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
2. form the method for the polyimide mulch film that contains dielectric filler at metal material surface, it is with the polyimide electroplate liquid that contains dielectric filler, form the method for the polyimide mulch film contain dielectric filler by the electro dipping method at metal material surface, wherein above-mentioned electroplate liquid is to contain dielectric filler and form in the polyimide electroplate liquid; It is characterized in that, on copper product, form the metal seed layer of nickel or cobalt, on this metal seed layer, use contains the polyimide electroplate liquid of dielectric filler, form the polyimide mulch film that contains dielectric filler at metal material surface through the electro dipping method, above-mentioned electroplate liquid contain as being of dielectric filler approximate globular have the dielectric medium powder of perovskite structure, the median size D of this dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and operating weight accumulation particle diameter D
50With the resulting median size D of image analysis
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
3. according to claim 1 and 2ly form the method for the polyimide mulch film contain dielectric filler at metal material surface, it is characterized in that, the content that contains the dielectric filler in the polyimide electroplate liquid of dielectric filler is 50g/L～350g/L.
4. according to each describedly forms the method for the polyimide mulch film contain dielectric filler at metal material surface in the claim 1～3, it is characterized in that dielectric filler is a burnt barium titanate or without the incinerating barium titanate.
5. according to each described method that forms the polyimide mulch film that contains dielectric filler at metal material surface in the claim 1～4, it is characterized in that dielectric filler is the barium titanate of crystalline structure with admixture of simple cube crystalline substance or cube crystalline substance and regular crystal.
6. the capacitor layer used of printing distributing board forms the manufacture method of the copper-clad laminate of usefulness, it is to have the manufacture method that capacitor layer that the printing distributing board of layer structure of polyimide dielectric layer/the 2nd Copper Foil of the 1st Copper Foil/contain dielectric filler uses forms the copper-clad laminate of usefulness, it is characterized in that, use Copper Foil with the polyimide mulch film that contains dielectric filler, with the Copper Foil that forms Kapton at a side surface of the 2nd Copper Foil, the polyimide mulch film face that contains dielectric filler of aforementioned Copper Foil with the polyimide mulch film that contains dielectric filler is joined with the aforementioned Kapton face of having the Copper Foil of Kapton carry out overlapping lamination with Kapton; Aforementioned is the polyimide electroplate liquid that contains dielectric filler by use with the Copper Foil of polyimide mulch film that contains dielectric filler, forms on the surface of the 1st Copper Foil through the electro dipping method to contain the polyimide mulch film of dielectric filler and form; Above-mentioned electroplate liquid be by the polyimide electroplate liquid and as being of dielectric filler the dielectric medium powder of approximate globular with perovskite structure mix; The median size D of above-mentioned dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and operating weight accumulation particle diameter D
50Median size D with the image analysis gained
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
7. the capacitor layer used of printing distributing board forms the manufacture method of the copper-clad laminate of usefulness, it is to have the manufacture method that capacitor layer that the printing distributing board of layer structure of polyimide dielectric layer/the 2nd Copper Foil of the 1st Copper Foil/contain dielectric filler uses forms the copper-clad laminate of usefulness, it is characterized in that, use Copper Foil with the polyimide mulch film that contains dielectric filler, with the Copper Foil that forms Kapton at a side surface of the 2nd Copper Foil, the Kapton face of the polyimide mulch film face that contains dielectric filler of above-mentioned Copper Foil with the polyimide mulch film that contains dielectric filler and above-mentioned Copper Foil with Kapton is joined carry out overlapping lamination with Kapton; Above-mentioned Copper Foil with the polyimide mulch film that contains dielectric filler is by form the metal seed layer of nickel or cobalt on the surface of the 1st Copper Foil, on the face that has formed this metal seed layer, use contains the polyimide electroplate liquid of dielectric filler, forms through the electro dipping method to contain the polyimide mulch film of dielectric filler and form; Above-mentioned electroplate liquid be by the polyimide electroplate liquid with as being of dielectric filler the dielectric medium powder of approximate globular with perovskite structure mix; The median size D of this dielectric medium powder
IABe the measured weight build-up particle diameter D of 0.05～1.0 μ m, laser diffraction and scattering formula particle size distribution method
50Be 0.1～2.0 μ m, and operating weight accumulation particle diameter D
50Median size D with the image analysis gained
IA, with D
50/ D
IAThe value of the condensation degree of expression is below 4.5.
8. form the manufacture method of the copper-clad laminate of usefulness according to the capacitor layer of claim 6 or 7 described printing distributing boards, it is characterized in that, the content that contains the dielectric filler in the polyimide electroplate liquid of dielectric filler is 50g/L～350g/L.
9. form the manufacture method of the copper-clad laminate of usefulness according to the capacitor layer of each described printing distributing board in the claim 6～8, it is characterized in that, dielectric filler is a burnt barium titanate or without the incinerating barium titanate.
10. form the manufacture method of the copper-clad laminate of usefulness according to the capacitor layer of each described printing distributing board in the claim 6～9, it is characterized in that dielectric filler is the barium titanate of crystalline structure with admixture of simple cube crystalline substance or cube crystalline substance and regular crystal.
11. the capacitor layer of printing distributing board forms the copper-clad laminate of usefulness, it is characterized in that, the manufacture method that is formed the copper-clad laminate of usefulness by the capacitor layer of each described printing distributing board in the claim 6～10 makes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002191517A JP4080799B2 (en) | 2002-06-28 | 2002-06-28 | Method for forming polyimide film containing dielectric filler on metal material surface, method for producing copper clad laminate for forming capacitor layer for printed wiring board, and copper clad laminate obtained by the method |
| JP191517/2002 | 2002-06-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1665966A true CN1665966A (en) | 2005-09-07 |
| CN100357496C CN100357496C (en) | 2007-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038152487A Expired - Fee Related CN100357496C (en) | 2002-06-28 | 2003-06-27 | Method of forming polymide coating containing dielectric filler on surface of metallic material process for producing copper clad laminate for formation of capacitor layer for printed wiring board and |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20050161149A1 (en) |
| JP (1) | JP4080799B2 (en) |
| CN (1) | CN100357496C (en) |
| TW (1) | TWI270580B (en) |
| WO (1) | WO2004003259A1 (en) |
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| EP3693493A1 (en) | 2014-03-28 | 2020-08-12 | SiO2 Medical Products, Inc. | Antistatic coatings for plastic vessels |
| CN116982977A (en) | 2015-08-18 | 2023-11-03 | Sio2医药产品公司 | Medicaments and other packages with low oxygen transmission rate |
| WO2017154167A1 (en) * | 2016-03-10 | 2017-09-14 | 三井金属鉱業株式会社 | Multilayer laminate plate and production method for multilayered printed wiring board using same |
| US20180097322A1 (en) * | 2016-09-30 | 2018-04-05 | Faraday&Future Inc. | Flexible bus bar |
| US10964476B2 (en) | 2018-12-27 | 2021-03-30 | Industrial Technology Research Institute | Capacitor with multiple dielectric layers having dielectric powder and polyimide |
| TWI725538B (en) * | 2019-09-04 | 2021-04-21 | 台燿科技股份有限公司 | Metal-clad laminate, printed circuit board, and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322976A (en) * | 1987-02-24 | 1994-06-21 | Polyonics Corporation | Process for forming polyimide-metal laminates |
| EP0663417B1 (en) * | 1993-08-03 | 2000-03-29 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyimide laminate comprising thermoplastic polyimide polymer or thermoplastic polyimide film, and process for producing the laminate |
| DE69832444T2 (en) * | 1997-09-11 | 2006-08-03 | E.I. Dupont De Nemours And Co., Wilmington | Flexible polyimide film with high dielectric constant |
| JP3391268B2 (en) * | 1998-01-20 | 2003-03-31 | 株式会社村田製作所 | Dielectric ceramic and its manufacturing method, and multilayer ceramic electronic component and its manufacturing method |
| JP4265048B2 (en) * | 1999-10-06 | 2009-05-20 | Ｊｓｒ株式会社 | Aqueous dispersion for electrodeposition, high dielectric constant film and electronic component |
| US6657849B1 (en) * | 2000-08-24 | 2003-12-02 | Oak-Mitsui, Inc. | Formation of an embedded capacitor plane using a thin dielectric |
| JP2002356653A (en) * | 2001-05-30 | 2002-12-13 | Jsr Corp | Electrodepositing water dispersion, high dielectric constant film and electronic part |
-
2002
- 2002-06-28 JP JP2002191517A patent/JP4080799B2/en not_active Expired - Fee Related
-
2003
- 2003-06-25 TW TW092117210A patent/TWI270580B/en not_active IP Right Cessation
- 2003-06-27 WO PCT/JP2003/008194 patent/WO2004003259A1/en active Application Filing
- 2003-06-27 CN CNB038152487A patent/CN100357496C/en not_active Expired - Fee Related
- 2003-06-27 US US10/518,030 patent/US20050161149A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100440388C (en) * | 2006-09-01 | 2008-12-03 | 天津理工大学 | Producing ABO3 type perrovskite structure double oxide ion conductor by laser fusion synthetic method |
| CN111235555A (en) * | 2008-12-08 | 2020-06-05 | 株式会社杰希优 | Two-layer flexible copper-clad laminate substrate and method for producing same |
| CN111235555B (en) * | 2008-12-08 | 2022-04-29 | 株式会社杰希优 | Two-layer flexible copper-clad laminate substrate and method for producing same |
| CN114381782A (en) * | 2021-12-29 | 2022-04-22 | 江苏诺德新材料股份有限公司 | Environment-friendly high-Tg low-dielectric copper-clad plate and preparation process thereof |
| CN114381782B (en) * | 2021-12-29 | 2022-10-21 | 江苏诺德新材料股份有限公司 | Environment-friendly high-Tg low-dielectric copper-clad plate and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI270580B (en) | 2007-01-11 |
| WO2004003259A1 (en) | 2004-01-08 |
| JP2004035917A (en) | 2004-02-05 |
| JP4080799B2 (en) | 2008-04-23 |
| TW200402481A (en) | 2004-02-16 |
| US20050161149A1 (en) | 2005-07-28 |
| CN100357496C (en) | 2007-12-26 |
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