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08/19/2004 16:52 FAX 9494768640 



CHRISTIE PARKER 



iaoi7 



© 



Europalsches Patentamt 
European Patent Office 
Office europ^en des brevets 



© Publication number 



0 313 961 

A2 



EUROPEAN PATENT APPLICATION 



0 Application number: 88117300.9 
© Date or niing: iaiO.&8 



® Int. CI ": H05K 1/03 , B32B 5/28 , 
C08J S/04 , //C08L27/12 



(») Priority: 26.10.87 US 113533 


© Applicant ROGERS CORPORATION 


@ Date of publication of application; 


Main Street 


Rogers, Conn. 06263(US) 


03.05.89 Bulletin B^fiB 


© rnventor McGinnis, Leon 




© Designated Contracting States; 




BE DE FR GB IT NL SB 


deceased(U$) 




Inventor Carroll, James R: 




41 d Barbara Orfve 




Tempe Arizona 85281(11$) 




Inventor R/lilter, Tenry 1. 




11233 South 163rd Street 




Gilbert Arizona 85234<US). 




Inventor: Nor ris, Michael 




12611 East Ballejo 




Chandler Arizona 8524S(liS) 




© Representative: Meyers, Ernest ©t al 




Office de. Brevets Freyiinger & Associes 46 




rue du Clmetiere B.P. 1153 




L-1011 Luxembourg(LU) 



CM 

o 

CO 

o 
Ui 



© Glass fiber reinforced fliit^ropolymeric circuit laminate, 

@ A fluoropolymGric circuit laminate consisting of one or more layers of fluoropol/mer impregnated woven 
giass cloth sandwiched between one or more layers of ''random" microfiberglass reinforced fluoropolymer is 
presented. This composite of fluoropolymer^ woven glass ^nc and random glass microfibers may be clad on 
one or both outer surfaces with a suitable conductive material such as- copper or certain known resistive foils. 
The fluoropolymer impregnated woven glass layer of layers will be nested between microfiberglass reinforced 
Hgoropolymer layers to provide the outer surfaces of the circuit with smooth surfaces for fine line circuitry. The 
circuit laminate of the present invention exhibits good dimensional stability, smooth surfaces for fine line 
circuitry, good electrical properties, and strong foil and interlaminar adhesion properties. 



FIG. 1 




. Xbtox CGpy Cenlra 



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CHRISTIE PARKER 



121018 



ep 0 313 961 A2 



GLASS RBER ReiNFORCEO FLUOROPOLYMERIC CIRCUIT LAMINATE 



This invention relates to lan^inated circuit materials. More particularly, this invention relates to ■ 
fluoropotymeric glass reinforced drctiit materials having excellent dimensional stability, electrical properties 
and a smooth surface. This circuit material is particularly well suited for applications requiring microwave 
5 operating frequendes. 

Most common printed wiring board materials undergo dimensional changes during processing. These 
changes are induced by stress relaxation as metal claddings are removed and/or by absorption with 
processing solutions, and/or by temperature, pressure or humidity excursions. The addition of reinforcing 
fibers to polymer systems is intended, in part« to reduce the dimensional changes that occur during 
10 pnscessing. 

With respect to glass reinforced fluoropolymer boards, particularly boards composed of poly- 
lelrafluoroethylene (PTFE), there have been three common prior art types. 



IS Type 1 

The first type contemplates the use of a homogeneous dielectric layer of random microfiber glasis 
reinforced PTFE. This approach produce^ a laminate with superior electrical performance, primarily 
because of the low weight percent of glass present These random microfiberglass reinforced PTFG 

20 materials have smooth surfaces for the productioh of Hne line circuitry needed In microwave applications. 
However, of Ih© three common PTFE laminate- types, it has the largest dinrvsnsional change upon 
processing. It will be appreciated that the lack of dimensional stability is a significant drawback as there are 
many well known problems associated with poor dimensional stability. One particuiarly troublesome 
problem involves the necessity for a double etching pnacedure. Such a procedure involves creation gf two 

25 sets of artwork, the initial set processing geometries larger than that desired. After photoimaging and 
etching, much of the dimensional change will be realiziad. The final artwork ts then photoimaged and 
etched. It will be appreciated that this double etching procedure leads to significantly higher costs due to 
additionai labor, materials <e.g. photoimagable photoresist etching soiution). artwork costs and assodated 
handling damage. Random glass Rber reinforced circuit boards of this type have a dielectric constant of 

ao 220 to 2.33. are well known in the art by the designations QR and GP; and are specified to military 
designation MIL-P-13949/7E. 



Type 2 

35 ^ 

The second type of circurt material involves the use of PTFE impregnated woven glass cioths and 
produces a laminate exhibiting a higher dissipation factor than that described in the first type. Such 
laminates typically possess better dimensionai stability than those described above principally because of 
the presence of continuous glass fibers (rather than short discontinuous microfibers). These materials have 
40 a dielectric constant of 2,4 to 2,6 and are known in the art fay the designation GX and GT. GX and GT 
materials are specified in MIL-P-13949/14A. 



Type 3 

The third type of fluoropolymer circuit materials comprise composites consisting of alternating layers of 
unreinforced PTFE (i,e-, no glass filler) and PTFE Impregnated woven glass cloth. This third type offers low 
dieletric constant, dissipation factor, and improved dimensionai stability relative to type GR materials. 
However, because of the presence of unreinforced layers of PTFE , the laminate suffers from poor foil 
so adhesion and interiaminar or interstitial de(amination problems. Such laminates also do not withstand 
thermal cycling, thermal stress or molten solder temperatures without significant bond degradation. Because 
of the poor foil adhesion, copper peel strength drops substantially after temperature excursions such as 
those associated with multilayer bonding or temperature cycling. These laminates also suffer from 
significant changes in i-axis dielectric constant because of the stratified construction. These laminates have 
dielectric contents of about 2.17 and are desingated as MIL-P-13949/14A type GY, 

2 



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CHRISTIE PARKER 



ii]019 



EP 0 313 961 A2 

While al( of the above discussed types of ftuoropolymsnc circtjit maiterials include certain advantageous 
and desirable features, each also suffers from certain limitations and drawbacks. Unfortunately, ttier© is 
presently no one glass reinforced fluoropolymBric circuit material which combines the best fe^res of the 
known materials (e.g., good dlmen$ional stability, good electrical properties and smooth surfaces for fine 
5 tme production) without $ome of the problems associated with these prior art materials. 

The purpose of the present invention is to overcome or alleviate * the above-discussed and other 
deficiencies and drawbacks of the prior art. In accordance with the present invention, a circuit laminate (s 
provided which is composed of one or more layers of fluoropolymer impregnated woven glass doth 
sandwiched between one or more layers of "random" microfibergiass reinforced fluoropolymer. This 
10 composite of fluoropolymer. woven glass fabric and random glass microfibers may be clad on one or both 
outer surtaces wtlh a suitable conductive material such as copper or certain known resistive foils. The 
fluoropolymer impregnated woven gi^ss layer or layers will be nested between microfibergfass reinforced 
fluoropolymer layers to provide the outer surfaces of the circuit with smooth surfaces for fine line circuitry. 
The circuit laminate of the present Invention combines all of the best qualities of known fluoropolymer 
15 circuit materials without any of the various disadvantages. For example, the present invention exhibits good 
dimensional Ability (like GX, GT and (5Y), smooth surfaces for. tine line circuitry (like GR, GP), good 
electrical properdes (like GR.GP|GY) and strong foil and interiaminar adhesion properties (unlike QY). 

The above-discussed and other features and advantages of the present invention will be appreciated 
and understood by those skilted in the art from the following detailed description and drawings. 
20 Referring now to the drawings wherein like elements are numbered alike In the several figures : 

RGURE 1 is a cxoss sectional elevation view of a circuit laminate in accordance wrth the present 
Invention: 

FIGURE 2 Is a cross sectional elevatton view of another circuit laminate in accordance with the 
present Invention; and 

25 RGURE 3 is a cross sectional elevation view of still anofl^er circuit laminate in accordance- with the 

present invention. 

Referring first to FIGURE 1, a fluoropolymer composite circuit laminate in accordance with the present 
invention is identified at 10. Generally, the dielectric substrate 12 of circuit laminate 10 connprises glass 

30 microfiber reinforced fluoropolymer layers interieaved with at least one layer of fluoropolymer impregnated 
woven glass cloth. The total dielectric thickness will preferably range fronn 0.076 mm to 12,7 mm. In -the 
particular embodiment of the present invention depicted in RGURE 1. a relatively* si rnplo dielectric 
construction Is shown Including a pair of microglass fiber reinforced fluoropolymer layers 14 and 16 
sandwiching therebelweert a layer 18 of ftuoropolymer impregnated woven glass cloth. However, it will be 

35 appreciated that layers 14, 16 and 18 may be comprised of multiple layers or plys of the respective 
glass/fluoropolymer composites. 

The diefoctric substrate t2 includes one or two cortductrve layers on its opposed outer surfaces. In the 
FIGURE 1 embodiment, two conductive layers 20 and 22 are provided on tho exposed surfaces of dielectric 
layers 14 and 16. Conductive layers 20 and 22 may be comprised of a suitable conductive metal such as 

40 copper. AitemafivBiy, the conductive layers may include portions of kriown resistive foils such as the type 
disclosed in U.S. Patent No 3,808.576. which is Incorporated herein by reference; and which is commer- 
cially available under tho trademark "Ohmega-Piy Foil". 

The fluoropolymeric material used in both the microfiber glass and woven- glass layers 14. 1G and IB is 
preferably polytetrafluoroethylen^ (PTFE). However, other fluoropolymeric materials could also be used 

4S including, but not limited to a copolymer of tetrafluoroethylene and perfluorbalkyi vinyl ether (PFA). a 
copolymer of hexafluoropropylene and tetrafluoroethylene (FEP) and a copolymer of tetrafluoroethylene and 
ethylene (Tefzel). 

Preferably, the length, diameter and percentage of glass fibers (which may consist of commercially 
available E-glass) in the homogeneously and randomly dispersed microfiber glass reinforced fluoropolymer 
50 layers (e.g. layers 14 and 16) will vary within the following ranges : 
Length: less than 5000 micrometers 
Diameter: 0.3 to 0.7 micrometers 
Weight percentage: 2 % to 25 % 

Preferably, the fluoropolymer impregnated woven glass cloth layer (e.g. layer 18) will consist of a 
55 suitable commercially available weave of ^-glass with weight percent of fiuorbpolymer of between about 30 
% to about 85 These weaves may include, in addition to style 1080. styles 108, 106. 112 and similar 
Styles. All of the style numbers are common industry designations. 

As mentioned, the structure of the laminate of the present invention consists of ono or more layers of 



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OP 0 313 961 A2 



fluoropoiym^r impregnated woven glass doth separated by one or more layers of random microfiber 
reinforced fluoropolynner. The fluoropolymer impregn^tGd woven glass cloth will preferably compriso from 
about 10 % to 30 % of the overall lamfnat© thicknoss, sxclusive of claddings. 

In FIGUR5 2, a more complex embodiment of the present invention is shown generally at 24. Circuit 
5 laminate 24 comprises a similar dielectric substrate 12,, but additionally includes upper and lower 
nuoropolymeric (e.g. PTFE) bonding layers 26 and 28 on glass reinforced fluoropolymer layers 14' and ie' 
respectively. These bounding films 25, 26 are quite thin (e.g. 0.025 mm thick) and are used to improve Ihe 
adhesion with the metal cladding. The embodiment of RGURE 2 further includes an upper outer layer 30 
comprising a known resistive foil which consists of a resistive layer plated onto a copper foil: and a lovver 
w outer layer 32 comprising a suitable conductive foil such as copper. The Structure of circuit laminate 24 is 
discussed in more detail hereinafter with regard to example I. 

Sfili another embodiment of the present invention is shown generally at 34 in RGURE 3. Circuit 
laminate 34 Is substantially similar to circuit laminate 24 of FIGURE 2, The only difference between the 
circuits is that laminate 34 includes an additionar layer 36 of fluoropofymer impregnated woven glass and an 
IS additional layer 38 of microglas« roinforced fluoropolymer. Note that woven glass layer 36 Is sandwiched 
between random- mlcroglass layers is' and 38, FIGURE 3 will be discussed in more deta» with regard to 
Examples 6, 7, 12 and 13- 

The following are non-limited examples of the circuit laminate of the present invention : 

20 

Example i 

The ctrcuit laminate used for th© first example has an overall constaiction as shown In FIGURE 2. The 
following Is a det^led descilption of each of the layers in the laminate composite with reference \o the 
25 identifying numerals of FIGURE 2. 

The microglass reinforced layers 14' and 16' are RT/duroid 5080® a commercially available material ' 
manufactured by Rogers Conporation, RT/durocd 59800 is a glass microfiber reinforced PTFE composite 
having a random homogeneous dispersion of glass microflbers within the ranges described hereinabove. In 
the construction described above, the microglass reinforced layers 14* and 16' comprise a total of 3.80 mm 
OT of the 5 mm of dielectric, or 1,90 mm per side. 

The woven glass layer 16 is polytetraflworoethylene (PTFE) coated commercially available woven glass 
fabric. The glass reinforcement is a woven glass fabric comprised of E-gla3$ woven in style 1060 (a 
common industry designation). The PTFE comprised 76 % of the weight of the PTFE coated woven glass 
fabric, the remaining porfion is the E-glass. In the above construction, the PTFE impregnated, woven glass 
35 comprises 0.076 mm of the 0,50 mm total thickness. 

The PTFE bonding films 26 and 28 are commerciaily available skived or cast PTf^ films 0,025 mm 
thick. These films are 100 % PTFE (no glass, or other, reinforcements). These Hlms improve mechanical 
adhesion of metal claddings because of their lower melt viscosity. In the construction described above, the 
films account for a total of 0,050 mm (two pieces of 0.025 mm film) out of a total dielectric thickness of 0.05 
mm- 

Resistive layer 30 is Ohmega foil, a commercially available resistive foil available from Ohmega 
Technologies. The foil consists of a resistive layer plated onto a copper foil 

Conductive layer 32 is a copper foil which is a commercially available electrodeposited foil meeting IPC 
spedfication #IPC-CF-150E- Foil weight is 28 g (nominal thickness 0.03S mm). 
4S In Table 1. a data summary for the circuit laminate of Example i Is set forth for three different lots {A- 
C). This data is compared to the same properties of a standard microfiber glass reinfonsed circuit 
(RT/duroid 5880<S>). As is Clear from Table 1, the circuit laminate of the present Invention has a low dielectric 
constant (2.222 to 2.229) and excellent dimensional stability, especially when compared to prior art type GR 
materials (e.g. RT/duroid 5880®). 



ss 



4 



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CHRISTIE PARKER 



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In the foKowing examples, the same overall structure of FIGURE 2 Jias been used, however certain 
variations and Changes in nnateriai percentages and compositions have been made. The changes are as 
ss follovtfs; 

The microglass layers 14 . 16' of th© laminate is RT/duroid 5870© commercially avaiiabi© from nogers 
Corporation (rather than RT/duroid 5880 <» used in Example 1). Laminates with total dielectric thickness of 
0.25 mm through 1,575 mm have been evaluated. The annount of microglass reinforced dielectric (item 12 



5 



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CHRISTIE PARKER 



@022 



EP 0 313 961 A2 

in RGURE 2) used in tfiese laminates varied from 0,15 mm (in the case of the 2,5 mm laminate), to 1,40 
mm (in ti^o c^e of the 1.575 mm laminate). Se© the attached table 2 for detailed information on the 
. composftional percentages of each componanti 

The PTpn bonding films 26 and 28 used in these laminates were as described above, but varied In 
5 thickness from 0.0127 mm to 0,05 mm. See the attached table 2 tor more details. 

The PTFE coated woven glass fabric is' used in these laminations was identical to that used for the 
laminations described above in example I. 

In addftion to the evaluations of the above-noted structures, a composite based on the laminate 
depicted in FIGURE 3 was also evaluated. Reference should be made to table 2 lor a detailed analysis of 
w the composition of the FIGURE 3 laminates which correspond to Examples 6, 7, X2 and 13. 



*5 



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The electrical and mechanical properties of Examples 2-13 are set forth in Table 3 and are in 
accordance with the results set forth In tatile (. 

As IS clear from a review of the foregoing results, the circuit laminate of the present invention provicJes 
3(1 of the advantages of the px\^x art flaoropolymeric materials discussed afaove in thQ background section 
(e-g. innproved dimensional stabUity, smooth surface for fine lines, good electrical properties including lo.w 
dielectric constant, low dissipation factor and good surface isotropy) without any of the various deficiencies 



a 

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@025 



EP 0 313 961 A2 

aid drawbacks of these prior matenals. Moreover, the circuit laminate, of the present invention may, in some 
instances, preclude the necessity for double etching procedures because of its improved dimensiooaJ 
stability. The circuit laminate of the present invention also exhibit strong foil and Interlaminar adhesion 
properties, * * - 

Claims 

1. A circuit substrate laminate comprising: 

10 at least one first layer (18) of a fluoropalymer impregnated woven glass cloth having opposed first and 
- second surfaces: 

at least one first layer (14) of a random microglass reinforced fjuoropolymer on said first surface of said first 
layer (18) of fluoropolytner impregnated woven glass clothi and 

at least one second layer (16) of a random microglass reinforced. fluoropolymer on said second surface of 
15 said first layer of fluoropolymer impregnated woven gtess cloth. 

2. A laminate as claimed in claim 1, wherein each of said ftrst and second microglass reinforced 
fluoropolymer layers (14.16) includes an exposed .surfece opposite said at least one layer (18) of 
fluoropolymer impregnated woven glass cloth and including : 

conductive material (20.22) on at least a portion of at least one of said exposed surfaces of said first and 
20 second layers (14,16) of microglass reinforced fluoropolymer. 

3. A laminate as claimed in claim 2, wherein said condufctive material is copper. 

4. A laminate as claimed in claim 2, wherein said conductive matenat is a resistive foil. 

5. A laminate as claimed in claim 1. wherein ^aid fluoropolymer is at least one of the fluoropolymers 
selected from the group consisting of : 

25 polytetnafluorofethyiene, a copolymer of tetrafluoroethylene and perfluoroakyt vinyl ether, a copolymer of 
hexafluoropropylene and tetrafluoroethylene or a copolymer of tetrafluoroethylene and ethylene. 

^. A laminate S5 claimed in claim 1, wherein said fluoropolymer impregnated woven glass cloth layer 
has about 30 to 85 weight percent of fluoropolymer. 

7. A laminate as claimed in claim i , wherein said at least one fluoropolymer impregnated woven glass 
30 cloth layer comprises about lO to 60 percent of the total laminate thiclcness. 

8. A laminate as claimed in claim i. wherein' said micraglass is microfiberglass and wherein said 
microfibergiass has a length of less than 5000 micrometers and a diameter of between about 0,3 to 0.7 
micrometers- 

9. - A laminate as clamed fn claim 1 or 8, wherein each of said layers of microglass reinforced 
3S fluoropolymer comprises about 2 to 25 weight percent of microglass. 

10- A laminate as claimed in claim 1. wherein said laminate has a total thickness of between about- 
0,076 to 12.7 mm. 

1 1 . A laminate as claimed in claim 2, Including: 
a fluoropolymeric bonding layer between said conductive material and said layer of microglass relnforcod 
40 fluoropolymer. 



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08/19/2004 16:55 FAX 9494768640 



CHRISTIE PARKER 
EP 0 313 961 A2 



@026 




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08/19/2004 16:55 FAX 9494768640 



CHRISTIE PARKER 



121027 




Europaisches Patentannt 
European Patent Office 
Office europeen des brevets 



© Publication numben 



0 313 961 

A3 



EUROPEAN PATENT APPLICATION 



@ Application number. aB117300.9 
(g) Date of filing: iai0.88 



© Int. CL5: H05K 1/03, B32B 5/28, 
C08J 5/04, //C08L27/12 



@ Priority: 26.10.87 US 113533 

® Date of publication of application: 
03.05.89 Bulletin Bd/18 

<w) Designated Contracting States: 
BE FR GB IT NL SE 

@ Date of deferred publication of ttic search report: 
05.Qd.90 Bulletin 90/36 



0 Applicant ROGERS CORPORATION 
Main Street 

Rogers. Conn. 06263(US) 

(5) Inventor: McGInnIs, Leon 

deceascd(US) 
Inventor: Carroll, J^mes R- 
4ia Barbara Drive 
Tempe Arizona 8S281(US) 
Inventor MHCer, Terry L. 
11233 Soutti 163rd Street 
Gilbert Arizona 8S234(US) 
Inventor: Norris, Michael B. 
12611 East Ballejo 
Chandler Arizona 8S249(US) . 



0 Representative: Meyers, Ernest ©t al 

Office de Brevets FREYUNGER & ASSOCIES 

1 321. route d*Arlon 
L-eool Strassen(LU) 



@ Gla$$ fiber reinforced fluoropolymorlc circuit laminate. 



0 A fluofopolymeric circuit laminate consisting of 
one or more layers of fluoropoiymer impregnated 
woven glass cloth (18) sandwiched between one or 
more layers (14.16) of "random" microfiberglass re- 
inforced fluoropolymer is presented. This composite 



of fluoropolymer. woven glass fabric and random 
glass microfibers may be clad on one or both outer 
surfaces with a suitable conductive material <20.22) 
such as copper or certain known resistive foils. 



< 

CD 

rt 

IT- 
CO 



Q. 
Ill 




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08/19/2004 16:55 FAX 9494768640 



CHRISTIE PARKER 



@026 



£uropean Patent 
Office 



EUROPEAN SEARCH REPORT 



AppliQtian Number 



EP 88 11 7300 



DOCUMENTS CONSIDERED TO BE RELEVANT 



CAtegory 



A 
A 



citation of docmnent with indicaliaii, where appropriate, 
>f rckvanT pamag" 



EP-A-0 217 311 (KANEGAFUCHI KAGAKU 
KOGYO K,K-) 

US-A-4 634 631 (ROGERS CORP.) 

US-A-3 393 117 (CINCINNATI MILLING 
MACHINE) 

EP-A-0 160 439 (JUNKOSHA CO. , LTD) 



Hie present search rq»ott has been drawn up for all claims 



Place of xcarch 

THE HAGUE 



Date or oanHcllon (he tearcb 

11-06-1990 



to claim 



CLASSmCAHON OF TIIE 
APMJCATION (Int- CI. 4) 



H 05 K 1/03 
B 32 B 5/28 
C 08 J 5/04 // 

C 08 L 27/12 



TECHNICAL FIELDS 
SeA)(CHED<Lit.CL4) 



H 05 K 
B 32 B 



SCHUERMANS M.F.G. 



CATEGORY OF aiEP DOCUMENTS 

X 7 p:?rticn!aTfy rdcvum If ukcn atoire 

Y ; panicutsiiy r-eimm H oambl[kcd Hth another 

dacunicn( Qf ibe »<nc ait^ary 
A : tccbnolo^cal baclCgroond 
O : DorHirH^lcR disdosurc 



T : thcoiy or prindplft updcriylog ibe InveniioA 
E : curlier pai^i dacumeitt, b(jt pHblisbod Oh, or 

P : 4iKuin«at dteq in ihe application 

X, z document cited for olho- rcasOIiS 

& : member of ibe $atn£ piEear family, corrcspoiuliii^ 



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