CN105437672A - Ultrathin CCL (copper clad laminate) and production method thereof - Google Patents
Ultrathin CCL (copper clad laminate) and production method thereof Download PDFInfo
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- CN105437672A CN105437672A CN201511003345.3A CN201511003345A CN105437672A CN 105437672 A CN105437672 A CN 105437672A CN 201511003345 A CN201511003345 A CN 201511003345A CN 105437672 A CN105437672 A CN 105437672A
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- copper foil
- clad plate
- adhesive liquid
- resin adhesive
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000010949 copper Substances 0.000 title abstract 2
- 229910052802 copper Inorganic materials 0.000 title abstract 2
- 239000004744 fabric Substances 0.000 claims abstract description 106
- 229920005989 resin Polymers 0.000 claims abstract description 95
- 239000011347 resin Substances 0.000 claims abstract description 95
- 239000011889 copper foil Substances 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims description 54
- 230000001070 adhesive effect Effects 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 45
- 239000003365 glass fiber Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 31
- 238000007598 dipping method Methods 0.000 claims description 25
- 238000005470 impregnation Methods 0.000 claims description 22
- 238000003475 lamination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 13
- 238000004026 adhesive bonding Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- 238000009954 braiding Methods 0.000 claims description 9
- 238000005491 wire drawing Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 4
- -1 pottery Chemical compound 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 5
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 abstract 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 abstract 1
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 238000010422 painting Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
-
- 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
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of CCLs (copper clad laminates) and particularly relates to an ultrathin CCL with high dielectric constant. The ultrathin CCL comprises a copper foil, a piece of setting cloth and an insulating layer which is arranged between the copper foil and the setting cloth and formed by curing resin glue liquid, wherein the resin glue liquid comprises the following components in parts by weight: 50-100 parts of epoxy resin, 1-35 parts of a cross-linking curing agent, 0-5 parts of a cross-linking curing accelerator and 50-100 parts of filler with high dielectric constant; and the filler with high dielectric constant refers to one or more of titanium dioxide, ceramic, barium titanate, lead titanate andbarium strontium titanate. According to the invention, on one hand, by adopting the setting cloth as a reinforcing material, the defects such as warping and instable size frequently occurring in an ultrathin CCL are solved; and on the other hand, by combining the setting cloth with the resin glue liquid with high dielectric constant, the produced ultrathin CCL has good comprehensive performance, and particularly the dielectric performance of CCL is improved; and the invention also relates to a production method of the ultrathin CCL.
Description
Technical field
The present invention relates to copper-clad plate technical field, particularly relate to a kind of ultra-thin copper-clad plate with high-k and preparation method thereof.
Background technology
Glass fibre (glassfiber or fiberglass), also known as glass fiber, is a kind of Inorganic Non-metallic Materials of excellent performance, and composition is silica, aluminium oxide, calcium oxide, boron oxide, magnesia, sodium oxide molybdena etc.It is for raw material is made into glass-fiber-fabric through high temperature melting, wire drawing, doff, the technique such as to weave cotton cloth with glass marble or discarded glass, and finally form various product, wherein, the diameter of glass fiber single filament is from several micron to twenties microns, be equivalent to 1/20 ~ 1/5 of a hairline, every bundle fiber precursor all by hundreds of even thousands of monofilament form.Glass-fiber-fabric is typically used as reinforcing material, electrically insulating material and heat-insulating material in composite, and the substrate etc. of printed circuit board (PCB) (that is, pcb board), is widely used in national economy every field.
When glass-fiber-fabric is applied to printed circuit board (PCB), existing technique carries out gluing, solidification to glass-fiber-fabric, forms bonding sheet, just can be made into copper-clad plate at this bonding sheet coated with Copper Foil etc., and at present traditionally, to glass fiber starching, after braiding process, again destarch smoldering is carried out to glass-fiber-fabric blank and the glass-fiber-fabric obtained, particularly slim glass-fiber-fabric, there is following defect when being applied to printed circuit board (PCB) in it: glass-fiber-fabric is due to the braiding structure of itself, when gluing, glass fiber is wherein easy to the small inhomogeneities of the tension force because being subject to, skew of weft phenomenon is there is after causing glass-fiber-fabric gluing, and then make the glass-fiber-fabric poor dimensional stability after gluing, serious and the apparent out-of-flatness of warpage, the making of above-mentioned defect to slim PCB and superfine wire PCB brings extreme difficulties, and glass-fiber-fabric is when preparing copper-clad plate, in order to improve resistance to Ion transfer (CAF) performance of copper-clad plate, needing the filling of enough resin adhesive liquid, further increasing the difficulty preparing superthin PCB and superfine wire PCB.
And along with the high speed development of current microelectronic industry, the size of most electronic product is more and more less; And mobile Internet industry high speed development, the Anneta module of smart mobile phone, intelligent automobile, its inside of panel computer is also towards the future development such as miniaturized, intelligent; These all need the inside PCB of densification and the electronic devices and components of microminiaturization to support.And according to electromagnetic theory, the relative dielectric constant of the size of Anneta module and base material (copper-clad plate) is inverse ratio, means and need the base material that relative dielectric constant is higher by the antenna module that size is less.
In order to solve the problem, the pcb board that obtain densification just requires that we obtain having the ultra-thin copper-clad plate of high-k.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of ultra-thin copper-clad plate with high-k;
Two of object of the present invention is the preparation method providing above-mentioned ultra-thin copper-clad plate.
To achieve these goals, technical scheme of the present invention is as follows:
Have a ultra-thin copper-clad plate for high-k, gross thickness is no more than 80 μm, comprises Copper Foil, setting cloth and is arranged at the insulating barrier solidified by resin adhesive liquid between described Copper Foil and described setting cloth;
Wherein said resin adhesive liquid by weight, comprising: epoxy resin 50 ~ 100 parts, crosslinking and curing agent 1 ~ 35 part, crosslinking curing promoter 0 ~ 5 part, high-k filler 50 ~ 100 parts; Described high-k filler is one or more in titanium dioxide, pottery, barium titanate, lead titanates, barium strontium titanate.
Compared to prior art, one aspect of the present invention introduces setting cloth, which obviates and adopts traditional glass-fiber-fabric to occur skew of weft in dipping gluing and bonding processes, and then the problem such as the slim copper-clad plate warpage causing obtaining, dimensional stability be bad; On the other hand, have employed the resin adhesive liquid of high-k to form insulating barrier, wherein high-k filler can improve the dielectric constant of resin adhesive liquid, further, improves the dielectric constant of ultra-thin copper-clad plate, can make the PCB that relative dielectric constant is higher.
Particularly, the preparation method of described setting cloth, comprises the steps:
Wire drawing, carries out wire drawing by after frit melting, forms glass fiber;
Impregnation is weaved cotton cloth, and is immersed in described resin adhesive liquid by described glass fiber and carries out gluing, carries out the process of oven dry semi-solid preparation, then be woven into glass-fiber-fabric blank after taking-up; Wherein, described resin adhesive liquid is less than 200CPS the viscosity of 25 DEG C;
Baking-curing, carries out baking-curing to described glass-fiber-fabric blank, described resin adhesive liquid is solidified completely, obtains setting cloth; Wherein, in described setting cloth, weight resin content is no more than 30%;
Wherein, the temperature of described baking-curing is 150 ~ 200 DEG C, and the time of baking-curing is 1 ~ 2 hour.
Relative to prior art, setting cloth used in the present invention weaves after directly carrying out impregnation to described glass fiber when making, on the one hand, replace traditional glass-fiber-fabric make in the various problems brought of starching, destarch smoldering, saved operation; On the other hand, resin adhesive liquid is adopted directly to carry out heat treatment to glass fiber, under the resin being closely covered in glass fiber (glass fibre) surface supports, being fixed through broadwise wherein, setting cloth dimensionally stable obtained like this, apparent smooth, avoid the problem that skew of weft, warpage appear in traditional glass-fiber-fabric in dipping gluing and bonding processes, be conveniently applied to and make ultra-thin CCL; And this setting cloth avoids and to flood bad and voiding problem that is that cause between organdy hollow or glass filament bundle, the ultra-thin CCL using this setting cloth to make there will not be Ion transfer (CAF) problem, effectively can improve the heat resistance of CCL, electrical property and ageing-resistant performance, ensure that product quality.In addition, in the present invention, adopt above-mentioned resin adhesive liquid impregnated glass, the dielectric constant making copper-clad plate can be improved, the requirement of modern microelectronic industry can be met.
Particularly, described impregnation is weaved cotton cloth and is comprised the steps:
(1) at least two described glass fiber are carried out doubling, form glass filament bundle;
(2) carry out dipping process by described glass filament bundle immersion resin adhesive liquid, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation organdy; Wherein, drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes;
(3) successively twist yarn, warping and braiding are carried out to described impregnation organdy, form described glass-fiber-fabric blank.
This kind of mode is adopted to make setting cloth, glass fiber just immerses in glue and carries out dipping process after doubling process, by glue, surface treatment is carried out to glass fiber, therefore in setting cloth braiding process, be filled with the space between glass fiber in time, and can effectively prevent from occurring skew of weft in follow-up braiding processing procedure, ensure that produced setting cloth dimensionally stable; Simultaneously because dipping process just carries out after doubling, the setting cloth that last baking-curing is formed is apparent smooth and there will not be space; Therefore, utilize this setting cloth to make the ultra-thin copper-clad plate obtained, there is dimensionally stable, apparent smooth and feature that is not war proclamation line, thus prevent this ultra-thin copper-clad plate from occurring short circuit or open circuit at making pcb board, reduce manufacture difficulty and the cost of manufacture of ultra-thin copper-clad plate; And setting cloth avoids the generation in space, make the resistance to Ion transfer of pcb board (CAF) made of this ultra-thin copper-clad plate, ensure that product quality.
Particularly, described impregnation is weaved cotton cloth and is comprised the steps:
(1) at least two described glass fiber are carried out doubling, twist yarn and warping successively, form warping yarn;
(2) carry out dipping process by described warping yarn immersion resin adhesive liquid, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation warping yarn; Wherein, drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes;
(3) described impregnation warping yarn is woven, form described glass-fiber-fabric blank.
Adopt and make setting cloth in this way, glass fiber first carries out doubling, twist yarn and warping process and forms warping yarn, then warping yarn is immersed in glue and carry out dipping process, because glue has carried out surface treatment to glass fiber, the space between glass fiber is filled with in time in setting cloth braiding process, and can effectively prevent from occurring skew of weft in follow-up braiding processing procedure, ensure that produced setting cloth dimensionally stable; Simultaneously because dipping process carries out after warping, the setting cloth that last baking-curing is formed is apparent smooth and there will not be space, this setting cloth is used to make the copper-clad plate obtained with this, there is dimensionally stable, apparent smooth and feature that is not war proclamation line, thus there is short circuit or open circuit in the pcb board preventing this copper-clad plate from making, improve performance and the qualification rate of pcb board, reduce manufacture difficulty and cost of manufacture; And setting cloth avoids the generation in space, make the resistance to Ion transfer of pcb board (CAF) made of this, ensure that product quality.
Preferably, the solid content of described resin adhesive liquid is 7% ~ 15%.
Preferably, the thickness of described insulating barrier is 10 ~ 70 μm, and described Copper Foil is rolled copper foil or electrolytic copper foil, and thickness is 9 ~ 70 μm.
A preparation method for ultra-thin copper-clad plate described above, applies described resin adhesive liquid with coating machine on the matsurface of Copper Foil, and the Copper Foil semi-solid preparation being coated with described resin adhesive liquid is formed resin coated copper foil; By described setting cloth and described resin coated copper foil pressing and baking-curing, form described ultra-thin copper-clad plate.
Preferably, described pressing is the one in roll-in or lamination; Described pressing-in temp is 80 ~ 160 DEG C.
Particularly, described " by described setting cloth and described resin coated copper foil pressing and baking-curing " is for carry out roll-in by the resin face of described resin coated copper foil and the one or both sides of described setting cloth, after roll-in, baking-curing forms described ultra-thin copper-clad plate, wherein, rolling pressure is 29 ~ 290PSI, roll-in Post RDBMS temperature is 80 ~ 160 DEG C, and hardening time is 30 ~ 90 minutes.
Particularly, described " by described setting cloth and described resin coated copper foil pressing and baking-curing " is for be cut into measure-alike sheet by described setting cloth and resin coated copper foil, and the setting cloth being cut into sheet to be folded on the resin face of the resin coated copper foil being cut into sheet and to align, form one deck stock; To at least be positioned in laminating machine and carry out lamination and solidify to form described ultra-thin copper-clad plate by one deck stock, wherein, lamination solidifying pressure be 300 ~ 500PSI, and lamination solidification temperature is 80 ~ 160 DEG C, and lamination hardening time is 30 ~ 90 minutes.
The present invention has the ultra-thin copper-clad plate of high-k, and adopt setting cloth carry out pressing with the Copper Foil being coated with resin adhesive liquid and obtain, its combination property is good, especially in dielectric properties; Due to the setting cloth wherein adopted, solve the defects such as warpage that ultra-thin copper-clad plate easily occurs, size be unstable, and effectively can improve the heat resistance of ultra-thin copper-clad plate, dielectric properties, ageing-resistant performance and resistance to Ion transfer etc.
Detailed description of the invention
For further setting forth the technological means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention.
The setting cloth that the ultra-thin copper-clad plate that the present invention has high-k uses is different from conventional glass-fiber-fabric, its preparation method based on conventional glass-fiber-fabric is improved, by to the direct impregnation of glass fiber, weave postcure resin glue again, under being supported by the resin being closely covered in glass fiber (glass fibre) surface, being fixed through broadwise in glass-fiber-fabric, and glass fibre is wherein finalized, setting cloth dimensionally stable obtained like this, apparent smooth, avoid traditional glass-fiber-fabric and occur skew of weft in dipping gluing and bonding processes, the problem of warpage, wherein the concrete preparation method of setting cloth has two kinds, as described below.
The first preparation method of setting cloth, comprises the steps:
First wire drawing, carries out wire drawing by after frit melting, forms glass fiber;
Impregnation is weaved cotton cloth subsequently, and dipping process method after employing doubling, is specially (1) and at least two glass fiber are carried out doubling, forms glass filament bundle; (2) carry out dipping process by described glass filament bundle immersion glue, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation organdy; Wherein, drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes; (3) successively twist yarn, warping and braiding are carried out to impregnation organdy, form glass-fiber-fabric blank; Wherein, described resin adhesive liquid is less than 200CPS the viscosity of 25 DEG C;
Last baking-curing, by above-mentioned glass-fiber-fabric blank in high temperature oven first time baking-curing, the resin adhesive liquid that impregnated on glass-fiber-fabric blank is solidified completely, namely obtains setting cloth; Wherein in setting cloth, weight resin content is no more than 30%.
The second preparation method of setting cloth, comprises the following steps:
First wire drawing, carries out wire drawing by after frit melting, forms glass fiber;
Impregnation is weaved cotton cloth subsequently, and dipping process method after employing warping, specifically comprises (1) and at least two glass fiber are carried out doubling, twist yarn and warping successively, forms warping yarn; (2) carry out dipping process by described warping yarn immersion glue, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation warping yarn; Wherein, drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes; (3) described impregnation warping yarn is woven, form described glass-fiber-fabric blank; Wherein, described resin adhesive liquid is less than 200CPS the viscosity of 25 DEG C;
Last baking-curing, carries out baking-curing by above-mentioned glass-fiber-fabric blank at high temperature oven, the resin adhesive liquid that impregnated on glass-fiber-fabric blank is solidified completely, namely obtains setting cloth; Wherein, the temperature of described baking-curing is 150 ~ 200 DEG C, and the time of baking-curing is 1 ~ 2 hour, and in setting cloth, weight resin content is no more than 30%.
Wherein in above-mentioned two kinds of preparation methods, in dipping process, resin adhesive liquid used is the resin adhesive liquid with high-k, and it for solidifying to form the insulating barrier with high-k, is held between Copper Foil and setting cloth equally; Wherein, this resin adhesive liquid by weight, comprising: epoxy resin 50 ~ 100 parts, crosslinking and curing agent 1 ~ 35 part, crosslinking curing promoter 0 ~ 5 part, high-k filler 50 ~ 100 parts; High-k filler is one or more in titanium dioxide, pottery, barium titanate, lead titanates, barium strontium titanate.The concrete formula of this resin adhesive liquid will be stated in an embodiment.
Embodiment 1
Have a ultra-thin copper-clad plate for high-k, its preparation method comprises the steps:
First prepare resin adhesive liquid and Copper Foil, wherein resin adhesive liquid by weight, comprising: epoxy resin 100 parts, crosslinking and curing agent 10 parts, crosslinking curing promoter 2 parts, barium titanate filler 50 parts and appropriate solvent; Copper Foil is the electrolytic copper foil of 9 μm;
Then setting cloth and resin coated copper foil is made: setting cloth adopts the first preparation method above-mentioned to obtain; Resin adhesive liquid be coated on the matsurface of Copper Foil, carry out semi-solid preparation after being dried, obtain being coated with Copper Foil resin, wherein resin layer thickness controls within the scope of 10 ~ 70 μm;
Pressing is solidified: adopt the mode of lamination painting Copper Foil resin and setting cloth to be combined 80 ~ 160 DEG C of temperatures, solidification, wherein lamination solidifying pressure is 300 ~ 500PSI, and lamination solidification temperature is 80 ~ 160 DEG C, lamination hardening time is, after 30 ~ 90 minutes, obtain ultra-thin copper-clad plate.
Embodiment 2
Have a ultra-thin copper-clad plate for high-k, its preparation method comprises the steps:
First prepare resin adhesive liquid and Copper Foil, wherein resin adhesive liquid by weight, comprising: epoxy resin 80 parts, crosslinking and curing agent 15 parts, barium strontium titanate 60 parts and appropriate solvent; Copper Foil is the rolled copper foil of 12 μm;
Then setting cloth and resin coated copper foil is made: setting cloth adopts above-mentioned the second preparation method to obtain; Resin adhesive liquid be coated on the matsurface of Copper Foil, carry out semi-solid preparation after being dried, obtain being coated with Copper Foil resin, wherein resin layer thickness controls within the scope of 10 ~ 68 μm;
Pressing is solidified: adopt the mode of roll-in painting Copper Foil resin and setting cloth to be forced together at 80 ~ 160 DEG C of temperature lower rolls, solidification, wherein roll-in solidifying pressure is 29 ~ 290PSI, after roll-in, the baking-curing time is 30 ~ 90 minutes, and solidification temperature is 80 ~ 160 DEG C, obtains ultra-thin copper-clad plate.
Embodiment 3
Have a ultra-thin copper-clad plate for high-k, its preparation method comprises the steps:
First prepare resin adhesive liquid and Copper Foil, wherein resin adhesive liquid by weight, comprising: epoxy resin 50 parts, crosslinking and curing agent 10 parts, crosslinking curing promoter 1 part, titanium dioxide and 70 parts, pottery and appropriate solvent; Copper Foil is the rolled copper foil of 12 μm;
Then setting cloth and resin coated copper foil is made: setting cloth adopts above-mentioned the second preparation method to obtain; Resin adhesive liquid be coated on the matsurface of Copper Foil, carry out semi-solid preparation after being dried, obtain being coated with Copper Foil resin, wherein resin layer thickness controls within the scope of 10 ~ 68 μm;
Pressing is solidified: adopt the mode of lamination to be cured after setting cloth is together with 80 ~ 160 DEG C of temperature laminated by painting Copper Foil resin, wherein lamination solidifying pressure is 300 ~ 500PSI, lamination solidification temperature is 80 ~ 160 DEG C, and lamination hardening time is, after 30 ~ 90 minutes, obtain ultra-thin copper-clad plate.
Comparative example 1
A kind of ultra-thin copper-clad plate, its preparation method comprises the following steps:
Prepare resin adhesive liquid and Copper Foil: wherein resin adhesive liquid by weight, comprising: epoxy resin 50 parts, crosslinking and curing agent 10 parts, crosslinking curing promoter 1 part and appropriate solvent; Copper Foil is the rolled copper foil of 12 μm;
Prepare prepreg and resin coated copper foil: the glass-fiber-fabric (1080 series) adopting above-mentioned resin adhesive liquid to prepare conventional method carries out conventional dipping process, and after drying, semi-solid preparation obtains prepreg; Resin adhesive liquid be coated on the matsurface of Copper Foil, carry out semi-solid preparation after being dried, obtain being coated with Copper Foil resin, wherein resin layer thickness controls within the scope of 10 ~ 68 μm;
Pressing is solidified: adopt the mode of lamination to be cured after prepreg is together with 80 ~ 160 DEG C of temperature laminated by painting Copper Foil resin, wherein lamination solidifying pressure is 300 ~ 500PSI, lamination solidification temperature is 80 ~ 160 DEG C, lamination hardening time is, after 30 ~ 90 minutes, obtain ultra-thin copper-clad plate.
Comparative example 2
A kind of ultra-thin copper-clad plate, its preparation method comprises the following steps:
Prepare resin adhesive liquid: it is identical with the resin adhesive liquid prepared in embodiment 3; Copper Foil is the rolled copper foil of 12 μm;
Prepare prepreg and resin coated copper foil: the glass-fiber-fabric (1080 series) adopting above-mentioned resin adhesive liquid to prepare conventional method carries out conventional dipping process, and after drying, semi-solid preparation obtains prepreg; Resin adhesive liquid be coated on the matsurface of Copper Foil, carry out semi-solid preparation after being dried, obtain being coated with Copper Foil resin, wherein resin layer thickness controls within the scope of 10 ~ 68 μm;
Pressing is solidified: adopt the mode of roll-in painting Copper Foil resin and prepreg to be cured after 80 ~ 160 DEG C of temperature lower rolls force together, wherein roll-in solidifying pressure is 29 ~ 290PSI, after roll-in, the baking-curing time is 30 ~ 90 minutes, solidification temperature is 80 ~ 160 DEG C, obtains ultra-thin copper-clad plate.
The performance of the copper-clad plate that the ultra-thin copper-clad plate with high-k obtain above-described embodiment and comparative example obtain detects, and detects data as shown in table 1 below.
Table 1
The method of testing of above characteristic is as follows:
Glass transition temperature is tested: adopt dynamic thermomechanical analysis apparatus (DMA2980, TA company of the U.S.); Give the vibration frequency of 1Hz, in a nitrogen atmosphere with the heating rate of 3 DEG C/min from room temperature to 250 DEG C, obtain glass transition temperature peel strength in maximum survey place of dielectric loss angle tangent (Tan δ): test according to IPC-TM-6502.4.9 method
Dielectric constant: use AgilentN5230A, measures the dielectric constant under 1GHz
Resistance to dip solderability: to observe its layering cream time according to IPC-TM-6502.4.13.1
Anti-flammability: test with reference to UL94 standard.
CAF tests: 85 DEG C/85%R.H voltage 100V, time 1000h.
From above-mentioned table 1, setting cloth is adopted to carry out pressing with the Copper Foil being coated with the resin adhesive liquid with high-k in the present invention and the ultra-thin copper-clad plate that obtains has high-k, its combination property is good, and the setting cloth owing to wherein adopting, solve the defect such as warpage, size instability that ultra-thin copper-clad plate easily occurs.
In sum, compared to prior art, one aspect of the present invention introduces setting cloth, which obviates and adopts traditional glass-fiber-fabric to occur skew of weft in dipping gluing and bonding processes, and then the problem such as the slim copper-clad plate warpage causing obtaining, dimensional stability be bad; On the other hand, have employed there is high-k resin adhesive liquid to form insulating barrier, wherein high-k filler can improve the dielectric constant of ultra-thin copper-clad plate, can make the PCB that relative dielectric constant is higher.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Claims (10)
1. a ultra-thin copper-clad plate, is characterized in that: comprise Copper Foil, setting cloth and be arranged at the insulating barrier solidified by resin adhesive liquid between described Copper Foil and described setting cloth;
Wherein said resin adhesive liquid by weight, comprising: epoxy resin 50 ~ 100 parts, crosslinking and curing agent 1 ~ 35 part, crosslinking curing promoter 0 ~ 5 part, high-k filler 50 ~ 100 parts; Described high-k filler is one or more in titanium dioxide, pottery, barium titanate, lead titanates, barium strontium titanate.
2. ultra-thin copper-clad plate according to claim 1, is characterized in that, the preparation method of described setting cloth, comprises the steps:
Wire drawing, carries out wire drawing by after frit melting, forms glass fiber;
Impregnation is weaved cotton cloth, and is immersed in described resin adhesive liquid by described glass fiber and carries out gluing, carries out the process of oven dry semi-solid preparation, then be woven into glass-fiber-fabric blank after taking-up;
Baking-curing, carries out baking-curing to described glass-fiber-fabric blank, described resin adhesive liquid is solidified completely, obtains setting cloth; Wherein, in described setting cloth, weight resin content is no more than 30%.
3. ultra-thin copper-clad plate according to claim 2, is characterized in that, described impregnation is weaved cotton cloth and comprised the steps:
(1) at least two described glass fiber are carried out doubling, form glass filament bundle;
(2) carry out dipping process by described glass filament bundle immersion resin adhesive liquid, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation organdy; Wherein, described resin adhesive liquid is less than 200CPS the viscosity of 25 DEG C, and drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes;
(3) successively twist yarn, warping and braiding are carried out to described impregnation organdy, form described glass-fiber-fabric blank.
4. ultra-thin copper-clad plate according to claim 1, is characterized in that, described impregnation is weaved cotton cloth and comprised the steps:
(1) at least two described glass fiber are carried out doubling, twist yarn and warping successively, form warping yarn;
(2) carry out dipping process by described warping yarn immersion resin adhesive liquid, carry out the process of oven dry semi-solid preparation after dipping process, thus form impregnation warping yarn; Wherein, described resin adhesive liquid is less than 200CPS the viscosity of 25 DEG C, and drying semi-solid preparation treatment temperature is 100 ~ 150 DEG C, and drying the semi-solid preparation processing time is 3 ~ 5 minutes;
(3) described impregnation warping yarn is woven, form described glass-fiber-fabric blank.
5. ultra-thin copper-clad plate according to claim 1, is characterized in that: the solid content of described resin adhesive liquid is 7% ~ 15%.
6. ultra-thin copper-clad plate according to claim 1, is characterized in that: the thickness of described insulating barrier is 10 ~ 70 μm, and described Copper Foil is rolled copper foil or electrolytic copper foil, and thickness is 9 ~ 70 μm.
7. ultra-thin copper-clad plate according to claim 2, is characterized in that: the temperature of described baking-curing is 150 ~ 200 DEG C, and the time of baking-curing is 1 ~ 2 hour.
8. a preparation method for ultra-thin copper-clad plate as described in any one of claim 1 ~ 7, is characterized in that: on the matsurface of Copper Foil, apply described resin adhesive liquid with coating machine, and the Copper Foil semi-solid preparation being coated with described resin adhesive liquid is formed resin coated copper foil; By described setting cloth and described resin coated copper foil pressing and baking-curing, form described ultra-thin copper-clad plate.
9. the preparation method of ultra-thin copper-clad plate according to claim 8, is characterized in that: described pressing is the one in roll-in or lamination.
10. the preparation method of ultra-thin copper-clad plate according to claim 8, is characterized in that: described pressing-in temp is 80 ~ 160 DEG C.
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