TWI628211B - 具有均勻介電性質之預浸材及層合物 - Google Patents
具有均勻介電性質之預浸材及層合物 Download PDFInfo
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- TWI628211B TWI628211B TW104114604A TW104114604A TWI628211B TW I628211 B TWI628211 B TW I628211B TW 104114604 A TW104114604 A TW 104114604A TW 104114604 A TW104114604 A TW 104114604A TW I628211 B TWI628211 B TW I628211B
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- resin
- prepreg
- dielectric constant
- materials
- high dielectric
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- 229920005989 resin Polymers 0.000 claims abstract description 112
- 239000011347 resin Substances 0.000 claims abstract description 112
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- 239000010949 copper Substances 0.000 claims description 11
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002113 barium titanate Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 8
- -1 felt Substances 0.000 claims description 5
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- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011152 fibreglass Substances 0.000 claims description 4
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-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
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XTOKBQLTBGASEX-UHFFFAOYSA-N benzene-1,4-diol;hydrazine Chemical compound NN.OC1=CC=C(O)C=C1 XTOKBQLTBGASEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000002657 fibrous material Substances 0.000 description 1
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/245—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using natural fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C08J2300/24—Thermosetting resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0237—High frequency adaptations
- H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0237—High frequency adaptations
- H05K1/0248—Skew reduction or using delay lines
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
本發明係關於自樹脂組合物製成之具有游離樹脂部分及經樹脂浸漬之增強材料部分之預浸材及層合物,其中該樹脂包含一或多種基本樹脂及一或多種高Dk材料,其中該一或多種高Dk材料係以足夠賦予該樹脂組合物固化DkW的量存在於該樹脂組合物中,該固化DkW與經施加該樹脂組合物之經樹脂浸漬之增強材料之DkWR匹配在正或負(±)15%內。
Description
本申請案係2013年3月14日申請之同在申請中之美國專利申請案第13/803698號之部分接續申請案,美國專利申請案第13/803698號主張2013年2月6日申請之美國臨時專利申請案第61/761,669號之優先權,各案之說明書以引用的方式併入本文中。本申請案亦係2014年10月2日申請之PCT/US2014/58824的接續,PCT/US2014/58824之說明書以引用的方式併入本文中。
本發明係關於包含一或多種高Dk材料及基本樹脂之樹脂組合物,其中該(等)高Dk材料之介電常數大於該固化基本樹脂之介電常數。本發明亦係關於以本發明之樹脂組合物製成之預浸材及層合物,其等具有橫跨預浸材或層合物橫截面之均勻介電常數。
預浸材及敷銅層合物係通常用以製造印刷電路板之平面材料。預浸材及層合物通常係包含增強材料(諸如編織玻璃、非編織玻璃、紙或其他纖維及非纖維材料)及用作基質材料之聚合樹脂(施加至或用以浸漬增強材料之材料)的複合結構。
隨著電子裝置之操作頻率不斷增大,謹慎地控制預浸材及層合物之介電性質變得日益重要。當前預浸材及層合物之一個問題係增強
材料及基質材料之介電性質非常不同。當非常高速之訊號傳輸通過使用此類敷金屬層合物構建之結構(諸如印刷電路板)時,隨著該訊號在異向性區域上傳播,該訊號經歷偏斜及速度差異。當不同訊號運行及在最壞情況下此問題進一步加劇,長距傳播速度之差異導致主要訊號完整性問題及在一些情況下導致總訊號消失。此問題已成為電子裝置設計者主要關注的問題,尤其針對機載頻率邁向14GHz並在四個通道上傳輸超過100十億位元/秒,其中預期偏斜係主要之設計挑戰。
本發明係關於藉由消除該基質之介電常數與該(等)增強材料之介電常數之間之差距解決偏斜問題之預浸材及層合物。因此,本發明之一個態樣係包括一或多種基本樹脂及一或多種高Dk材料之樹脂組合物,其中該一或多種高Dk材料係以足夠賦予該樹脂組合物固化Dk的量存在於該樹脂組合物中,該固化Dk與經施加該樹脂組合物之該增強材料之Dk匹配在正或負(±)15%內。
本發明之另一態樣係包括至少一種基本樹脂及約5至約60重量%選自由以下各物組成之群之顆粒或更多高Dk材料的樹脂組合物:鈦酸鍶、鈦酸鋇、鈦酸鉛、鋯鈦酸鉛、鋯鈦酸鉛鑭及其組合,其中該樹脂組合物之Dk與經施加該樹脂組合物之編織玻璃織物增強材料之Dk匹配在正或負(±)15%內。
本發明之又一態樣係預浸材,其包括具有DkR之增強材料及包含一或多種具有DkW之基本樹脂之樹脂組合物,其中DkR大於DkW超過15%,該樹脂組合物進一步包含一或多種以足夠賦予該樹脂組合物固化DkW之量存在於該樹脂組合物中的高Dk材料,該固化DkW與經施加該樹脂組合物之該增強材料之DkR匹配在正或負(±)15%內。
本發明之又一態樣係預浸材,其包括:經至少部分固化樹脂浸漬之增強材料部分;及游離樹脂部分,其中該樹脂包含至少一種高介
電常數材料,該游離樹脂部分具有介電常數DKW及該經樹脂浸漬之增強材料部分具有介電常數DKWR,其中該高介電常數材料係以足夠匹配DKWR與DKW使得DKWR與DKW相差不大於(±)15%之量併入該樹脂中。
10‧‧‧預浸材
12‧‧‧游離樹脂部分
14‧‧‧增強材料部分
16‧‧‧頂部
18‧‧‧底部
20‧‧‧側面
22‧‧‧側面
Y‧‧‧橫截面
圖1係本發明之預浸材或層合物實施例(其包含橫跨其橫截面之均勻的介電常數)之橫截面。
本發明大致係關於電子工業中使用之經增強之預浸材及層合物,其包含樹脂或基質組分及增強組分。本發明之預浸材及層合物中使用之初始組分具有相差大於15%之介電常數。特定言之,該樹脂組分具有DKW及該增強組分具有DKR且DKW與DKR相差大於15%。實際上,DKR與無高Dk材料之樹脂材料之DK(DK0)通常容易相差大於30%。
術語「初始組分介電常數」係指在合併初始材料以形成經樹脂浸漬之增強材料之前及/或在將其等併入至經增強之預浸材及/或層合物之前各初始材料的介電常數。
在本發明之一項實施例中,該樹脂組分係經高介電常數材料修飾以形成預浸材或層合物,其中該基質組分介電常數及該增強材料介電常數係「均勻」或「匹配」。術語「均勻」或「匹配」在本文係類似地用於指兩種介電常數彼此相差不大於正或負(±)15%,及更佳不大於正或負(±)5%。
本發明之另一實施例係橫跨橫截面具有匹配或均勻之介電常數之預浸材及層合物。對預浸材或層合物而言,此意為該預浸材或層合物之經樹脂浸漬之增強材料部分之介電常數(DKWR)匹配該預浸材或層合物之游離樹脂部分之介電常數(DKW)。在此實施例中,該樹脂之
介電常數匹配該經樹脂浸漬之增強材料之介電常數以形成橫跨橫截面具有匹配的介電常數之層合物。
在上述實施例中,該(等)增強材料之介電常數(DkR)通常係固定的。此外,無高介電常數材料之該樹脂或基質材料之介電常數(Dk0)通常顯著不同於增強材料之介電常數(DkR),即,相差大於±15%。因此,本發明藉由在結合基質材料與增強材料之前將一或多種高介電常數(Dk)材料併入樹脂(亦稱為基質材料)中以匹配介電常數。
現參照圖1,其顯示具有橫截面「Y」之本發明之預浸材(10)。該預浸材包含游離樹脂部分(12)及經樹脂浸漬之增強材料部分(14)。該游離樹脂部分具有DkW。該經樹脂浸漬之增強材料部分具有DkWR。該預浸材或層合物之游離樹脂部分包含任何具有可獨立於DkWR測定之DkW之樹脂。術語「游離樹脂」係指如下的一種樹脂:其為該預浸材或層合物之部分但在將該樹脂併入該經樹脂浸漬之增強材料部分中之後距任何增強層表面(頂部(16)底部(18)或側面(20)及(22))至少1微米。該游離樹脂通常將係b階段化或c階段化樹脂。此包含(例如)在將經樹脂塗覆之銅片以樹脂向下的方式施加至經核心樹脂浸漬之增強材料以形成經銅塗覆之預浸材或層合物之後剩餘的游離樹脂。
本文討論之「介電常數」及本文提及之介電常數範圍或數字係藉由Bereskin測試方法,或另一選擇,藉由分離後方法測定。在討論介電常數之比較之情況下,則藉由相同測試方法測定比較之介電常數。使用完全固化樹脂樣品測定該樹脂之介電常數。使用經完全固化樹脂浸漬之增強材料之樣品測定該經樹脂浸漬之增強材料部分的介電常數DkWR。
該增強材料可係任何已知對製造用以製造預浸材或層合物(其用於製造印刷電路板)之基材片有用的片狀或基礎材料。然而如前所述,可使用基礎材料(諸如基礎玻璃纖維材料),但該增強材料較佳係
片狀材料。例如,該增強片狀材料可係包含各種玻璃布(例如,紗束布、布、短切氈及表面氈)、金屬纖維布及類似物之無機纖維布;由液晶纖維(例如,全芳族聚醯胺纖維、全芳族聚酯纖維及聚苯并唑(polybenzazole)纖維)製成之編織或非編織布;由合成纖維(例如,聚乙烯醇纖維、聚酯纖維及丙烯酸系纖維)製成之編織或非編織布;天然纖維布(例如,棉布、麻布及毛氈);碳纖維布;及天然纖維素布(例如,牛皮紙、棉紙及紙-玻璃組合之纖維紙)。
在本發明之一個態樣中,該增強材料係編織玻璃織物材料。此類編織玻璃織物材料將具有約3.5至7.0或更大之DkR。此類編織玻璃纖維材料之實例包含(例如)具有約3.5至約4.5之DkR之低Dk玻璃,E級玻璃;R級玻璃、ECR級玻璃、S級玻璃、C級玻璃、Q級玻璃及任何其他已知對製造經玻璃織物增強之預浸材及層合物有用的編織玻璃織物種類。
本發明之樹脂組合物將包含一或多種此項技術中已知對製造預浸材及層合物材料有用的基本樹脂。該基本樹脂通常將係熱固性或熱塑性樹脂。有用之基本樹脂之實例包含環氧樹脂、基於聚苯醚之樹脂、氰尿酸酯樹脂、雙馬來醯亞胺樹脂、聚醯亞胺樹脂、酚系樹脂、呋喃樹脂、二甲苯甲醛樹脂、酮甲醛樹脂、尿素樹脂、三聚氰胺樹脂、苯胺樹脂、醇酸樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙酯樹脂、氰尿酸三烯丙酯樹脂、三嗪樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂及其任何組合或混合物。
在本發明之一個態樣中,該基本樹脂係或包含環氧樹脂。有用之環氧樹脂之一些實例包含酚型,諸如彼等基於雙酚A之二縮水甘油醚者、基於苯酚甲醛酚醛樹脂或甲酚-甲醛酚醛樹脂之聚縮水甘油醚者、基於叁(對羥基酚)甲烷之三縮水甘油醚者或基於四苯基乙烷之四縮水甘油醚者;胺型,諸如彼等基於四縮水甘油基-亞甲基二苯胺者
或基於對胺基二醇之三縮水甘油醚者;環脂族型,諸如彼等基於3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯者。術語「環氧樹脂」亦係指含有過量環氧(例如,前述類型之環氧)之化合物與芳族二羥基化合物的反應產物。此等化合物可係經鹵素取代。較佳係作為雙酚A之衍生物的環氧樹脂,特別係FR-4。FR-4係由過量雙酚A二縮水甘油醚與四溴雙酚A之進行反應製成。亦可應用環氧樹脂與雙馬來醯亞胺樹脂、氰酸酯樹脂及/或雙馬來醯亞胺三嗪樹脂之混合物。
除基本樹脂外,該等樹脂組合物通常將包含引發劑或觸媒、一或多種可選阻燃劑及溶劑。該阻燃劑可係任何已知對用以製造用於製造印刷電路板之預浸材及層合物之樹脂組合物有用的阻燃劑材料。該(等)阻燃劑可含有鹵素或其等可不含鹵素。另一選擇或此外,該等樹脂可包含鹵素(諸如溴)以賦予該固化樹脂阻燃性質。
該樹脂組合物亦可包含聚合引發劑或觸媒。一些有用之引發劑或觸媒之實例包含(但不限於)過氧化物或偶氮型聚合引發劑(觸媒)。通常,所選之引發劑/觸媒可係任何已知對樹脂合成或固化(無論其是否執行此等功能中之一者)有用的化合物。
該樹脂組合物將包含一或多種溶劑,其等通常用以溶解適當之樹脂組合物成分及/或控制樹脂黏度及/或以將該等樹脂成分維持於懸浮分散液中。可使用任何熟習此項技術者已知之對結合熱固性樹脂系統有用的溶劑。特別有用之溶劑包含甲基乙基酮(MEK)、甲苯、二甲基甲醯胺(DMF)或其混合物。如下所示,該等樹脂組合物用以製造預浸材及層合物。在製造過程期間,該等增強材料係經該等樹脂組合物浸漬或以其他方式結合該等樹脂組合物及自該等樹脂組合物中移除一些更多之溶劑以形成預浸材及層合物。因此,當列出樹脂組合物之重量百分率量時,除非另有說明,否則基於乾燥無溶劑計對其等作出記錄。
該等樹脂組合物可包含各種其他可選成分,包含填充劑、增韌劑、助黏劑、消泡劑、整平劑、染料及顏料。例如,可向該樹脂組合物添加痕量螢光染料以造成自其製得之層合物在板店之光學檢驗設備中曝露於UV光時發螢光。本發明之樹脂組合物亦可包含熟習此項技術者已知之對用以製造印刷電路板層合物之樹脂有用的其他可選成分。
本發明之樹脂組合物亦可包含一或多種高Dk材料。該等高Dk材料可係任何可併入液體樹脂中使得固化或部分固化之包含該高Dk材料之樹脂組合物的Dk不同於及較佳高於該(等)樹脂組合物樹脂成分之Dk的材料。在一項實施例中,該高Dk材料將具有大於約200及更佳大於約500之Dk。
一類有用之高Dk材料係鐵電材料。一些有用之鐵電材料之實例包含鈦酸鍶、鈦酸鋇、鈦酸鉛、鋯鈦酸鉛、鋯鈦酸鉛鑭及其組合。特別有用之高Dk材料係鈦酸鍶及鈦酸鋇。
該等高Dk材料可作為顆粒材料併入該等樹脂組合物中。若使用特定材料,則該高Dk材料通常將具有約1nm至40微米範圍內之粒度。
該高Dk材料將以足夠形成均勻預浸材或層合物之量包含於該樹脂組合物中。在一項實施例中,均勻預浸材或層合物將具有在增強材料DkR之±15%內及較佳在±5%內之樹脂組合物或基質DkW。在一項替代實施例中,該均勻預浸材或層合物將具有游離樹脂部分,其具有在該經樹脂浸漬之增強材料部分DkWR之±15%內及較佳在±5%內之DkW。
併入該樹脂組合物中之高Dk材料的量將取決於該基本樹脂之DK0及該增強材料之DKR而變化。通常,Dk0與DkR之間之差異越大,則將包含於該樹脂組合物中之高Dk材料之量越大。通常,需要高Dk材料
之量大於該樹脂組合物之約2重量%(基於乾重計)以使基本樹脂Dk改變。可併入該樹脂組合物中而不顯著影響樹脂組合物性質之高Dk材料之最大量係約70重量%(基於乾燥無溶劑計)。在一替代實施例中,該高Dk材料將以約5至約60重量%(基於乾重計)之範圍內的量存在於該樹脂組合物中。吾人已經發現向具有約4之Dk0之基本樹脂中添加約5至約60重量%之顆粒鈦酸鋇會使該樹脂組合物之DkW在5重量%負載時僅超過4增加至在60重量%時高於7.5。
上述樹脂組合物對製備用以製造印刷電路板之預浸材及/或層合物尤其有用。為對製造印刷電路板有用,可使該等層合物部分固化或b階段化以形成工業中所知的預浸材,其等在該階段中可與額外之材料片疊層以形成c階段化或完全固化層合片。或者,可將該等樹脂製成c階段化或完全固化材料片。
在一種有用之處理系統中,上述樹脂組合物/增強材料之組合對分批或以連續過程製造預浸材有用。通常使用展開成一系列驅動輥之核心材料(諸如一捲編織玻璃網(織物))製造預浸材。然後使該網進入塗覆區域中,使該網在該區域中通過含有本發明之熱固性樹脂系統、溶劑及其他組分的槽,該玻璃網在該槽中變得飽含該樹脂。然後使該飽和玻璃網通過一對計量輥,該等計量輥自該飽和玻璃網移除過量樹脂及此後,該經樹脂塗覆之網在所選時間段內行進乾燥塔長度直至溶劑自該網蒸發。可藉由重複此等步驟將樹脂之第二及隨後之塗層施加至該網上,直至完成預浸材之製備,隨後將該預浸材捲於輥上。可以編織織物材料、紙、塑膠片、毛氈、及/或顆粒材料(諸如玻璃纖維顆粒或顆粒材料)代替編織玻璃網。
在製造預浸材或層合物材料之另一方法中,在周圍溫度及壓力下,將本發明之熱固性樹脂預混合於混合容器中。該預混合物之黏度係~600-1000cps且可藉由自樹脂添加或移除溶劑來調節。將織物基
材(諸如E級玻璃)牽引通過包含該經預混合之樹脂之浸漬槽,通過烘箱塔,在該烘箱塔中驅除過量溶劑且取決於玻璃編織類型、樹脂含量及厚度要求而將該預浸材輥軋或製片至一定大小,在各種結構中於Cu箔之間疊層。
亦可使用狹縫模具式或其他相關塗覆技術將該樹脂組合物以薄層形式施加至Cu箔基材(RCC-經樹脂塗覆之Cu)。
可使用上述樹脂、預浸材及經樹脂塗覆之銅箔分批或以連續過程製造層合物,諸如彼等用以製造印刷電路板者。在製造本發明之層合物之示例性連續過程中,呈銅、樹脂預浸材及薄織物片中之各者之形式的連續片連續展開成一系列驅動輥以形成與樹脂預浸材片相鄰之織物層網,該樹脂預浸材片係與銅箔相鄰使得該預浸材位於該銅箔與該織物片之間。然後使該網經受熱及壓力條件達一段足以使樹脂遷移至織物材料中並使該樹脂完全固化的時間。在所得之層合物中,樹脂材料遷移至織物中會使樹脂層厚度(銅箔材料與編物片狀材料間之距離)變小並趨向於零,因為上述組合層由三層網變為單一層合物片。在本方法之一替代方法中,可將單一預浸材樹脂片施加至織物材料層之一側並將該組合夾於兩銅層間,之後向該疊層施加熱及/或壓力以使樹脂材料流動並完全浸漬織物層並使兩銅箔層均黏附至中心層合物。
在又一實施例中,可同時製造經樹脂組合物塗覆之銅片,該層合物係藉由向兩個不同之連續移動之銅片施加樹脂薄塗層,自該等片中移除過量樹脂以控制樹脂厚度及然後在熱及/或壓力條件下使該樹脂部分固化以形成經b階段化樹脂塗覆之銅片來製造。然後該(等)經b階段化樹脂塗覆之銅片可直接用於層合物製造過程中。
在又一實施例中,可將經或未經預處理之織物材料連續進料至樹脂組合物浴中使得該織物材料經該樹脂組合物浸漬。可在該方法之
此階段下使該樹脂組合物視需要部分固化。接著,一或兩個銅箔層可結合該經樹脂組合物浸漬之織物片之第一及/或第二平面以形成網,之後對該網施加熱及/或壓力以使該樹脂組合物完全固化。
已以圖解說明之方式描述本發明。當瞭解所用術語意欲按照字面描述性質而非限制。根據以上教示可存在本發明之許多修改及變化。因此,在隨附申請專利之範圍內,可不同於如特定描述實施本發明。
Claims (18)
- 一種預浸材,其包括:經至少b階段化樹脂浸漬的增強材料部分;及游離樹脂部分,其中該樹脂包含至少一種高介電常數材料,該游離樹脂部分具有介電常數DkW及該經樹脂浸漬之增強材料部分具有介電常數DkWR,其中該高介電常數材料係以足夠匹配該DkWR與該DkW使得該DkWR與DkW相差不大於(±)15%之量合併入該樹脂中,且其中該增強材料之介電常數(DkR)係不同於該DkW。
- 如請求項1之預浸材,其中該一或多種高介電常數材料各具有至少約500之Dk。
- 如請求項1之預浸材,其中該一或多種高介電常數材料係顆粒材料。
- 如請求項3之預浸材,其中該一或多種高介電常數材料之粒度在約1nm至約40微米範圍內。
- 如請求項1之預浸材,其中該一或多種高介電常數材料係鐵電材料。
- 如請求項5之預浸材,其中該等鐵電材料係選自包含鈦酸鍶、鈦酸鋇、鈦酸鉛、鋯鈦酸鉛、鋯鈦酸鉛鑭及其組合之群。
- 如請求項1之預浸材,其中該樹脂係熱固性或熱塑性樹脂。
- 如請求項1之預浸材,其中一或多種高介電常數材料係以約2至約70重量%之量存在於該組合物中。
- 如請求項1之預浸材,其中該增強材料係選自編織玻璃布、紙、毛氈、玻璃纖維及塑膠片。
- 如請求項9之預浸材,其中該增強材料係低介電常數玻璃織物 片。
- 如請求項10之預浸材,其中該低介電常數玻璃織物片具有約3.5至約7.0範圍內之Dk。
- 如請求項1之預浸材,其中該游離樹脂係距任何增強層表面至少1微米之任何樹脂。
- 如請求項1之預浸材,其中該樹脂包括至少一種基本樹脂及約5至約60重量%之選自由以下各物組成之群之顆粒或更多高介電常數材料:鈦酸鍶、鈦酸鋇、鈦酸鉛、鋯鈦酸鉛、鋯鈦酸鉛鑭及其組合。
- 如請求項1之預浸材,其中該DKWR與DKW相差不大於(±)5%。
- 如請求項1之預浸材,其中該DkR與無該高介電常數材料之該樹脂之介電常數相差大於30%。
- 一種層合物,其包含完全固化之如請求項1之預浸材。
- 如請求項16之層合物,其包含至少一個銅層。
- 一種印刷電路板,其包含至少一層完全固化之如請求項1之預浸材。
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