CN106427136A - High-dielectric material and preparation method and application thereof - Google Patents
High-dielectric material and preparation method and application thereof Download PDFInfo
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- CN106427136A CN106427136A CN201610872063.5A CN201610872063A CN106427136A CN 106427136 A CN106427136 A CN 106427136A CN 201610872063 A CN201610872063 A CN 201610872063A CN 106427136 A CN106427136 A CN 106427136A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- H05K1/02—Details
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
-
- 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
- H05K2201/0158—Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Textile Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a high-dielectric material and a preparation method and application thereof. The high-dielectric material composed of a fiberglass paper prepreg layer and metal foils at top and bottom thereof; the fiberglass paper prepreg layer is made with fiberglass paper and a resin composition with ceramic filler attached to the fiberglass paper by impregnation drying; the ceramic filler in the resin composition accounts for 86-92% by weight. The high-dielectric material of the invention may have the good comprehensive properties, such as high dielectric constant, high peel strength, and good uniformity of all-directional CETs of a board, and the requirement on the properties of high-dielectric material may be met.
Description
Technical field
The present invention relates to high dielectric material technical field, more particularly, to a kind of high dielectric material, preparation method and its usage.
Background technology
With the development of the emerging micro-processing technology such as microelectronics, micromechanics, in the tide with high-density installation technology as background
In stream, the constantly miniaturization development such as capacitor, integrated circuit, circuit module, antenna rf module.Miniaturization, built-in
Change, multiband, intellectuality are the development trends of mobile terminal miniature antenna, the size of printed antenna and the relative dielectric constant of substrate
It is inversely proportional to, in order to realize the targets such as its miniaturization, lightweight it is necessary to exploitation has the copper-clad plate product of high-k.Electric capacity
Module miniaturization also requires that printing plate has high capacitivity, and capacitivity is directly proportional to the relative dielectric constant of substrate, improves
The dielectric constant of substrate is imperative.
CN103101252A discloses a kind of epoxy, the composite-based copper clad plate of hydroxyl extinguishing chemical preparation although dielectric constant
More than common epoxy substrate, but dielectric constant is less than 10；CN103351578A discloses a kind of epoxy, the preparation of high dielectric filler
Glass cloth base copper-clad plate, dielectric constant increases, but still less than 20.
In high-k copper-clad laminate, using glass fabric it is difficult to obtain dielectric constant covering more than 22
Copper coin laminate.For problem above, the present invention proposes one kind and has high-k, high-peeling strength, each side of sheet material
Wait well the sheet material of excellent comprehensive performance to CTE uniformity.
Content of the invention
The invention provides a kind of high dielectric material, it has high-k, high-peeling strength, sheet material all directions
CTE uniformity waits well excellent comprehensive performance, improves the problem being less than 22 (1GHz) using process medium dielectric constant microwave medium, can meet
The performance requirement of high dielectric material.
In order to achieve the above object, present invention employs following technical scheme：
An object of the present invention is to provide a kind of high dielectric material, and it is by glass fiber paper prepreg and its upper and lower both sides
Metal forming composition, described glass fiber paper prepreg by glass fiber paper and by impregnation drying after attached thereto filling out containing pottery
The resin combination composition of material；
In described resin combination, the quality percentage shared by ceramic packing is 86%～92%.
According to the present invention, described glass fiber paper, it is also called all-glass paper or non-woven fabrics, it is with glass fabric (glass cloth)
There is identical chemical composition, but be provided without through knitting device in manufacture craft.
The present invention all using glass fiber paper prepreg, it is overlapped with metal forming, obtained having high-k,
The high dielectric material of the excellent properties such as high-peeling strength, sheet material all directions CTE uniformity be good.
The present invention makes prepreg using glass fiber paper, compares and adopts glass cloth, and it can make dielectric material have higher Jie
Electric constant (Dk), can make dielectric constant reach more than 22.
In the present invention, glass fiber paper and ceramic packing have therebetween synergistic function, except making Jie of dielectric material
Electric constant reaches outside more than 22, also can improve the peel strength of dielectric material and make sheet material all directions CTE uniformity good, from
And so that the performance of dielectric material is greatly improved.
According to the present invention, in described resin combination, the quality percentage shared by ceramic packing is defined as follows：
Quality percentage wt%=wtFiller/(wtResin+wtFiller) × 100%, wherein wt% are the quality shared by ceramic packing
Percentage, wtResinFor the quality of resin in the resin combination in prepreg, wtFillerFor making pottery in the resin combination in prepreg
The quality of porcelain filling.
According to the present invention, in described resin combination, the quality percentage shared by ceramic packing is 86%～92%, for example
86%th, 86.5%, 87%, 87.5%, 88%, 89%, 89.5%, 90%, 91%, 91.5% or 92%, and above-mentioned numerical value
Between concrete point value, as space is limited and for simple and clear consideration, it is concrete that scope described in the present invention no longer exclusive list includes
Point value.
In order that the performance of dielectric material reaches more excellent, percent mass in described resin combination, shared by ceramic packing
Rate preferably 87%～92%, further preferred 88%～92%, so both can guarantee that dielectric material dielectric constant be more than 22, and
This dielectric material can be made the to have premium properties such as high-peeling strength, sheet material all directions CTE uniformity be good.
According to the present invention, described high dielectric material, that is, refer to the dielectric material that dielectric constant is 22～40, such as dielectric constant
For 22,22.5,23,23.5,24,24.5,25,26.5,27,28,29,30,31,32,33,34,36,38 or 40 and above-mentioned
Concrete point value between numerical value, as space is limited and for simple and clear consideration, scope described in the present invention no longer exclusive list includes
Concrete point value.
Heretofore described high dielectric material, its dielectric constant preferably 25～35.
According to the present invention, in the resin combination of described glass fiber paper prepreg, ceramic packing is selected from has Ca-Ti ore type
The high-dielectric constant inorganic particle of crystalline texture or composite perofskite type crystalline texture, preferably barium titanate, strontium titanates, magnesium titanate,
Calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide
Hafnium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, niobic acid barium
In lead, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, lead titanates-lead magnesio-niobate any one or extremely
Few two kinds of mixture.
The typical but non-limiting mixture of heretofore described ceramic packing, such as barium titanate and hafnium oxide mixed
Compound, the mixture of lead titanates and titanium niobate barium, the mixture of strontium titanates and barium strontium titanate, calcium barium titanate, lead zirconate titanate and titanium
The mixture of lead plumbate-lead magnesio-niobate, the mixture of lead bariun niobate, copper titanate and potassium tantallum niobate (KTH), barium titanate, strontium titanates and strontium titanates
The mixture of barium, calcium barium titanate, the mixture of lead zirconate titanate, lead titanates-lead magnesio-niobate and titanium niobate barium.
By selecting to filler in the present invention, when using above-mentioned filler, compare using titanium dioxide or titanium dioxide
Silicon filler, it can make dielectric material have higher dielectric constant；Meanwhile, above-mentioned filler also can be played with glass fiber paper between the two
Synergistic function, improves the dielectric constant of dielectric material further, makes dielectric constant (Dk) may be up to 40, realize dielectric material
High dielectric property.
In order that the performance such as the dielectric constant of high dielectric material, peel strength and sheet material all directions CTE uniformity reaches
To more excellent, in the particle diameter of described ceramic packing, angle value is 10nm～1500nm, such as 10nm, 20nm, 50nm, 120nm, 180nm,
250nm, 350nm, 450nm, 550nm, 750nm, 950nm, 1000nm, 1100nm, 1150nm, 1300nm, 1400nm or
Concrete point value between 1500nm, and above-mentioned numerical value, as space is limited and for simple and clear consideration, the present invention no longer exclusive list
The concrete point value that described scope includes.
Preferred 100nm～the 800nm of angle value in the particle diameter of ceramic packing of the present invention, further preferred 200nm～
700nm；The maximum particle diameter of ceramic packing is not to be exceeded 1500nm.
In resin combination of the present invention " containing " it is intended that it removes described group especially, other components can also be included,
These other components give described resin combination different characteristics.In addition, of the present invention " containing ", can also replace
Be changed to enclosed " for " or " by ... form ".
The heretofore described resin combination containing ceramic packing can be combined with various high polymers and is used together, as long as
It does not damage the proper property of resin combination.Concrete for example can for liquid crystal polymer, thermosetting resin, thermoplastic resin,
Different flame-retardant compounds or additive etc..They can be used alone as needed or multiple combination uses.
In addition, the described resin combination containing ceramic packing can also contain various additives, as concrete example, permissible
Enumerate antioxidant, heat stabilizer, antistatic additive, ultra-violet absorber, pigment, colouring agent, lubricant etc..
According to the present invention, described glass fiber paper is 25g/m2-105g/m2Glass fiber paper, such as 25g/m2、35g/m2、45g/m2、
50g/m2、55g/m2、62g/m2、70g/m2、85g/m2、98g/m2、100g/m2、102g/m2Or 105g/m2, and above-mentioned numerical value
Between concrete point value, as space is limited and for simple and clear consideration, it is concrete that scope described in the present invention no longer exclusive list includes
Point value.
In the present invention, when the substance of glass fiber paper is less than 25g/m2When, intensity too small it is difficult to carry out production line production；Work as glass
Fine paper substance is more than 105g/m2When, because glass fiber paper thickness is excessive, immersion can be deteriorated, the plate defect prepared is more；Its
The preferred 50g/m of middle glass fiber paper2～75g/m2Glass fiber paper, it can reach higher resin content, be conducive to technological operation again,
It is beneficial to and obtain the high dielectric material that dielectric constant is 22～40.
According to the present invention, in described glass fiber paper prepreg, the quality percentage shared by glass fiber paper is 1.6%～13%, example
As 1.6%, 2%, 2.3%, 3%, 4.2%, 5%, 5.5%, 6%, 7.2%, 8%, 9%, 10.5%, 11%, 12%,
Concrete point value between 12.5% or 13%, and above-mentioned numerical value, as space is limited and for simple and clear consideration, the present invention is no longer poor
Enumerate to the greatest extent the concrete point value that described scope includes.
In glass fiber paper prepreg of the present invention, quality percentage preferably 3%～11% shared by glass fiber paper, excellent further
Select 5%～9%.
According to the present invention, in described glass fiber paper prepreg, the quality percentage shared by glass fiber paper is defined as follows：
Quality percentage wt%=wtGlass fiber paper/(wtResin+wtFiller+wtGlass fiber paper) × 100%, wherein wt% are shared by glass fiber paper
Quality percentage, wtResinFor the quality of resin in the resin combination in prepreg, wtFillerFor the resin combination in prepreg
The quality of middle ceramic packing, wtGlass fiber paperQuality for the glass fiber paper in prepreg.
According to the present invention, in the described resin combination containing ceramic packing, contain resin；Described resin be selected from epoxy resin,
Cyanate ester resin, polyphenylene oxide resin, polybutadiene, butadiene styrene resin, bismaleimide-triazine resin (BT), span come
Imide resin, polyflon, polyimide resin, phenolic resin, acrylic resin, liquid crystalline resin, benzoxazine
Any one in resin, phenoxy resin, nitrile rubber, nbr carboxyl terminal or hydroxy'terminated butadiene nitrile rubber or at least two
Mixture, but not limited to this.
The typical but non-limiting mixture of heretofore described resin, such as epoxy resin and cyanate ester resin mixed
The mixture of compound, polyphenylene oxide resin and polybutadiene, the mixture of butadiene styrene resin and BT resin, polyflon
With the mixture of polyimide resin, the mixture of phenolic resin and acrylic resin, epoxy resin, cyanate ester resin and polyphenyl
The mixture of ether resin, the mixture of polybutadiene, butadiene styrene resin and BT resin, polyflon, polyimides
The mixture of resin, phenolic resin and acrylic resin.
According to the present invention, described metal forming is in copper, brass, aluminium, nickel, copper alloy, brass alloys, aluminium alloy or nickel alloy
Any one or at least two combination, but not limited to this.
The typical but non-limiting combination of heretofore described metal forming, the combination of such as copper and brass, al and ni
Combination, the combination of brass alloys and copper alloy, the combination of copper, nickel and aluminium alloy.
According to the present invention, the thickness of described metal forming is 5 μm～150 μm, such as 5 μm, 10 μm, 15 μm, 18 μm, 25 μm,
Between 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 110 μm, 130 μm, 140 μm or 150 μm, and above-mentioned numerical value
Concrete point value, as space is limited and for simple and clear consideration, the concrete point value that scope described in the present invention no longer exclusive list includes.
The second object of the present invention is to provide a kind of prepreg, and it includes glass fiber paper and is attached to after impregnation is dried
The resin combination containing ceramic packing as described in one of the object of the invention on glass fiber paper.
According to the present invention, in described prepreg glass fiber paper and the resin combination containing ceramic packing specifically chosen and
Mentioned identical in one of its content and the object of the invention, will not be described here.
The prepreg that the present invention provides, when being applied to printed circuit board, its dielectric constant is more than 22, and has height
The excellent comprehensive performance such as peel strength, sheet material all directions CTE uniformity be good.
The preparation method of prepreg of the present invention does not specifically limit, as long as it is by containing of the present invention
The resin combination of ceramic packing and glass fiber paper is had to be combined the method to prepare prepreg.The preparation method of exemplary prepreg
For：The resin combination containing ceramic packing forming prepreg is prepared into glue, impregnates described glue, warp using glass fiber paper
Remove solvent after drying, obtain glass fiber paper prepreg.
In the above-mentioned resin combination containing ceramic packing for preparing glass fiber paper prepreg, can make as needed
With organic solvent, there is no particular limitation to organic solvent for the present invention, as long as molten with each group split-phase appearance of resin combination
Agent.Described solvent, as concrete example, can enumerate：The alcohols such as methyl alcohol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, second
The ethers such as glycol-methyl ether, diethylene glycol ether, butyl, acetone, butanone, methyl ethyl ketone, methyl-isobutyl first
The ketones such as ketone, cyclohexanone, toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon, ethoxyethyl acetate, ethyl acetate etc.
Esters, the nitrogen-containing solvent such as DMF, DMA, METHYLPYRROLIDONE.Above-mentioned solvent
Can be used alone one kind it is also possible to two kinds or two or more be used in mixed way.
Present invention also offers a kind of preparation method of high dielectric material as previously mentioned, methods described comprises the steps：
(1) resin combination containing ceramic packing forming prepreg is prepared into glue, impregnates institute using glass fiber paper
State glue, after drying, remove solvent, obtain glass fiber paper prepreg；
(2) the glass fiber paper prepreg made described at least is placed in the middle of two metal formings, then puts laminating machine into
In by hot-press solidifying be obtained high dielectric material.
At least one glass fiber paper prepreg, refers to that the quantity of glass fiber paper prepreg is one or more than one, that is, one
Or two or multiple.
The third object of the present invention is to provide a kind of copper-clad laminate, it include at least one as the object of the invention it
Prepreg described in two and the Copper Foil of the upper and lower both sides of prepreg after being overlying on overlapping.Every prepreg includes glass fiber paper and by containing
Dip dry dry after be attached on glass fiber paper the resin combination containing ceramic packing.
According to the present invention, in described prepreg, glass fiber paper and the resin combination containing ceramic packing specifically chosen
And its mentioned identical in one of content and the object of the invention, will not be described here.
The preparation method of copper-clad laminate of the present invention can be prepared by known method, exemplary side
Method is such as：The resin combination containing ceramic packing forming prepreg is prepared into glue, impregnates described glue using glass fiber paper,
Remove solvent after drying, obtain prepreg；Then one or more above-mentioned prepreg is taken to be superimposed together according to certain order,
Copper Foil is covered respectively in the prepreg both sides being superimposed with each other, solidify in hot press and copper-clad laminate is obtained, its solidification temperature
Spend for 150～250 DEG C, solidifying pressure is 25kgf/cm2～60kgf/cm2.
The fourth object of the present invention is to provide a kind of purposes of high dielectric material as described in one of the object of the invention, described
High dielectric material is used for printed circuit board.
Compared with prior art, the present invention at least has the advantages that：
The high dielectric material that the present invention provides, it passes through the synergy of glass fiber paper and ceramic packing, and dielectric constant is up to
More than 22, and there is the excellent comprehensive performances such as high-peeling strength, sheet material all directions CTE uniformity be good.
Brief description
Fig. 1 is the structural representation of high dielectric material of the present invention；
In figure：1- metal forming, 2- glass fiber paper prepreg.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or restriction the scope of the present invention, protection scope of the present invention is defined by claims.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Heretofore described high dielectric material, its concrete structure is by the metal of glass fiber paper prepreg and its upper and lower both sides
Paper tinsel forms, and described glass fiber paper prepreg is by glass fiber paper and the tree containing ceramic packing attached thereto after impregnation is dried
Oil/fat composition forms.
Fig. 1 shows the structural representation of the high dielectric material of the present invention, and wherein, described high dielectric material is pre- by glass fiber paper
The metal forming 1 of leaching material 2 and its upper and lower both sides forms, and wherein, glass fiber paper prepreg 2 can be one or more, and here is not spy
Different restriction.
In the present invention, metal forming 1 can specifically adopt brass, aluminium, nickel, copper alloy, brass alloys, aluminium alloy or nickel alloy
In at least one, the present invention do not do particular determination.
For the present invention is better described, readily appreciate technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows：
Embodiment 1
By 21.6g polyphenylene oxide resin, 45g brominated epoxy resin (epoxy resin B) and 20g phenoxy resin (C), it is dissolved in
In EGME, and add the o-cresol phenolic resin with respect to epoxy resin 0.7 mol ratio and 2-MI (2- methyl miaow
Azoles), adding angle value in particle diameter is the barium titanate of 10nm, and the quality percentage of barium titanate is 86%, then mixes at room temperature
Obtain glue.Impregnate above-mentioned glue using glass fiber paper, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, control
The quality percentage of glass fiber paper is 1.6%, obtains glass fiber paper prepreg.
Then, the glass fiber paper prepreg making is placed between 5 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Embodiment 2
By 27g bisphenol A epoxide resin (epoxy resin A), 45g brominated epoxy resin (epoxy resin B) and 25g phenol oxygen tree
Fat (C), is dissolved in EGME, and add with respect to epoxy resin 0.7 mol ratio o-cresol phenolic resin and
2-MI (2-methylimidazole), adding angle value in particle diameter is the barium titanate of 500nm, and the quality percentage of barium titanate is 92%, so
It is mixed to get glue afterwards at room temperature.Impregnate above-mentioned glue using glass fiber paper, in 155 DEG C of baking oven, then toast 5 minutes admittedly
Turn to B-stage, the quality percentage controlling glass fiber paper is 13%, obtains glass fiber paper prepreg.
Then, the glass fiber paper prepreg making is placed between 50 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Embodiment 3
By 27g bisphenol A epoxide resin (epoxy resin A), 45g brominated epoxy resin (epoxy resin B) and 25g phenol oxygen tree
Fat (C), is dissolved in EGME, and add with respect to epoxy resin 0.7 mol ratio o-cresol phenolic resin and
2-MI (2-methylimidazole), adding angle value in particle diameter is the barium titanate of 500nm, and the quality percentage of barium titanate is 92%, so
It is mixed to get glue afterwards at room temperature.Impregnate above-mentioned glue using glass fiber paper, in 155 DEG C of baking oven, then toast 5 minutes admittedly
Turn to B-stage, the quality percentage controlling glass fiber paper is 2.5%, obtains glass fiber paper prepreg.
Then, the two glass fiber paper prepregs making are placed between 50 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Embodiment 4
By 46g polyphenylene oxide resin, 45g brominated epoxy resin (epoxy resin B) and 20g phenoxy resin (C), it is dissolved in second
In glycol methyl ether, and add the o-cresol phenolic resin with respect to epoxy resin 0.7 mol ratio and 2-MI (2- methyl miaow
Azoles), adding angle value in particle diameter is the strontium titanates of 1500nm, and the quality percentage of strontium titanates is 88%, then mixes at room temperature
Conjunction obtains glue.Impregnate above-mentioned glue using glass fiber paper, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven, control
The quality percentage of glass fiber paper processed is 8.3%, obtains glass fiber paper prepreg.
Then, multiple the glass fiber paper prepregs making are placed between 100 μm of Copper Foil, are laminated in 190 DEG C in press
And solidify, obtain Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in
Table 1.
Embodiment 5
By 27g bisphenol A epoxide resin (epoxy resin A), 45g brominated epoxy resin (epoxy resin B) and 25g phenol oxygen tree
Fat (C), is dissolved in EGME, and add with respect to epoxy resin 0.7 mol ratio o-cresol phenolic resin and
2-MI (2-methylimidazole), adding angle value in particle diameter is the strontium titanates of 500nm, and the quality percentage of strontium titanates is 92%, so
It is mixed to get glue afterwards at room temperature.Impregnate above-mentioned glue using glass fiber paper, in 155 DEG C of baking oven, then toast 5 minutes admittedly
Turn to B-stage, the quality percentage controlling glass fiber paper is 2.5%, obtains glass fiber paper prepreg.
Then, the two glass fiber paper prepregs making are placed between 50 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Embodiment 6
By 27g bisphenol A epoxide resin (epoxy resin A), 45g brominated epoxy resin (epoxy resin B) and 25g phenol oxygen tree
Fat (C), is dissolved in EGME, and add with respect to epoxy resin 0.7 mol ratio o-cresol phenolic resin and
2-MI (2-methylimidazole), adding angle value in particle diameter is the barium strontium titanate of 500nm, and the quality percentage of barium strontium titanate is
92%, then it is mixed to get glue at room temperature.Impregnate above-mentioned glue using glass fiber paper, in 155 DEG C of baking oven, then toast 5
Minute is cured as B-stage, and the quality percentage controlling glass fiber paper is 2.5%, obtains glass fiber paper prepreg.
Then, the two glass fiber paper prepregs making are placed between 50 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Embodiment 7
By 27g bisphenol A epoxide resin (epoxy resin A), 45g brominated epoxy resin (epoxy resin B) and 25g phenol oxygen tree
Fat (C), is dissolved in EGME, and add with respect to epoxy resin 0.7 mol ratio o-cresol phenolic resin and
2-MI (2-methylimidazole), adding angle value in particle diameter is the barium titanate of 500nm, and adding angle value in particle diameter is the titanium of 1500nm
The quality percentage of lead plumbate, barium titanate and lead titanates is respectively 46%, is then mixed to get glue at room temperature.Using glass fiber paper
Impregnate above-mentioned glue, then baking is cured as B-stage for 5 minutes in 155 DEG C of baking oven, the quality percentage of control glass fiber paper is
2.5%, obtain glass fiber paper prepreg.
Then, the two glass fiber paper prepregs making are placed between 50 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
1.
Comparative example 1
The barium titanate filer content of embodiment 1 is down to 85%, remaining is same as Example 1.
Comparative example 2
The barium titanate filer content of embodiment 1 is down to 70%, remaining is same as Example 1.
Comparative example 3
Use 205g/m2Glass fiber paper in glass cloth alternative embodiment 1, the quality percentage controlling glass cloth is 41%, its
Remaining same as Example 1.
Comparative example 4
The titanium dioxide being 10nm with angle value in particle diameter, the quality percentage of titanium dioxide is in 86% alternative embodiment 1
Barium titanate, remaining is same as Example 1.
Comparative example 5
The silica being 10nm with angle value in particle diameter, the quality percentage of silica is in 86% alternative embodiment 1
Barium titanate, remaining is same as Example 1.
Comparative example 6
Use 205g/m2Glass fiber paper in glass cloth alternative embodiment 2, the quality percentage controlling glass cloth is 41%, its
Remaining same as Example 2.
Comparative example 7 (compared with Example 1, using glass cloth, filler is titanium dioxide, and quality percentage is 70%)
By 21.6g polyphenylene oxide resin, 45g brominated epoxy resin (epoxy resin B) and 20g phenoxy resin (C), it is dissolved in
In EGME, and add the o-cresol phenolic resin with respect to epoxy resin 0.7 mol ratio and 2-MI (2- methyl miaow
Azoles), adding angle value in particle diameter is the titanium dioxide of 10nm, and the quality percentage of titanium dioxide is 70%, then at room temperature
It is mixed to get glue.Impregnate above-mentioned glue using glass cloth, then baking is cured as B-stage in 5 minutes in 155 DEG C of baking oven,
The quality percentage controlling glass cloth is 41%, obtains glass cloth prepreg.
Then, the glass cloth prepreg making is placed between 5 μm of Copper Foil, in press in 190 DEG C of laminations simultaneously
Solidification, obtains Measuring Dielectric Constant, bending strength, peel strength, horizontal CTE and longitudinal CTE after solidfied material.Specific performance is shown in Table
2.
In above-described embodiment and comparative example, used material is specific as follows：
Polyphenylene oxide resin：Husky Bick SA9000
Brominated epoxy resin：Taiwan Changchun BEB531A80P
Phenoxy resin：Nippon Steel YP-50EK35
O-cresol phenolic resin：KOLON KCE-F2118
2-MI：BASF (German) 2MI
Barium titanate/strontium titanate/barium strontium titanate：Shanghai allusion quotation raises science and technology
Lead titanates：Hubei peach of immortality culminant star electronics
Silica：East Sea silicon powder DS1032
Titanium dioxide：The brilliant auspicious VK-T200 in Xuancheng
Glass fiber paper：Xinping Ward
Glass cloth：Taiwan Xiu Beier
Table 1
Table 2
The method of testing of above characteristic is as follows：
1st, dielectric properties：SPDR (splite post dielectric resonator) method is tested, test condition
For A state, 1.1GHz.
2nd, bending strength：According to " under room temperature " experiment condition in IPC-TM-650 2.4.4 method, test the bending of sheet material
Intensity.
3rd, peel strength (PS)：According to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, test sheet material
Peel strength.
4th, horizontal CTE method of testing：According to " TMA " experiment condition in IPC-TM-650 2.4.24.5 method, test sheet material
Horizontal CTE.
5th, longitudinal CTE method of testing：According to " TMA " experiment condition in IPC-TM-650 2.4.24 method, test sheet material
Longitudinal CTE.
Can be seen that from above-described embodiment and comparative example：
(1) compared with comparative example 1 and comparative example 2, embodiment 1 has the bending strength of higher dielectric constant and Geng Gao,
The filler that this explanation embodiment 1 is 86% using content, compares the filler that comparative example 1 is 85% using content and comparative example 2 is adopted
The filler being 70% with content, it can make dielectric material have higher dielectric constant, reaches more than 22, also can make it have more
High bending strength, thus can also illustrate can be obtained to more than 86% and had more high-k by the content improving filler
The dielectric material of more high bending strength；
(2) compared with comparative example 3, embodiment 1 has a peel strength of higher dielectric constant and Geng Gao, horizontal CTE and
More preferably, this explanation embodiment 1 adopts glass fiber paper to the uniformity of longitudinal CTE, compares comparative example 3 and adopts glass cloth, it can make dielectric
Material has the peel strength of higher dielectric constant and Geng Gao, and the uniformity of horizontal CTE and longitudinal CTE is more preferable；Likewise, with
Comparative example 6 is compared, and embodiment 2 also can obtain the dielectric material with more high-k and more high-peeling strength using glass fiber paper
Material, the uniformity of horizontal CTE and longitudinal CTE is more preferable；
Meanwhile, compared with comparative example 4 and comparative example 5, embodiment 1 has higher dielectric constant and the stripping of Geng Gao is strong
Degree, this explanation embodiment 1 adopts barium titanate as filler, compares comparative example 4 and adopts two using titanium dioxide filler and comparative example 5
Cilicon oxide filler, it can make dielectric material have the peel strength of higher dielectric constant and Geng Gao；
Be can be seen that by glass cloth is replaced with glass fiber paper and by dioxy by above-described embodiment 1 and comparative example 3-5
When change titanium or silica replace with barium titanate as filler, it all improves the dielectric constant of dielectric material and peel strength,
Thus can also illustrate, compare single factors, the glass fiber paper that the present invention adopts and filler have synergistic function therebetween,
It achieves the high-k of dielectric material and high-peeling strength jointly, and sheet material all directions CTE uniformity is good；
(3) compared with comparative example 7, embodiment 1 has higher dielectric constant, and the uniformity of horizontal CTE and longitudinal CTE is more
Good, using glass fiber paper, barium titanate filler and when controlling filer content more than 86%, it can make Jie to this explanation embodiment 1
Electric material realizes the excellent comprehensive performances such as high-k, sheet material all directions CTE uniformity be good.
In summary, the dielectric material of the present invention can reach high-k, high-peeling strength, sheet material all directions
CTE uniformity waits excellent comprehensive performance well, thus meeting the performance requirement of high dielectric material.
Applicant states, the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, do not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, the equivalence replacement to part selected by the present invention
And the increase of accessory, selection of concrete mode etc., all fall within protection scope of the present invention and open within the scope of.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. a kind of high dielectric material is it is characterised in that described high dielectric material is by glass fiber paper prepreg and its upper and lower both sides
Metal forming forms, and described glass fiber paper prepreg contains ceramic packing by glass fiber paper and by attached thereto after impregnation drying
Resin combination composition；
In described resin combination, the quality percentage shared by ceramic packing is 86%～92%.
2. high dielectric material as claimed in claim 1 is it is characterised in that in described resin combination, shared by ceramic packing
Quality percentage is 87%～92%, preferably 88%～92%；
Preferably, the dielectric constant of described high dielectric material is 22～40, preferably 25～35.
3. high dielectric material as claimed in claim 1 or 2 has Ca-Ti ore type it is characterised in that described ceramic packing is selected from
The high-dielectric constant inorganic particle of crystalline texture or composite perofskite type crystalline texture, preferably barium titanate, strontium titanates, magnesium titanate,
Calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide
Hafnium, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate
Any one in barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, lead titanates-lead magnesio-niobate or at least two
Mixture；
Preferably, in the particle diameter of described ceramic packing, angle value is 10nm～1500nm, preferably 100nm～800nm, further preferably
200nm～700nm.
4. the high dielectric material as described in one of claims 1 to 3 is it is characterised in that described glass fiber paper is 25g/m2-105g/m2
Glass fiber paper, preferably 50g/m2～75g/m2Glass fiber paper.
5. the high dielectric material as described in one of Claims 1 to 4 is it is characterised in that contain resin in described resin combination；
Described resin carrys out acyl selected from epoxy resin, cyanate ester resin, polyphenylene oxide resin, polybutadiene, butadiene styrene resin, span
Imines-cyanate resin, bimaleimide resin, polyflon, polyimide resin, phenolic resin, acrylic acid tree
In fat, liquid crystalline resin, benzoxazine resin, phenoxy resin, nitrile rubber, nbr carboxyl terminal or hydroxy'terminated butadiene nitrile rubber
Any one or at least two mixture.
6. the high dielectric material as described in one of Claims 1 to 5 it is characterised in that described metal forming be copper, brass, aluminium,
In nickel, copper alloy, brass alloys, aluminium alloy or nickel alloy any one or at least two combination；
Preferably, the thickness of described metal forming is 5 μm～150 μm.
7. a kind of prepreg is it is characterised in that described prepreg includes glass fiber paper and is attached to glass fiber paper after impregnation is dried
On the resin combination containing ceramic packing as described in one of claim 1～6.
8. prepreg as claimed in claim 7 is it is characterised in that quality percentage in described prepreg, shared by glass fiber paper
For 1.6%～13%, preferably 3%～11%, further preferred 5%～9%.
9. a kind of copper-clad laminate, including at least prepreg as claimed in claim 7 or 8 and be overlying on pre- after overlapping
The Copper Foil of leaching material both sides.
10. a kind of purposes of the high dielectric material as described in one of claim 1～6 is it is characterised in that described high dielectric material
For printed circuit board.
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Cited By (2)
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|---|---|---|---|---|
| CN107509312A (en) * | 2017-06-29 | 2017-12-22 | 安徽升鸿电子有限公司 | A kind of preparation method of Dk ＞ 10 copper-clad plate |
| CN109760384A (en) * | 2018-12-24 | 2019-05-17 | 嘉兴佳利电子有限公司 | A kind of preparation method of high dielectric constant composite laminate |
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|---|---|---|---|---|
| CN103402311A (en) * | 2013-07-19 | 2013-11-20 | 广东生益科技股份有限公司 | Material of embedded capacitor as well as preparation method and application thereof |
| CN104448718A (en) * | 2014-12-08 | 2015-03-25 | 陕西生益科技有限公司 | Resin composition and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402311A (en) * | 2013-07-19 | 2013-11-20 | 广东生益科技股份有限公司 | Material of embedded capacitor as well as preparation method and application thereof |
| CN104448718A (en) * | 2014-12-08 | 2015-03-25 | 陕西生益科技有限公司 | Resin composition and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107509312A (en) * | 2017-06-29 | 2017-12-22 | 安徽升鸿电子有限公司 | A kind of preparation method of Dk ＞ 10 copper-clad plate |
| CN109760384A (en) * | 2018-12-24 | 2019-05-17 | 嘉兴佳利电子有限公司 | A kind of preparation method of high dielectric constant composite laminate |
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