CN103429423B - Superthin layer pressing plate - Google Patents
Superthin layer pressing plate Download PDFInfo
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- CN103429423B CN103429423B CN201280010154.8A CN201280010154A CN103429423B CN 103429423 B CN103429423 B CN 103429423B CN 201280010154 A CN201280010154 A CN 201280010154A CN 103429423 B CN103429423 B CN 103429423B
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- resin
- laminate
- cloth
- copper foil
- thickness
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- 238000003825 pressing Methods 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 162
- 229920005989 resin Polymers 0.000 claims abstract description 160
- 239000004744 fabric Substances 0.000 claims abstract description 90
- 239000011889 copper foil Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000007711 solidification Methods 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 238000009413 insulation Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002648 laminated material Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 54
- 239000010949 copper Substances 0.000 abstract description 50
- 229910052802 copper Inorganic materials 0.000 abstract description 50
- 239000010410 layer Substances 0.000 description 94
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 11
- 239000004753 textile Substances 0.000 description 11
- 210000001519 tissues Anatomy 0.000 description 11
- 238000000034 method Methods 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010923 batch production Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1H-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- -1 3,4-epoxycyclohexyl Chemical group 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N Diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000003984 copper intrauterine device Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- WWWTWPXKLJTKPM-UHFFFAOYSA-N 2-aminooxyethanol Chemical compound NOCCO WWWTWPXKLJTKPM-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- 241000963007 Anelosimus may Species 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101700020405 IR08 Proteins 0.000 description 1
- FTDXCHCAMNRNNY-UHFFFAOYSA-N OC1=CC=CC=C1.OC1=CC=CC=C1 Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 210000002356 Skeleton Anatomy 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The present invention relates to ultrathin copper clad laminates including a fabric sheet, it includes the fabric sheet bed of material and at least one copper foil, the described fabric sheet bed of material has the first plane surface, the second plane surface and its original depth and is about 10 to about 30 microns, at least one copper foil described is attached on the plane surface of piece of cloth material by solidification resin, and wherein the thickness of substrate layer pressing plate is about 1.0 to about 1.75 mils.
Description
This application claims in the priority of provisional application the 61/446458th that on February 24th, 2011 submits to.
Background of invention
(1) technical field
The present invention relates to comprise the thin glass fabric layer that is laminated between the copper foil layer that two-layer is relative for manufacturing printing electricity
The ultrathin copper clad laminates including a fabric sheet of road plate and its manufacture method.
(2) background technology
Along with electronic device becomes less, the element forming these devices also becomes less.Meanwhile, element function is wanted
Ask more and more higher.Along with component size and the reduction of size of electronic devices, the thickness of the circuit board loading these elements needs class
As reduce.But, along with the reduction on thickness of the board layer pressing plate, holding circuit plate thickness over its entire surface is permanent
Surely it is more difficult from.Additionally, circuit board is the thinnest, manufacture institute in the printed circuit board (PCB) of the electrical requirements persistently meeting circuit-board industry
Laminate the most difficult.Therefore, constantly demand is the thinnest board layer laminate material and for continuing and can weigh
The method manufacturing thin laminate circuit laminate again.
Summary of the invention
One aspect of the present invention is a kind of laminate, and it comprises the group of substrate layer pressing plate and at least one copper foil
Closing, described substrate layer pressing plate includes the resin dipping with the first plane surface (planar surface) and the second plane surface
Piece of cloth material (fabric sheet material), the original depth of piece of cloth is about 10 to about 30 microns, described Copper Foil
Sheet is attached on the plane surface of fabric sheet by solidification resin, and wherein the thickness of substrate layer pressing plate is about 1.0 to about 1.75
Mil (25-45 micron).
In optional embodiment, it is every that laminate can include being attached in the first and second surfaces of piece of cloth material
Copper foil on one surface.Optionally further, laminate can have the average minimum insulation of not less than about 0.75 mil
The average greatest thickness (19-38 micron) of thickness (dielectric thickness) and no more than about 1.5 mils, or the least
Average minimum insulation thickness and the average greatest thickness (20-30 micron) of no more than about 1.2 mils in about 0.8 mil.
Lamination Copper Foil can have the thickness of about 15 to about 40 microns, or the thickness of about 15 to about 25 microns.
Substrate layer pressing plate can have extra useful character.Such as, it is laminated when the rectangle taking advantage of 24 inches at 18 inches
When the center of plate and four angles measure, the thickness of substrate layer pressing plate preferably differs less than 20%.
Laminated resin can also include several optional feature.In one embodiment, resin can the most not
Including filler.In addition to not including filler, resin can include the flow control agent (flow control agent) substituted,
Such as phenoxy resin, its based on dried resin to be present in resin to the amount of about 2wt.% more than 0wt.%.
In another embodiment, textile material is glass cloth, and it optionally has the glass stacked less than about 2
Glass silk, wherein the diameter of glass fiber is about 3 microns to about 5 microns, or glass fiber diameter is about 4 microns.
Another aspect of the present invention is a kind of laminate, and it includes following combination: (1) substrate layer pressing plate, it includes tool
There is the glass cloth that the resin of the first plane surface and the second plane impregnates；And (2) copper foil, it is attached to by solidification resin
On each plane surface in first and second substrate layer pressing plate plane surfaces, its laminate has not less than about 80 mils
Average minimum insulation thickness and the average greatest thickness (20-30 micron) of no more than about 1.2 mils, wherein glass cloth has not
The glass fiber stacked more than about 2.In present embodiment or all embodiments, the T of resingCan be 180-200 DEG C.
Another aspect of the invention is the method manufacturing superthin layer laminate material, and it comprises the following steps: (1) is by the first bronze medal
Paillon foil contacts with the first plane surface of the piece of cloth that thickness is 10 to about 30 microns, wherein tissue layer impregnated by resin or
Person has one layer of resin or both to have between the first copper foil and piece of cloth the first plane surface；And (2) are to stacked
Material applies pressure and heat, and through being enough to make the resin substantially fully cured time, with cambium layer presser blade, it has about
The substrate layer thickness of compressive plate of 1.0 to about 1.75 mils (25-45 micron).
In an embodiment of this aspect of the present invention, before applying pressure and heat to stacked material, by second
Copper sheet contacts with the second plane surface of piece of cloth, and wherein tissue layer is impregnated by resin or at the second copper foil and fabric
One layer of resin or both is had to have between sheet the second plane.It addition, Copper Foil can comprise b b stage resin b (b-staged resin)
Layer, wherein b b stage resin b has gel time and the viscosity of 15-25 pascal second of 40-50 second.
In other embodiments, laminate can have the minimum average B configuration insulation thickness of not less than about 80 mils and be not more than
The maximum average insulation thickness (20-30 micron) of about 1.2 mils.It addition, piece of cloth can be glass pieces of cloth, and tree can be made
The piece of cloth of fat dipping contacts with the first copper foil and the second copper foil and uses resin impregnated fabric sheet before.It addition, with tree
Before fat dipping piece of cloth, piece of cloth can be pre-wetted.
On the other hand, the present invention is the method manufacturing superthin layer laminate material, and it comprises the following steps: (1) is by first
Copper foil contacts with the first plane surface of the glass pieces of cloth that thickness is 10 to about 30 microns, and wherein piece of cloth is soaked by resin
Stain or have one layer of resin bed or both to have between the first copper foil and piece of cloth the first plane surface；And (2) to
Stacked material applies pressure and heat, through being enough to make the resin substantially fully cured time, with cambium layer presser blade, and its tool
(20-30 is micro-the average maximum insulation thickness of the minimum insulation thickness of not less than about 0.80 mil and no more than about 1.2 mils
Rice).
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the layer of the laminate comprising the present invention before lamination；
Fig. 2 A and 2B is several non-limiting embodiment of the superthin layer pressing plate of the present invention；
Fig. 3 is to show the figure that can be used for manufacturing some preferred aspect of the glass cloth material of the superthin layer pressing plate of the present invention；
Fig. 4 is the schematic diagram of the continuous process of the superthin layer pressing plate for preparing the present invention；And
Fig. 5 shows the method for measuring minimum inner core insulation thickness.
The description of current embodiment
The present invention relates to a kind of ultrathin copper clad laminates including a fabric sheet, it is thin that it includes that the copper being coated with one layer or two layers of resin is associated
Tissue layer.Laminate includes having first surface and the textile sheets of second surface and be attached to the first He by resin material
One or two scale copper in second piece of cloth surface.Total " thickness of substrate layer pressing plate " is being removed from laminate
The thickness of the tissue layer of the inner core resin dipping of the ultrathin copper clad laminates including a fabric sheet measured with the machinery of such as micrometer after layers of copper
Degree can be about 1.0 to about 1.75 mils (25-45 micron) and preferably from about 1.3 to about 1.75 mils (33-45 micron).
The superthin layer pressing plate of the present invention is to use a piece of or copper of two panels b b stage resin b coating and piece of cloth to be formed.Or,
Laminate is prepared by the piece of cloth using a piece of or two panels copper and resin dipping.Laminate can use and be laminated in batches or continuously
Prepared by method.When using the copper sheet of b b stage resin b coating, by by the resin side of each resin-coated copper sheet and flimsy material sheet
Plane surface staggered relatively to form coating (layup) and to apply pressure and/or heat to coating and manufacture the lamination of the present invention
Plate.Apply pressure and/or heat to coating to make soften to the resin associated with resin-coated layers of copper and penetrate into flimsy material sheet,
Meanwhile, pressure or the heat of applying makes resin be fully cured to form thin c rank copper clad laminate.
In a kind of replaceable technique, piece of cloth is impregnated by resin completely and resin portion is cured as prepreg
Or b rank.Then copper foil is applied to one or two plane surface of piece of cloth of partially cured resin dipping to be formed
Coating, and make that coating is the most above-mentioned carries out heat and/or pressure treatment makes coating be fully cured.
In order to contribute to the resin dipping to piece of cloth, can be with such as resin solvent or uncured or partially cured
The liquid of epoxy resin solution piece of cloth is carried out pretreatment or pre-wets.If piece of cloth being carried out pre-profit with resin solution
Wet, then the solid content of resin solution will be generally less than the solid content of the resin for impregnating piece of cloth.Such as, resin is pre-wetted
Solid content can be more than 0% to about 50% or more.In one embodiment, pre-wet piece of cloth with epoxy resin solution,
This solution includes the about 5wt.% solid to about 25wt.% and the solvent of remainder.
The superthin layer pressing plate of the present invention can be to be the form of copper clad laminate, and it includes being attached to Ultrathin substrate laminate
The copper foil layer of each plane surface.Or, one or two in copper foil layer partly or completely can be etched or with it
Its mode is removed from one or two plane surface of Ultrathin substrate laminate, to form ultrathin insulating lamination material layer.
With reference now to Fig. 1, it is shown that the view that the thin copper laminate of the present invention is unassembled.Copper clad laminate includes being clipped in
Tissue layers (10) between the copper (20) that two panels is resin-coated.Each resin-coated copper sheet (20) include copper foil layer (22) and
Coat the resin bed (24) of first plane surface (26) of copper foil layer (22).Second plane surface (28) of copper foil layer (22) can
With applied or uncoated.
Then by interrelated to form coating for unassembled laminated material, it is then passed through being enough to make resin flow and impregnate
The heat of tissue layer (10) and/or pressure treatment.Two embodiments of the superthin layer pressing plate of Fig. 2 A and 2B display present invention.Two
Embodiment all includes the base material laminate layer (30) with the textile material of solidification resin dipping.These embodiments also wrap
Include one or more copper foil layer (22), although can by etching or by any method known to other by two copper foil layers from
Laminate is removed, with the ultrathin insulating layer being formed.
Tissue layer (10) can be any textile material, and its thickness is preferably less than about 1 mil (about 25 microns).More preferably
Ground, the thickness of tissue layer (10) is less than about 1 mil (about 25 microns) but greater than about 0.5 mil (about 13 microns).Real at another
Executing in mode, tissue layer is glass fabric layer.Some examples of available glass cloth material include but not limited to 101,104 and 106
Glass fabric layer.Additionally available is 1000 and 1017 glass pieces of cloth or volumes, such as manufacture by the Nittobo of Tokyo that
A bit.The character of some available glass cloth sheet material is listed in the table below in 1.
Table 1
1017 glass cloth are the high density versions of 1000 glass cloth, and it has in each measurement unit of warp-wise and broadwise
There is extra silk.Compared with 101 glass cloth, 1000 and 1017 glass cloth are all that laminate provides higher mechanical stability.
And, 1000 and 1017 glass cloth all more smooth than 101 glass cloth about 60%.Additionally, as it is shown on figure 3, at 1000 and 1017 glass
In cloth, warp thread and weft yarn all separate extension so that most 2 silks are stacked up and down.As shown in Table 1, this causes glass fibre to have
Have more than the air permeability of 200.Compared with having the glass cloth more than 2 silks stacked up and down, this glass cloth character also causes non-
The thinnest layer of web material.Additionally, it has been found that be about the glass filate of 3 microns to 5 microns the most about 4 microns by diameter
The glass cloth become is used especially for manufacturing superthin layer pressing plate.
Resin-coated copper foil used in some embodiment of the present invention can be used any in this area
Partially cured resin-coated copper sheet material.In one embodiment, resin-coated Copper Foil is the Copper Foil of b b stage resin b coating
Sheet.In order to produce superthin layer presser blade, the Copper Foil of preferred resin coating has the thinnest partially cured resin bed and very
Thin copper foil layer.Therefore, in one embodiment, the thickness of the resin bed of resin-coated copper can be less than about 50 microns
And greater than about 5 microns.In another embodiment, the thickness of resin bed can be less than 25 microns and more than 8 microns.At another
In embodiment, the thickness of resin bed can be about 15 microns.
It is preferably thin copper foil or volume for manufacturing the copper foil of the superthin layer pressing plate of the present invention, such as less than 2 ounces
And Copper Foil below more preferably 1 ounce copper.Usually, the thickness of Copper Foil is about 15 to about 40 microns.Narrower and available
Copper thickness scope be about 15 to about 25 microns.It addition, Copper Foil can be conventional or the Copper Foil of reversion process.A reality
Executing in mode, the copper foil surface that be associated with resin bed or with resin dipping piece of cloth plane surface is associated has about 3
To the roughness of about 5 microns.Or, can deposit by sputtering, chemical gaseous phase or known in the art can be used on base material
It is coated with any other method of the thinnest metal level, copper is coated on prepreg or b rank base material with the thinnest layer, or
Coat on the thinnest prepreg or b b stage resin b sheet.
The average of currently preferred superthin layer pressing plate (takes advantage of 24 inches to be laminated on plates and 4 points or more at 18 inches
Point is measured) " insulation thickness " scope is about 0.75 to 1.5 mil (19-38 micron), even more preferably about 0.8 to about 1.2 mil
(20-30 micron).Term " insulation thickness " refers to the minimum thickness measured by the textile material part that the resin to laminate impregnates
Scope between degree and maximum gauge, and do not include the thickness of any layers of copper being associated with laminate.Superthin layer pressing plate exhausted
Edge thickness scope is by preparing micro-cross section of laminate and measuring the minimum widith of insulated part of laminate under the microscope
Measure with Breadth Maximum.The mensuration of minimum insulation thickness is explained with reference to Fig. 5.Minimum insulation thickness measure be from laminate
The layers of copper (22) that is associated of side extend into the farthest copper tooth of substrate layer pressing plate (30) or the tip of skeleton (50)
The deepest copper tooth of substrate layer pressing plate (30) or dendroid is extended into from the layers of copper (23) being associated with the opposite side of laminate
Distance (X) between crystal (60).Maximum insulation thickness is the measurement from the first bronze medal plane to the distance of relative copper plane.
Another important properties of the superthin layer pressing plate of the present invention is laminate thickness distribution.It is desirable that laminate
The thickness measured on any point on its whole surface should be identical.But in practice, as a consequence it is hardly possible to reach homogeneous distribution.
Thickness deviation on whole laminating surface is the most, and the most more likely laminate will not pass through such as voltage-withstand test (Hipot
Testing), the quality control test of peel strength test etc..Therefore, in one embodiment, the laminate of the present invention
Dimensional stability can be such that the layer measured by 18 inches of centers of rectangle laminate sheet material taking advantage of 24 inches and four angles
The change of pressing plate " base thickness " is no more than about 20%, and more preferably no more than about 10%.
The laminate of the present invention uses resin to provide insulation barrier and/or strengthening layer of web material.The application's is upper and lower
Term " resin " used in literary composition typically refers to present or future can be used in printed circuit board (PCB) or other electronic application
Any curable resin composition used in the production of laminate.Most often, epoxy resin is used to manufacture such layer
Pressing plate.Term " epoxy resin " generally refers at C.A.May, Epoxy Resins, 2nd Edition, (New York&
Basle:Marcel Dekker Inc.), the curable compositions of the compound containing oxirane ring described in 1988.
In order to provide desired basis machinery and the thermal property of solidification resin and the laminate that is produced from, to resin combination
Thing adds one or more epoxy resin.Available epoxy resin is known to those skilled in the art for can be used for electronics composite wood
Those of material and the resin combination used by laminate.
The example of epoxy resin includes phenol type, such as based on bisphenol A diglycidyl ether (" double-A epoxy resin "), base
In phenol-formaldehyde novolaRs or the glycidyl ether of cresol-formaldehyde novolac, contract based on three (para hydroxybenzene phenol) methane three
Water glycerin ether or based on tetraphenyl ethane four glycidyl ether those, or such as based on four glycidyl group diphenylamino first
Alkane or based on those types to 2-aminooxyethanol triglycidyl ether；Alicyclic ring type, such as based on 3,4-epoxycyclohexyl first
Those of base 3,4-7-oxa-bicyclo[4.1.0 formic acid esters.The scope of term " epoxy resin " also includes containing excess epoxy radicals (as
Above-mentioned type) the product of compound and aromatic dihydroxy compound.These compounds can be optionally substituted by halogen.
Resin system used in resin-coated Copper Foil can include well known by persons skilled in the art for manufacturing tree
The additive of lipid layer pressing plate and excipient, such as fire retardant.It is preferable, however, that resin used in the laminate of the present invention does not include appointing
What filler, such as Pulvis Talci, PTFE etc..Owing to sometimes adding filler in resin system as flow control agent, so at Jiang Shu
Before fat is coated copper foil layer or is directly used in dipping tissue layer, adding non-packing type flow control agent in resin can be to have
?.One class can flow control agent be phenoxy resin, its can based on dry weight with more than 0wt.% to about 2% amount add
Resin system used to the present invention.
Some examples of epoxy resin available in the manufacture of the laminate of the present invention are disclosed in such as United States Patent (USP) 5,
464,658,6,187,852,6,509,414 and 6, in 322,885, by the description of all these files by reference
It is expressly incorporated herein.
The epoxy resin being particularly useful can have the solidification T of about 180 DEG C to 200 DEG Cg.Additionally, when resin combines also with copper
During solidification, it should obtain the superthin layer pressing plate with the peel strength of about 4.5lb./in or above.Additionally, by resin-coated
Copper foil layer be applied to layer of web material before, the resin being associated with copper foil layer can be b rank so that during the gel of resin
Between and viscosity match, so that resin readily penetrates through glass cloth in laminate manufacturing process and solidifies.An embodiment party
In formula, select resin and make its b rank, thus making it have gel time and the viscosity of 5-40 pascal second of 30 to 90 seconds.
In another embodiment, select resin and make its b rank, thus making it have the gel time of 40-50 second and about 15-25 handkerchief
The viscosity of SIKA second.
In one embodiment, in the manufacture of the superthin layer pressing plate of the present invention, available resin-coated copper sheet is permissible
Manufacturing by uncured or partially cured liquid resin is coated copper foil, wherein to be about 8 micro-for the thickness of resin bed
Meter Zhi Yue 20 microns, and thickness is even more preferably about 10 to 15 microns.When using resin-coated copper sheet to manufacture thickness, to be about 1 close
When ear or less laminate, Copper Foil used can be that thickness is about 18 microns and surface roughness is about 1 ounce of 3 microns
Copper Foil.Resin can be coated a surface of Copper Foil with the thickness of about 14 microns and be partially cured to form the coating of b b stage resin b
Copper sheet.
Resin, fabric and resin-coated copper foil mentioned above can be used in a batch process or continuity method manufactures this
Bright laminate.In the exemplary continuous method for the laminate manufacturing the present invention, by copper, resin prepreg material and flimsy material sheet
Each the serialgram of form is deployed in a series of drive roll the net of the stacking to form fabric, this net constantly
Adjacent with resin prepreg tablet, this resin prepreg tablet is adjacent with copper foil so that resin prepreg tablet be positioned at copper foil with
Between piece of cloth.Then make net experience be enough to make resin transfer to enter in textile material and the heat of completely crued time and
Pressure condition.In the laminate formed, resin material migration in fabric cause along with combination layer as discussed above from
The net of three layers changes into and is individually laminated plate, the thickness (distance between copper foil material and piece of cloth material) of resin bed
Reduce and close to zero.In another optional method, single prepreg resin sheet can be coated layer of web material
Said composition is also clipped between two layers of copper by side, and this backward coating applies heat and/or pressure, so that resin material flows also
Thorough impregnation tissue layer and make two copper foil layers all be attached on substrate layer pressing plate.
In an optional embodiment, can in the following way, while manufacturing laminate, manufacture resin and be coated with
The copper sheet of cloth: coated by thin resinous coat on the copper sheet of two different continuous movings, removes any excess from this sheet
Resin, to control the thickness of resin, then makes resin portion be cured to form the coating of b b stage resin b under heat and/or pressure condition
Copper sheet.Then the copper sheet that b b stage resin b is coated with can be directly used in laminate manufacturing process.
In another embodiment, textile material, whether through pretreatment, resin all can be continuously fed into
In bath, so that textile material is impregnated by resin.In this stage in process, resin is the most partially cured.It
After, one or two copper foil layer can be associated to be formed with the first and/or second plane surface of the piece of cloth of resin dipping
Net, hereafter applies heat and/or pressure so that resin is fully cured to net.
It is shown in Fig. 4, wherein with the first resin for manufacturing another embodiment of the continuity method of the laminate of the present invention
The copper t(110 of coating), fabric (120) and the second resin-coated copper t(130) serialgram of respective form launched continuously
Enter in a series of drive roll (140) adjacent with the resin of resin-coated copper sheet to form the net fabric of multilamellar,
Resin-coated copper sheet is adjacent with mould release membrance (release film).Then net is led into treatment region with constant rate of speed
And experience heat and pressure condition be enough to make resin transfer enter textile material and be solidified into the time of c b stage resin b (150).Finally,
Laminate (160) leaves treatment region (150) and collects with the form of veneer roll (160).Method in Fig. 4 include two parallel
Feeding and (the feed and take up) system of receiving, wherein the first resin-coated copper (110 '), fabric (120 ') and the
The parallel volume combination of two resin-coated copper (130 ') forms the second net, and the second net is directed into treatment region
(150) laminate of gained and is collected with the form of volume (160 ').When two nets are simultaneously directed entrance treatment region (150)
Time, the barrier material of such as copper or aluminum metal film can be fed and guides by rolling up (170) at the first net (175) and the second net
Between shape thing (180), to allow two thin laminate material layers to can be easily separated when leaving treatment region (150).
As it has been described above, the superthin layer pressing plate of the present invention can also be manufactured by batch process.Embodiment party a batch process
In formula, on the resin bed of the copper foil that piece of cloth puts on the coating of b b stage resin b, the piece of cloth being then resisted against exposure applies the
The copper foil resin bed of two b b stage resin b coatings is down.This process may be repeated one or more times and includes multiple layer to produce
The stacking of pressing plate.Then being stacked and placed in forcing press by heap, this forcing press applies pressure and heat to coating, so that the solidification of b b stage resin b
And along with resin solidification is compeled to enable its flow in textile material.Remove pressure and heat and laminate is separated from each other.
Laminating method and parameter for manufacturing the superthin layer pressing plate of the present invention can be with wide variation and generally by ability
Well known to the those skilled in the art of territory.In typical cure cycle in batches, stacking is maintained at the pressure of about 40psi to about 900psi
Under power and in the vacuum of about 30in/Hg.Within the period of about 20 minutes, the temperature of stacking is increased to about 375 °F from about 180 °F.
To be stacked at a temperature of about 375 °F and keep 75 minutes, afterwards within the period of 20 minutes, by cold from the temperature of 375 °F for stacking
But to the temperature of 75 °F.
The following example illustrates the different aspect of the present invention, but is not used in and limits its scope.
Embodiment 1
In this embodiment it is that can be used for manufacturing the resin system of the ultra-thin resin system of the present invention.Joining of resin system
Side is as follows.
The preparation of resin is by being added to mixing container by propylene glycol monomethyl ether, then adding in same mixing container
Remaining compositions all in addition to 2-phenylimidazole, and composition is mixed 30 minutes.2-phenylimidazole is dissolved in propylene glycol monomethyl ether, then
Add to mixture.Being homogenized by mixture 30 minutes, resin can use.
Embodiment 2
It is the laying method in batches by using hydraulic press for manufacturing a method of the superthin layer pressing plate of the present invention
(batch lay up process).According to the method, extra thin fabric material is placed between the copper that two panels is resin-coated so that
Resinous coat contacts with piece of cloth to form coating.Being placed in hydraulic press by coating, pressure is 15-20bar and initial temperature is
110℃(230°F).Press temperature is increased to 190 DEG C (375 °F) with the speed of 5-7 centigrade per minute.By coating 190
DEG C keep 70 minutes.Then coating is made to cool down 30 minutes to room temperature.
Fig. 2 A represents lamination, the most a layers of copper (22) is etched away from coating.In lay-up process, from resin
The resin of the copper of coating penetrates textile material to form substrate layer pressing plate (30).
By said method, the copper sheet resin-coated for TRL8 and TRL15 using Circuitfoil to produce (has 8 or 15
The resin thickness of micron) and 1000 and 1017 glass cloth prepare several 7 inches and take advantage of the laboratory level coating of 8 inches.Etching
Coating is to remove copper removal, and after the etching, measures coating at each angle (upper right/upper left/bottom right/lower-left) of coating and center
Thickness.Result is as shown in table 2 below.
Table 2
These results show the good dimensional stability of whole coating.
Claims (19)
1. a laminate, it includes following combination:
Glass cloth sheet material, it has the first plane surface, the second plane surface, the original depth of described glass pieces of cloth be 10 to
30 microns, and
At least one resin-coated copper foil, it is resin-coated with described by the plane surface making described glass cloth sheet material
The resin bed of copper foil contact and make the resin solidification of described resin-coated copper foil to be attached to described glass cloth sheet material
On the plane surface of material, to obtain the substrate layer pressing plate that thickness is 1.0 to 1.75 mils, and wherein said laminate has the least
In average minimum insulation thickness and the average maximum insulation thickness of no more than 1.2 mils of 0.8 mil, and wherein said resin
The copper foil of coating includes the b b stage resin b that thickness is 8 to 25 microns.
2. laminate as claimed in claim 1, wherein copper foil is attached to the first and second flat of described glass cloth sheet material
On each plane surface in surface, face.
3. laminate as claimed in claim 1, the thickness of wherein said substrate layer pressing plate is 1.3 to 1.6 mils.
4. laminate as claimed in claim 1, wherein said copper foil has the thickness of 15 to 40 microns.
5. laminate as claimed in claim 1, wherein said copper foil has the thickness of 15 to 25 microns.
6. laminate as claimed in claim 1, wherein when the rectangle taking advantage of 24 inches at 18 inches be laminated plate center and
When four angles measure, the thickness difference of substrate layer pressing plate is less than 20%.
7. laminate as claimed in claim 1, wherein said resin does not include filler.
8. laminate as claimed in claim 7, wherein said resin includes flow control agent.
9. laminate as claimed in claim 8, wherein said flow control agent is phenoxy resin, its based on dried resin with greatly
Amount in 0wt.% to 2wt.% is present in resin.
10. laminate as claimed in claim 1, wherein said glass pieces of cloth have the glass fiber stacked less than about 2,
A diameter of 3 microns to 5 microns of wherein said glass fiber.
11. laminates as claimed in claim 10, a diameter of 4 microns of the glass fiber of wherein said glass pieces of cloth.
12. laminates as claimed in claim 1, the thickness of wherein said glass pieces of cloth is 0.5 to 1 mil.
13. 1 kinds of laminates, it includes following combination:
Glass pieces of cloth, it has the first plane surface, the second plane surface；And
Resin-coated copper foil, it is by making the first plane surface of described glass pieces of cloth and the second plane surface each and institute
The b b stage resin b layer that thickness is 8 to 25 microns stating resin-coated copper foil contacts and makes the b of described resin-coated copper foil
B stage resin b solidifies and is attached on each plane surface in the first and second plane surfaces of described glass pieces of cloth to obtain
Described laminate, wherein said laminate has not less than the average minimum insulation thickness of 0.8 mil and no more than 1.2 mils
Average maximum insulation thickness, wherein said glass pieces of cloth have the glass fiber stacked less than about 2.
14. laminates as claimed in claim 13, the T of wherein said resingFor 180-200 DEG C.
15. 1 kinds of methods manufacturing superthin layer laminate material, it comprises the following steps:
First plane surface of first copper foil and the glass pieces of cloth that thickness is 10 to 30 microns with b b stage resin b layer is connected
Touching, wherein said b b stage resin b layer has the gel time of 40-50 second, the viscosity of 15-25 pascal second and the thickness of 8 to 25 microns
Degree so that described b b stage resin b layer is between the first copper foil and the first plane surface of glass pieces of cloth；And
Pressure and heat is applied to stacked material, through being enough to make the resin completely crued time, with cambium layer presser blade, its tool
There is the substrate layer thickness of compressive plate of 1.0 to 1.75 mils, and wherein said laminate has exhausted not less than the average minimum of 0.8 mil
Edge thickness and the average maximum insulation thickness of no more than 1.2 mils.
16. methods as claimed in claim 15, wherein before applying pressure and heat to stacked material, by the second copper foil
Contact with the second plane surface of described glass pieces of cloth, wherein the second copper foil and glass pieces of cloth the second plane surface it
Between have one layer of resin.
17. methods as claimed in claim 16, wherein said second copper foil includes b b stage resin b layer, wherein said b b stage resin b
There is gel time and the viscosity of 15-25 pascal second of 40-50 second.
18. methods as claimed in claim 15, wherein said method is continuity method.
19. methods as claimed in claim 15, wherein make the resin bed with the copper foil of b b stage resin b layer and glass pieces of cloth
Plane surface contact before, glass pieces of cloth are pre-wetted.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161446458P | 2011-02-24 | 2011-02-24 | |
| US61/446,458 | 2011-02-24 | ||
| PCT/US2012/026582 WO2012116310A1 (en) | 2011-02-24 | 2012-02-24 | Ultrathin laminates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103429423A CN103429423A (en) | 2013-12-04 |
| CN103429423B true CN103429423B (en) | 2016-11-30 |
Family
ID=
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0970922A (en) * | 1995-06-28 | 1997-03-18 | Mitsui Toatsu Chem Inc | Thin laminate and manufacture thereof |
| US6333384B1 (en) * | 1998-11-02 | 2001-12-25 | Gil Technologies | Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom |
| CN101166778A (en) * | 2005-04-27 | 2008-04-23 | 日立化成工业株式会社 | Composite, prepreg, laminated plate clad with metal foil, material for connecting circuit board, and multilayer printed wiring board and method for manufacture thereof |
| CN101348575A (en) * | 2004-03-04 | 2009-01-21 | 日立化成工业株式会社 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0970922A (en) * | 1995-06-28 | 1997-03-18 | Mitsui Toatsu Chem Inc | Thin laminate and manufacture thereof |
| US6333384B1 (en) * | 1998-11-02 | 2001-12-25 | Gil Technologies | Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom |
| CN101348575A (en) * | 2004-03-04 | 2009-01-21 | 日立化成工业株式会社 | Prepreg and metal foil-clad laminate and printed circuit board obtained by using the same |
| CN101166778A (en) * | 2005-04-27 | 2008-04-23 | 日立化成工业株式会社 | Composite, prepreg, laminated plate clad with metal foil, material for connecting circuit board, and multilayer printed wiring board and method for manufacture thereof |
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