US20010011111A1 - Molded resin composition exhibiting good adhesion to conductive material on a surface - Google Patents
Molded resin composition exhibiting good adhesion to conductive material on a surface Download PDFInfo
- Publication number
- US20010011111A1 US20010011111A1 US09/815,059 US81505901A US2001011111A1 US 20010011111 A1 US20010011111 A1 US 20010011111A1 US 81505901 A US81505901 A US 81505901A US 2001011111 A1 US2001011111 A1 US 2001011111A1
- Authority
- US
- United States
- Prior art keywords
- particles
- organic
- resin
- composite particles
- insulative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011342 resin composition Substances 0.000 title claims description 29
- 239000004020 conductor Substances 0.000 title claims description 21
- 230000001747 exhibiting effect Effects 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- 239000011246 composite particle Substances 0.000 claims abstract description 62
- 239000011146 organic particle Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 34
- 229920001187 thermosetting polymer Polymers 0.000 claims description 24
- 229920001169 thermoplastic Polymers 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 239000004416 thermosoftening plastic Substances 0.000 claims description 15
- 238000007772 electroless plating Methods 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004634 thermosetting polymer Substances 0.000 claims description 12
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 239000007771 core particle Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920006125 amorphous polymer Polymers 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims 5
- 239000000243 solution Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 239000012212 insulator Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000007719 peel strength test Methods 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012801 ultraviolet ray absorbent Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
- H05K2201/0212—Resin particles
-
- 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
- H05K2201/0218—Composite particles, i.e. first metal coated with second metal
-
- 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
- H05K2201/0242—Shape of an individual particle
- H05K2201/0254—Microballoons or hollow filler particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
Definitions
- the present invention relates to a resin composition, and more particularly to a resin composition exhibiting a good adhesion when a surface of the resin composition is subjected to a wet processing for forming a conductor on a surface of the molded resin composition.
- a plating process has been developed for the purpose of preventing static electricity on the surface of a molded resin composition.
- This plating process is also made for forming a patterned conductor on a predetermined part of the molded resin composition surface, typically forming a printed wiring board.
- Such plating processes may be isolated into two processes. The first one is a dry process using thin film technologies of such as evaporation and sputtering. The second one is a wet process, wherein a catalyst core is adsorbed on the resin composition surface, and the resin composition is subsequently immersed into an electroless plating bath for precipitation of electroless plating.
- the maximum thickness of the conducive film is only a few micrometers, namely it is difficult to form a thin conductive film. This means that the thick conductive film is formed in the wiring board, then the impedance of the wiring is high, namely it is difficult to reduce the impedance of the conductive film wiring on the wiring board.
- the dry process allows a good adhesion of conductor with the resin composition. However, the dry process is inferior in the productivity and cost performance, for which reason the dry process is not suitable for mass production at low cost.
- the wet process is superior in cost performance but inferior in adhesion between resin composition and conductor.
- it is required to provide a roughness to the surface of the resin composition.
- Available methods for providing the roughness to the resin composition surface would be isolated into two typical ones. The first one is the mechanical and physical method.
- the second one is the chemical method using wet etching by chemical etchants.
- the mechanical and physical method is somewhat inferior in uniformity of roughness and adhesion to the fine patterns is not uniform. It is also difficult to obtain a sufficiently high adhesion with a hard resin.
- the chemical method is ineffective with chemical-resistant resins.
- ABS resin acrylonitrile-butadiene-styrene resin
- This resin has an island structure wherein the rubber component of butadiene is dispersed in the form of spherical particles in a body of acrylonitrile-butadiene (AB). If this resin is immersed in an oxidizing etchant, then the rubber component in the form of spherical particles positioned in the vicinity of surfaces of the body is selectively oxidized and dissolved into the etchant, whereby the surface of the resin is made rough. The plated film of conductor is securely engaged with the rough surface of the resin by the anchor effect.
- Chromatic acid is used as an oxidizing etchant for selecting etching the rubber component dispersed in the form of spherical particles.
- the use of chromatic acid as the oxidizing etchant is not preferable in the light of recently required reduction of environmental pollution. Blending rubber component reduces heat resistivity, stability in size, and insulation performance or anti-migration performance.
- the inorganic insulator since such inorganic insulators, however, include alkali metals or alkali earth metals, there is raised a problem with deterioration in moisture resistance of the resin. For this reason, it is preferable to not include a large amount of such inorganic insulators into the resin. Further, generally, the inorganic insulator has a larger specific gravity than resins. Particularly if liquid inorganic insulators such as varnish are used, then the inorganic insulator is non-uniformly present in the resin matrix, and the probability of the inorganic insulator existing in the vicinity of the surface of the resin matrix is lower.
- a resin matrix with resistances to alkali and acid includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component at a total amount in the range of 5-50% by volume, wherein the insulative organic particles and the organic component of the insulative composite particles are allowed to be corroded by either alkali or acid, and wherein not less than 90% by volume of any one of the insulative organic particles and insulative composite particles has a particle diameter in the range of 1-20 micrometers.
- the insulative organic particles and the organic component of the insulative composite particles comprise a thermoplastic amorphous polymer which has a glass transition temperature of not less than 90° C.
- the insulative organic particles and the organic component of the insulative composite particles comprise a thermoplastic crystal polymer which has a melting point of not less than 110° C.
- the insulative organic particles and the organic component of the insulative composite particles comprise a thermosetting polymer.
- parts of the insulative organic particles and the insulative composite particles comprise hollow particles.
- each of the insulative composite particles comprise inorganic core particles coated with a thermoplastic polymer layer.
- each of the insulative composite particles comprise inorganic core particles coated with a thermosetting polymer layer.
- each of the insulative composite particles comprise a homogeneous organic particle coated with calcium carbonate at an amount of 25% by weight or less.
- each of the insulative composite particles comprise a hollow organic particle coated with calcium carbonate at an amount of 25% by weight or less.
- the resin matrix has a photosensitivity.
- the resin matrix with the photosensitivity is any one of epoxy-acrylate having fluorene skeleton and benzocyclobutene and the organic particles and the organic component of the composite particles are at least one thermoplastic polymer selected from the group consisting of polymethylmethacrylate, polyacrylonitrile, polystyrene, nylon, polycarbonate, and polyvinylidene chloride.
- the resin matrix with the photosensitivity is any one of epoxy-acrylate having fluorene skeleton and benzocyclobutene and the organic particles and the organic component of the composite particles are at least one thermosetting polymer selected from the group consisting of epoxy resin, phenol resin, and diarylphthalate resin.
- a method of forming a conductor on a surface of a resin composition comprises the steps of:
- molding a resin which includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component at a total amount in the range of 5-50% by volume, wherein the organic particles and the organic component of the composite particles are allowed to be corroded by either alkali or acid and wherein not less than 90% by volume of said at least any one of said insulative organic particles and said insulative composite particles has a particle diameter in the range of 1-20 micrometers;
- the acid solution and the alkali solution are permanganate and a neutralizing solution thereof.
- Permanganate is used as a chemical for desmear treatment.
- a resin matrix has at least any one of resistances to alkali and acid.
- the resins with resistance to acid may, for example, be epoxy-acrylate, and polyamide imide.
- the resins with resistance to alkali may, for example, be polystyrene, and nylon.
- the resins with resistances to both alkali and acid may, for example, be polypropylene, polyester, epoxy resin, polyimide, and benzocyclobutene.
- epoxy-acrylate having fluorene skeleton and benzocyclobutene are preferable due to those high glass transition temperature and high hydrophobicity.
- the organic particles and the organic component of the composite particles are allowed to be corroded by either alkali or acid relative to the resin matrix.
- Thermoplastic polymers may, for example, be selected from polymethylmethacrylate, acryl resins such as polyacrylonitrile, polystyrene, polycarbonate, and acetal resins.
- the organic particles and the organic component of the composite particles comprise a thermoplastic amorphous polymer which has a glass transition temperature of not less than 90° C.
- the organic particles and the organic component of the composite particles comprise a thermoplastic crystal polymer which has a melting point of not less than 110° C.
- heat treatment of the resin is carried out to remove moisture from the molded resin for improvement in the adhesion of the surface of the resin.
- the heat treatment is preferably carried out at not less than 90° C. If the glass transition temperature is less than 90° C., or a melting point is less than 110° C., then any deformation such as expansion may appear on the surface of the molded resin.
- the resin matrix comprises a thermoplastic polymer
- the thermoplastic polymer has a glass transition temperature of not less than 90° C., and a melting point is less than 110° C. If the glass transition and melting point temperatures are lower than the above, then deformation may appear due to heat treatment.
- thermosetting resins have a bridge structure, for which reason the thermosetting resins are superior in resistance to chemicals. It is preferable to not roughen the surface of the resin in a short time. However, if the high heat resistance and size stability are required, then those thermosetting resins are superior than the thermoplastic resins. It is, therefore, preferable to blend the thermosetting resins, even if the time for roughening the surface of the resin is somewhat long.
- the resin matrix of epoxy-acrylate having fluorene skeleton and benzocyclobutene having a high glass transition temperature is blended with thermosetting resin such as epoxy resin, phenol resin, and diarylphthalate resin to obtain higher properties than when the thermosetting resin is used alone and obtain better adhesion.
- the inorganic component of the composite particles is not limited when used as core particles coated with an organic component to be corroded by acid and alkali solutions. In this case, the organic component is corroded, and the core particle is also removed, thereby exhibiting roughness effects. If the inorganic component is used for coating the core particles, then calcium carbonate is preferable due to its high solubility. Since, however, calcium carbonate includes alkali earth metals, the moisture resistance might be dropped. It is preferable to not use a large amount of calcium carbonate alone. It is preferable to reduce the blending amount of calcium carbonate to 25% by weight or less. The hollow particles are effective for shortening the corrosion time and reducing the blending amount thereof.
- the hollow particles have low specific gravity, and the particles are likely to be localized on the surface region of the particles. This makes it easy to obtain a rough surface on the resin.
- the blending amount of the particles is in the range of 5-50% by volume. If the blending amount is less than 5% by volume, then it is difficult to obtain the desired rough surface o the resin necessary for good adhesion to the conductor. If the blending amount is more than 50% by volume, then the properties of the resin matrix are remarkably changed. Not less than 90% by volume of the particles have a particle diameter in the range of 1-20 micrometers. Preferably, not less than 95% by volume of the particles have a particle diameter in the range of 3-15 micrometers.
- not less than 98% by volume of the particles have a particle diameter in the range of 5-10 micrometers. If the diameter is less than 1 micrometer, then it is difficult to obtain a sufficiently rough surface on the resin for required adhesion to the conductor. If the diameter is more than 20 micrometers, then the surface roughness is too great to form fine interconnections on the surface.
- insulative particles to the resin composition other than the particles to be corroded by alkali and acid solutions.
- inorganic particles such as silica, alumina, titanium oxide, and boron nitride may be included. It is also possible to include additives such as flame retardant, coloring agent, ultraviolet ray absorbent agent, and an antistatic agent.
- the chemicals to be used for corrosion are acid and alkali solutions.
- organic solvents For example, mineral acids such as sulfuric acid, and hydrochloric acid may be included, and an oxidizing agent may also be included.
- an alkali sodium hydroxide is generally used.
- Permanganate is used as a chemical for desmear treatment to remove residual resin to obtain good adhesion for deposition of the electroless plating.
- the desmear treatment comprises three steps of swelling the resin with an alkali solution containing a small amount of organic solvent, etching by an alkali solution of permanganate, and neutralizing for removal of residual manganese.
- this process may be applicable to either particles to be corroded by any one of acid and alkali solutions.
- the immersion of the resin in the chemicals is carried out for a few minutes to several tens of minutes. In the interval between these immersion processes, the resin needs to be washed by water. Further, it is possible for pre-treatment or post-treatment with alkali solution, before or after the desmear treatment.
- the method of forming the conductor on the resin surface will be described.
- the method comprises three steps of molding the resin, making the surface of molded resin rough with at least one of alkali and acid solutions, and subjecting the surface thereof to electroless plating for subsequent heat treatment.
- the method of molding is not limited. If the resin matrix is thermoplastic polymer, then it is possible to melt the resin composition to mold the resin in the desired shape. It is also possible to dissolve the resin composition into the solvent to apply on the substrate surface, or to inject into dies for subsequent volatilization If the resin matrix is the thermosetting polymer or non-thermoplastic polymer, it is possible to apply precursor varnish on the substrate surface for subsequent thermosetting by heat, light and radioactive ray.
- the surface of the molded resin is made rough for good adhesion with the electroless plated conductor by use of acid or alkali solutions.
- Permanganate is used as a chemical for desmear treatment.
- a mechanical polishing such as buff polishing is preferably carried out for obtaining the surface roughness. Particularly, if the surface is hard and the resistance to chemicals is high, the resin thin film is polished for removal thereof to show the particle surface.
- the rough surface of the resin is subjected to the electroless plating.
- a catalyst causing plating reaction by various methods.
- the catalyst noble metals such as palladium are available. Particularly, palladium of colloidal type is often used. It is also possible to carry out the sensitizing by immersion of the resin into stannic chloride solution and subsequent activation by immersion into palladium chloride. It is further possible to immerse the resin into metal salt solution such as copper solution and nickel solution before reduction thereof for deposition of the metal, and subsequent palladium-replacement plating in the palladium chloride solution.
- the electroless plating is carried out.
- Materials for plating are not limited and are selectable in accordance with various uses. If interconnections of the printed wiring board are formed, copper is preferable due to its low cost and low resistance. Nickel and gold are also available. Since the electroless plating is inferior in deposition rate, electroplating may be carried out following the electroless plating.
- photo-resist may be used for selective etching of the conductive film. Alternatively, only the necessary part of the conductive film is deposited after addition of the catalyst.
- Heat treatment is accomplished for improvement in adhesion between the molded resin surface and the plated film by removal of moisture from the interface between the molded resin surface and the plated film.
- the heat treatment is preferably carried out at a temperature of not less than 90° C., but not rapidly to prevent expansion of the plated film. Gradual heating is preferable. If a relatively small area pattern is preliminary formed, a rapid heating is also possible due to a sufficient pass for removing moisture.
- the resin surface was polished by #600 buff to make the surface rough before desmear chemicals were used for swelling, etching,. and neutralizing processes.
- a solution containing 0.05 mol of copper nitrate was applied to the rough surface for subsequent heat treatment at 150° C. for 3 hours, and oxygen-plasma treatment for 1 minute. Thereafter, particle free epoxy-acrylate varnish having a fluorene skeleton was treated in the same manner a described above until accomplishment of pre-baking processes for exposure through mask pattern and subsequent development with a solution containing 1% by weight of sodium carbonate for 5 minutes.
- This substrate was reduced in a solution containing 1 g/l of boron sodium hydride for 10 minutes to deposit metals in the patterns for subsequent washing by water before immersion into electroless copper plating solution KC-500 (available from Japan Energy) for 4 hours to deposit 20 micrometers-thick electroless copper and subsequent heat treatment at 150° C. for 1 hour.
- electroless copper plating solution KC-500 available from Japan Energy
- a photosensitive benzocyclobutene varnish being available from Dow Chemicals was blended with 20 parts by weight of calcium carbonate-treated bridge polymethylmethacrylate particles (M-305C, calcium carbonate/polymethylmethacrylate; ⁇ fraction (2/8) ⁇ in percent by weight) for subsequent stirring by mixture for 30 minutes to obtain a uniform dispersion of the particles.
- An alumina ceramic substrate is applied with 1 wt-% 3-aminopropyltriethoxysilane solution to spin-coat this varnish to a thickness of 10 micrometers thereonto for subsequent pre-baking at 75° C. for 30 minutes before exposure at 700 mj/cm 2 prior to a thermosetting at 210° C. for 30 minutes.
- a glass transition temperature of the resin after thermosetting was 250° C.
- the resin surface was polished by #320 buff to make the surface rough for pre-immersion into 20 wt-% hydrochloric acid solution for 15 minutes before desmear chemicals were used for swelling, etching and neutralizing processes.
- Palladium catalyst is adsorbed onto the rough surface for activation in the THP process before particle free epoxy-acrylate varnish having fluorene skeleton was treated in the same manner as described above prior to accomplishment of pre-baking processes for exposure through mask pattern, and subsequent development with kerosine for 2 minutes prior to the thermosetting.
- This substrate was returned to the THP process for reduction in a solution containing 1 g/l of boron sodium hydride for 10 minutes to deposit metals in the patterns. Subsequent washing by water is accomplished before immersion into electroless copper plating solution KC-500 (available from Japan Energy) for 2 hours to deposit 10 micrometers-thick electroless copper, and subsequent heat treatment at 160° C. for 1 hour.
- electroless copper plating solution KC-500 available from Japan Energy
- the resin surface was polished by #320 buff to make the surface rough before desmear chemicals were used for swelling, etching and neutralizing processes.
- Palladium catalyst is adsorbed onto the rough surface for activation in the THP process before electroless plating for 15 minutes to increase the thickness up to 18 micrometers.
- Hydrochloric acid is used to subsequently provide palladium to deposit electroless nickel plating at 1 micrometer for further flash gold plating. Heat treatment was carried out at 1000° C. for 1 hour.
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Abstract
A resin matrix with resistances to alkali and acid includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component with the total amount of these particles being in the range of 5-50% by volume, wherein the insulative organic particles and the organic component of the insulative composite particles are allowed to be corroded by either alkali or acid, and wherein not less than 90% by volume of the insulative organic particles and insulative component particles have a particle diameter in the range of 1-20 micrometers.
Description
- This application is a divisional of co-pending Application Ser. No. 08/986,104, filed on Dec. 5, 1997, the entire contents of which are hereby incorporated by reference
- The present invention relates to a resin composition, and more particularly to a resin composition exhibiting a good adhesion when a surface of the resin composition is subjected to a wet processing for forming a conductor on a surface of the molded resin composition.
- A plating process has been developed for the purpose of preventing static electricity on the surface of a molded resin composition. This plating process is also made for forming a patterned conductor on a predetermined part of the molded resin composition surface, typically forming a printed wiring board. Such plating processes may be isolated into two processes. The first one is a dry process using thin film technologies of such as evaporation and sputtering. The second one is a wet process, wherein a catalyst core is adsorbed on the resin composition surface, and the resin composition is subsequently immersed into an electroless plating bath for precipitation of electroless plating. If the dry process is used, then the maximum thickness of the conducive film is only a few micrometers, namely it is difficult to form a thin conductive film. This means that the thick conductive film is formed in the wiring board, then the impedance of the wiring is high, namely it is difficult to reduce the impedance of the conductive film wiring on the wiring board. On the other hand, the dry process allows a good adhesion of conductor with the resin composition. However, the dry process is inferior in the productivity and cost performance, for which reason the dry process is not suitable for mass production at low cost.
- Namely, the wet process is superior in cost performance but inferior in adhesion between resin composition and conductor. In order to improve the adhesion between resin composition and conductor, it is required to provide a roughness to the surface of the resin composition. Available methods for providing the roughness to the resin composition surface would be isolated into two typical ones. The first one is the mechanical and physical method. The second one is the chemical method using wet etching by chemical etchants. The mechanical and physical method is somewhat inferior in uniformity of roughness and adhesion to the fine patterns is not uniform. It is also difficult to obtain a sufficiently high adhesion with a hard resin. On the other hand, the chemical method is ineffective with chemical-resistant resins.
- Some typical electroless plating processes for resin surface will be described.
- The following description will be made in the case of acrylonitrile-butadiene-styrene resin (ABS resin). This resin has an island structure wherein the rubber component of butadiene is dispersed in the form of spherical particles in a body of acrylonitrile-butadiene (AB). If this resin is immersed in an oxidizing etchant, then the rubber component in the form of spherical particles positioned in the vicinity of surfaces of the body is selectively oxidized and dissolved into the etchant, whereby the surface of the resin is made rough. The plated film of conductor is securely engaged with the rough surface of the resin by the anchor effect.
- It is known in the art to make the adhesive layer rough. In Japanese patent publication Nos. 63-10752 and Japanese laid-open patent publication No. 3-18096, it is disclosed that the rubber component of the acrylonitrile-butadiene-styrene rubbers is introduced into the adhesive of epoxy resins to obtain the same effect as described above.
- Chromatic acid is used as an oxidizing etchant for selecting etching the rubber component dispersed in the form of spherical particles. The use of chromatic acid as the oxidizing etchant is not preferable in the light of recently required reduction of environmental pollution. Blending rubber component reduces heat resistivity, stability in size, and insulation performance or anti-migration performance.
- In Japanese laid-open patent publication No. 60-167492, it is disclosed that an inorganic insulator is used to be selectively etched by chemicals. Glass, magnesium oxide and calcium carbonate are, for example, available to obtain a desired adhesion.
- Since such inorganic insulators, however, include alkali metals or alkali earth metals, there is raised a problem with deterioration in moisture resistance of the resin. For this reason, it is preferable to not include a large amount of such inorganic insulators into the resin. Further, generally, the inorganic insulator has a larger specific gravity than resins. Particularly if liquid inorganic insulators such as varnish are used, then the inorganic insulator is non-uniformly present in the resin matrix, and the probability of the inorganic insulator existing in the vicinity of the surface of the resin matrix is lower.
- In the above circumstances, it was required to develop a novel resin composition free from the above problems and a novel method of forming a conductor on a surface of the resin component.
- Accordingly, it is an object of the present invention to provide a novel resin composition free from the above problems.
- It is a further object of the present invention to provide a novel resin composition on which a conductor fine pattern is adhered at a high adhesion.
- It is a still further object of the present invention to provide a novel resin composition having a surface allowing good adhesion to a conductor.
- It is yet a further object of the present invention to provide a novel resin composition having good production yield.
- It is a further more object of the present invention to provide a novel resin composition which may be produced at a low cost.
- It is still more object of the present invention to provide a novel method of forming a conductor on a surface of a resin composition free form the above problems.
- It is moreover object of the present invention to provide a novel method of forming a conductor on a surface of a resin composition with a good adhesion.
- It is another object of the present invention to provide a novel method of forming a conductor on a surface of a resin composition at a low cost.
- It is still another object of the present invention to provide a novel high production yield method of forming a conductor on a surface of a resin composition.
- The above and other objects, features and advantages of the present invention will be apparent from the following descriptions.
- In accordance with the present invention, a resin matrix with resistances to alkali and acid includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component at a total amount in the range of 5-50% by volume, wherein the insulative organic particles and the organic component of the insulative composite particles are allowed to be corroded by either alkali or acid, and wherein not less than 90% by volume of any one of the insulative organic particles and insulative composite particles has a particle diameter in the range of 1-20 micrometers.
- It is preferable that the insulative organic particles and the organic component of the insulative composite particles comprise a thermoplastic amorphous polymer which has a glass transition temperature of not less than 90° C.
- It is also preferable that the insulative organic particles and the organic component of the insulative composite particles comprise a thermoplastic crystal polymer which has a melting point of not less than 110° C.
- It is also preferable that the insulative organic particles and the organic component of the insulative composite particles comprise a thermosetting polymer.
- It is also preferable that parts of the insulative organic particles and the insulative composite particles comprise hollow particles.
- It is also preferable that each of the insulative composite particles comprise inorganic core particles coated with a thermoplastic polymer layer.
- It is also preferable that each of the insulative composite particles comprise inorganic core particles coated with a thermosetting polymer layer.
- It is also preferable that each of the insulative composite particles comprise a homogeneous organic particle coated with calcium carbonate at an amount of 25% by weight or less.
- It is also preferable that each of the insulative composite particles comprise a hollow organic particle coated with calcium carbonate at an amount of 25% by weight or less.
- It is also preferable that the resin matrix has a photosensitivity.
- It is also preferable that the resin matrix with the photosensitivity is any one of epoxy-acrylate having fluorene skeleton and benzocyclobutene and the organic particles and the organic component of the composite particles are at least one thermoplastic polymer selected from the group consisting of polymethylmethacrylate, polyacrylonitrile, polystyrene, nylon, polycarbonate, and polyvinylidene chloride.
- It is also preferable that the resin matrix with the photosensitivity is any one of epoxy-acrylate having fluorene skeleton and benzocyclobutene and the organic particles and the organic component of the composite particles are at least one thermosetting polymer selected from the group consisting of epoxy resin, phenol resin, and diarylphthalate resin.
- In accordance with the present invention, a method of forming a conductor on a surface of a resin composition comprises the steps of:
- molding a resin which includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component at a total amount in the range of 5-50% by volume, wherein the organic particles and the organic component of the composite particles are allowed to be corroded by either alkali or acid and wherein not less than 90% by volume of said at least any one of said insulative organic particles and said insulative composite particles has a particle diameter in the range of 1-20 micrometers;
- exposing the resin to at least any one of an acid solution and an alkali solution to make a surface of the molded resin rough; and
- subjecting the rough surface of the molded resin to an electroless plating for subsequent heat treatment of the resin.
- It is preferable that the acid solution and the alkali solution are permanganate and a neutralizing solution thereof. Permanganate is used as a chemical for desmear treatment.
- In accordance with the present invention, a resin matrix has at least any one of resistances to alkali and acid. The resins with resistance to acid may, for example, be epoxy-acrylate, and polyamide imide. The resins with resistance to alkali may, for example, be polystyrene, and nylon. The resins with resistances to both alkali and acid may, for example, be polypropylene, polyester, epoxy resin, polyimide, and benzocyclobutene. Particularly, epoxy-acrylate having fluorene skeleton and benzocyclobutene are preferable due to those high glass transition temperature and high hydrophobicity. The organic particles and the organic component of the composite particles are allowed to be corroded by either alkali or acid relative to the resin matrix. Thermoplastic polymers may, for example, be selected from polymethylmethacrylate, acryl resins such as polyacrylonitrile, polystyrene, polycarbonate, and acetal resins.
- It is preferable that the organic particles and the organic component of the composite particles comprise a thermoplastic amorphous polymer which has a glass transition temperature of not less than 90° C.
- It is also preferable that the organic particles and the organic component of the composite particles comprise a thermoplastic crystal polymer which has a melting point of not less than 110° C.
- In the method of forming the conductor on the surface of the resin, after the rough surface of the molded resin is subjected to the electroless plating, heat treatment of the resin is carried out to remove moisture from the molded resin for improvement in the adhesion of the surface of the resin. The heat treatment is preferably carried out at not less than 90° C. If the glass transition temperature is less than 90° C., or a melting point is less than 110° C., then any deformation such as expansion may appear on the surface of the molded resin.
- If the resin matrix comprises a thermoplastic polymer, then the thermoplastic polymer has a glass transition temperature of not less than 90° C., and a melting point is less than 110° C. If the glass transition and melting point temperatures are lower than the above, then deformation may appear due to heat treatment.
- Generally, thermosetting resins have a bridge structure, for which reason the thermosetting resins are superior in resistance to chemicals. It is preferable to not roughen the surface of the resin in a short time. However, if the high heat resistance and size stability are required, then those thermosetting resins are superior than the thermoplastic resins. It is, therefore, preferable to blend the thermosetting resins, even if the time for roughening the surface of the resin is somewhat long. The resin matrix of epoxy-acrylate having fluorene skeleton and benzocyclobutene having a high glass transition temperature is blended with thermosetting resin such as epoxy resin, phenol resin, and diarylphthalate resin to obtain higher properties than when the thermosetting resin is used alone and obtain better adhesion.
- On the other hand, the inorganic component of the composite particles is not limited when used as core particles coated with an organic component to be corroded by acid and alkali solutions. In this case, the organic component is corroded, and the core particle is also removed, thereby exhibiting roughness effects. If the inorganic component is used for coating the core particles, then calcium carbonate is preferable due to its high solubility. Since, however, calcium carbonate includes alkali earth metals, the moisture resistance might be dropped. It is preferable to not use a large amount of calcium carbonate alone. It is preferable to reduce the blending amount of calcium carbonate to 25% by weight or less. The hollow particles are effective for shortening the corrosion time and reducing the blending amount thereof. The hollow particles have low specific gravity, and the particles are likely to be localized on the surface region of the particles. This makes it easy to obtain a rough surface on the resin. The blending amount of the particles is in the range of 5-50% by volume. If the blending amount is less than 5% by volume, then it is difficult to obtain the desired rough surface o the resin necessary for good adhesion to the conductor. If the blending amount is more than 50% by volume, then the properties of the resin matrix are remarkably changed. Not less than 90% by volume of the particles have a particle diameter in the range of 1-20 micrometers. Preferably, not less than 95% by volume of the particles have a particle diameter in the range of 3-15 micrometers. More preferably, not less than 98% by volume of the particles have a particle diameter in the range of 5-10 micrometers. If the diameter is less than 1 micrometer, then it is difficult to obtain a sufficiently rough surface on the resin for required adhesion to the conductor. If the diameter is more than 20 micrometers, then the surface roughness is too great to form fine interconnections on the surface.
- It is possible to add insulative particles to the resin composition other than the particles to be corroded by alkali and acid solutions. In order to reinforce the molded resin and obtain dimension stability as well as improve heat conductivity, inorganic particles such as silica, alumina, titanium oxide, and boron nitride may be included. It is also possible to include additives such as flame retardant, coloring agent, ultraviolet ray absorbent agent, and an antistatic agent.
- The chemicals to be used for corrosion are acid and alkali solutions. In view of prevention of environmental pollution, it is preferable to not use organic solvents. For example, mineral acids such as sulfuric acid, and hydrochloric acid may be included, and an oxidizing agent may also be included. As an alkali, sodium hydroxide is generally used. Permanganate is used as a chemical for desmear treatment to remove residual resin to obtain good adhesion for deposition of the electroless plating. The desmear treatment comprises three steps of swelling the resin with an alkali solution containing a small amount of organic solvent, etching by an alkali solution of permanganate, and neutralizing for removal of residual manganese. Therefore, this process may be applicable to either particles to be corroded by any one of acid and alkali solutions. In accordance with the swelling and solubility, the immersion of the resin in the chemicals is carried out for a few minutes to several tens of minutes. In the interval between these immersion processes, the resin needs to be washed by water. Further, it is possible for pre-treatment or post-treatment with alkali solution, before or after the desmear treatment.
- The method of forming the conductor on the resin surface will be described. The method comprises three steps of molding the resin, making the surface of molded resin rough with at least one of alkali and acid solutions, and subjecting the surface thereof to electroless plating for subsequent heat treatment.
- The method of molding is not limited. If the resin matrix is thermoplastic polymer, then it is possible to melt the resin composition to mold the resin in the desired shape. It is also possible to dissolve the resin composition into the solvent to apply on the substrate surface, or to inject into dies for subsequent volatilization If the resin matrix is the thermosetting polymer or non-thermoplastic polymer, it is possible to apply precursor varnish on the substrate surface for subsequent thermosetting by heat, light and radioactive ray.
- The surface of the molded resin is made rough for good adhesion with the electroless plated conductor by use of acid or alkali solutions. Permanganate is used as a chemical for desmear treatment. Further, prior to the desmear treatment, a mechanical polishing such as buff polishing is preferably carried out for obtaining the surface roughness. Particularly, if the surface is hard and the resistance to chemicals is high, the resin thin film is polished for removal thereof to show the particle surface.
- The rough surface of the resin is subjected to the electroless plating. In order to carry out the electroless plating, it is required to add to the substrate surface a catalyst causing plating reaction by various methods. As the catalyst, noble metals such as palladium are available. Particularly, palladium of colloidal type is often used. It is also possible to carry out the sensitizing by immersion of the resin into stannic chloride solution and subsequent activation by immersion into palladium chloride. It is further possible to immerse the resin into metal salt solution such as copper solution and nickel solution before reduction thereof for deposition of the metal, and subsequent palladium-replacement plating in the palladium chloride solution.
- After the catalyst is added, the electroless plating is carried out. Materials for plating are not limited and are selectable in accordance with various uses. If interconnections of the printed wiring board are formed, copper is preferable due to its low cost and low resistance. Nickel and gold are also available. Since the electroless plating is inferior in deposition rate, electroplating may be carried out following the electroless plating.
- If the conductive pattern is formed, photo-resist may be used for selective etching of the conductive film. Alternatively, only the necessary part of the conductive film is deposited after addition of the catalyst.
- Heat treatment is accomplished for improvement in adhesion between the molded resin surface and the plated film by removal of moisture from the interface between the molded resin surface and the plated film. The heat treatment is preferably carried out at a temperature of not less than 90° C., but not rapidly to prevent expansion of the plated film. Gradual heating is preferable. If a relatively small area pattern is preliminary formed, a rapid heating is also possible due to a sufficient pass for removing moisture.
- 100 parts by weight of a varnish available from Shin-Nihon Seitetu and containing 50% by weight of epoxy-acrylate having fluorene skeleton as resin solid component were blended with 20 parts by weight of bridged polymethylmethacrylate particles (M-305, diameter; 5-20 micrometers) available from Matumoto Oils and Fats Pharmaceutical for subsequent stirring in mixture for 20 minutes to obtain a uniform dispersion of the particles. This varnish of 40 micrometers in thickness was then applied onto an FR-4 unclad plate surface by curtain coater for subsequent pre-baking at 75° C. for 25 minutes before exposure at 500 mj/cm 2 prior to a thermosetting at 160° C. for 30 minutes. A glass transition temperature of the resin after thermosetting was 180° C.
- Subsequently, the resin surface was polished by #600 buff to make the surface rough before desmear chemicals were used for swelling, etching,. and neutralizing processes.
- A solution containing 0.05 mol of copper nitrate was applied to the rough surface for subsequent heat treatment at 150° C. for 3 hours, and oxygen-plasma treatment for 1 minute. Thereafter, particle free epoxy-acrylate varnish having a fluorene skeleton was treated in the same manner a described above until accomplishment of pre-baking processes for exposure through mask pattern and subsequent development with a solution containing 1% by weight of sodium carbonate for 5 minutes.
- This substrate was reduced in a solution containing 1 g/l of boron sodium hydride for 10 minutes to deposit metals in the patterns for subsequent washing by water before immersion into electroless copper plating solution KC-500 (available from Japan Energy) for 4 hours to deposit 20 micrometers-thick electroless copper and subsequent heat treatment at 150° C. for 1 hour.
- 90 degree peel strength test was carried out to confirm a strength of at least 1 kg/cm.
- In place of bridged polymethylmethacrylate particles (M-305, diameter; 5-20 micrometers), nylon 12 particles (orgasole 2001, diameter; 8-12 micrometers, melting point: 175-179° C.) was used. Other conditions are the same as Example 1.
- 90 degree peel strength test was carried out to confirm a strength of at least 0.9 kg/cm.
- In place of bridged polymethylmethacrylate particles (M-305, diameter; 5-20 micrometers), composite particles of 7-10 micrometers in diameter comprising titanium oxide core particles of 3-5 micrometers in diameter coated with nylon 12 were blended by 25 parts by weight. Other conditions are the same as Example 1.
- 90 degree peel strength test was carried out to confirm a strength of at least 0.9 kg/cm.
- In place of bridged polymethylmethacrylate particles (M-305, diameter; 5-20 micrometers), phenol resin particles of 13-15 micrometers in diameter were used and the etching process is carried out for twice as long. Other conditions are the same as Example 1.
- 90 degree peel strength test was carried out to confirm a strength of at least 1 kg/cm.
- 100 parts by weight of a photosensitive benzocyclobutene varnish being available from Dow Chemicals was blended with 20 parts by weight of calcium carbonate-treated bridge polymethylmethacrylate particles (M-305C, calcium carbonate/polymethylmethacrylate; {fraction (2/8)} in percent by weight) for subsequent stirring by mixture for 30 minutes to obtain a uniform dispersion of the particles. An alumina ceramic substrate is applied with 1 wt-% 3-aminopropyltriethoxysilane solution to spin-coat this varnish to a thickness of 10 micrometers thereonto for subsequent pre-baking at 75° C. for 30 minutes before exposure at 700 mj/cm 2 prior to a thermosetting at 210° C. for 30 minutes. A glass transition temperature of the resin after thermosetting was 250° C.
- Subsequently, the resin surface was polished by #320 buff to make the surface rough for pre-immersion into 20 wt-% hydrochloric acid solution for 15 minutes before desmear chemicals were used for swelling, etching and neutralizing processes.
- Palladium catalyst is adsorbed onto the rough surface for activation in the THP process before particle free epoxy-acrylate varnish having fluorene skeleton was treated in the same manner as described above prior to accomplishment of pre-baking processes for exposure through mask pattern, and subsequent development with kerosine for 2 minutes prior to the thermosetting.
- This substrate was returned to the THP process for reduction in a solution containing 1 g/l of boron sodium hydride for 10 minutes to deposit metals in the patterns. Subsequent washing by water is accomplished before immersion into electroless copper plating solution KC-500 (available from Japan Energy) for 2 hours to deposit 10 micrometers-thick electroless copper, and subsequent heat treatment at 160° C. for 1 hour.
- 90 degree peel strength test was carried out to confirm a strength of at least 0.9 kg/cm.
- In place of calcium carbonate-treated bridge polymethylmethacrylate particles (M-305C, diameter; 5-20 micrometers), hollow polyvinylidene particles (F-104E, diameter; 1-2 micrometers) were blended at 5 parts by weight to 15 parts by weight of M-305C. The etching time is reduced by half. Other conditions are the same as Example 5.
- 90 degree peel strength test was carried out to confirm a strength of at least 1 kg/cm.
- 100 parts by weight of polypropylene resin dried at 90° C. for 1 hour were blended with 40 parts by weight of nylon 6/66 particles dried at 75° C. for 4 hours (diameter; 10-20 micrometers) for subsequent mixing at 190° C. by biaxial extruder to form a chip. This chip was again dried at 90° C. for 1 hour for subsequent injection molding at 190° C. to form a 1.2 mm-thick plate.
- Subsequently, the resin surface was polished by #320 buff to make the surface rough before desmear chemicals were used for swelling, etching and neutralizing processes.
- Palladium catalyst is adsorbed onto the rough surface for activation in the THP process before electroless plating for 15 minutes to increase the thickness up to 18 micrometers. Hydrochloric acid is used to subsequently provide palladium to deposit electroless nickel plating at 1 micrometer for further flash gold plating. Heat treatment was carried out at 1000° C. for 1 hour.
- 90 degree peel strength test was carried out to confirm a strength of at least 0.9 kg/cm.
- 100 parts by weight of polymethylpentene resin were solved into 500 parts by weight of cyclohexane and then blended with nylon 12 particles (orgasole 2001, diameter; 8-12 micrometers, melting point: 175-179° C.). Other conditions are the same as Example 7.
- 90 degree peel strength test was carried out to confirm a strength of at least 0.8 kg/cm.
- Whereas modifications of the present invention will be apparent to a person having ordinary skill in the art to which the invention pertains, it is to be understood that embodiments as shown and described by way of illustrations are by no means intended to be considered in a limiting sense. Accordingly, it is to be intended to cover by claims all modifications which fall within the spirit and scope of the present invention.
Claims (7)
1. A method of forming a conductor on a surface of a resin composition comprising the steps of:
molding a resin which includes at least any one of insulative organic particles and insulative composite particles having an organic component and an inorganic component at a total amount in the range of 5-50% by volume, wherein the organic particles and the organic component of the composite particles are allowed to be corroded by either alkali or acid and wherein not less than 90% by volume of said at least any one of said insulative organic particles and said insulative composite particles has a particle diameter in the range of 1-20 micrometers;
exposing the resin to at least any one of an acid solution and an alkali solution to make a surface of the molded resin rough; and
subjecting the rough surface of the molded resin to an electroless plating for subsequent heat treatment to the resin.
2. The method as claimed in , wherein the acid solution and the alkali solution are permanganate and neutralizing solution thereof.
claim 1
3. A resin with resistance to alkali and acid comprising:
a resin matrix comprising an epoxy-acrylate having a fluorine skeleton and benzocyclobutene; and
at least one of insulative organic particles and insulative composite particles;
wherein not less than 90 percent by volume of said organic particles and said composite particles have a particle diameter in the range of 1-20 micrometers, and the volume of said at least one of said organic particles and said composite particles is in the range of 5-50 percent of the resin volume, said composite particles having an organic component and an inorganic component;
said organic particles and said organic component of said composite particles being selected from the group consisting of a thermoplastic amorphous polymer having a glass transition temperature of at least 90° C., a thermoplastic crystalline polymer having a melting point of at least 110° C., and a thermosetting polymer, and
said organic particles and said organic component of said composite particles being corrosible by one of an acid or an alkali; and
wherein said organic particles and said organic component of said composite particles comprise a thermoplastic crystal polymer having a melting point of at least 110° C.
4. A resin with resistance to alkali and acid comprising:
a resin matrix comprising an epoxy-acrylate having a fluorine skeleton and benzocyclobutene; and
at least one of insulative organic particles and insulative composite particles;
wherein not less than 90 percent by volume of said organic particles and said composite particles have a particle diameter in the range of 1-20 micrometers, and the volume of said at least one of said organic particles aid said composite particles is in the range of 5-50 percent of the resin volume, said composite particles having an organic component and an inorganic component;
said organic particles and said organic component of said composite particles being selected from the group consisting of a thermoplastic amorphous polymer having a glass transition temperature of at least 90° C., a thermoplastic crystalline polymer having a melting point of at least 110° C., and a thermosetting polymer, and
said organic particles and said organic component of said composite particles being corrosible by one of an acid or an alkali; and
wherein said organic particles and said organic component of said composite particles comprise a thermosetting polymer.
5. A resin with resistance to alkali and acid comprising:
a resin matrix comprising an epoxy-acrylate having a fluorine skeleton and benzocyclobutene; and
at least one of insulative organic particles and insulative composite particles;
wherein not less than 90 percent by volume of said organic particles and said composite particles have a particle diameter in the range of 1-20 micrometers, and the volume of said at least one of said organic particles and said composite particles is in the range of 5-50 percent of the resin volume, said composite particles having an organic component and an inorganic component;
said organic particles and said organic component of said composite particles being selected from the group consisting of a thermoplastic amorphous polymer having a glass transition temperature of at least 90° C., a thermoplastic crystalline polymer having a melting point of at least 110° C., and a thermosetting polymer, and
said organic particles and said organic component of said composite particles being corrosible by one of an acid or an alkali; and
wherein each of said composite particles comprise inorganic core particles coated with a thermoplastic polymer layer.
6. A resin with resistance to alkali and acid comprising:
a resin matrix comprising an epoxy-acrylate having a fluorine skeleton and benzocyclobutene; and
at least one of insulative organic particles and insulative composite particles;
wherein not less than 90 percent by volume of said organic particles and said composite particles have a particle diameter in the range of 1-20 micrometers, and the volume of said at least one of said organic particles and said composite particles is in the range of 5-50 percent of the resin volume, said composite particles having an organic component and an inorganic component;
said organic particles and said organic component of said composite particles being selected from the group consisting of a thermoplastic amorphous polymer having a glass transition temperature of at least 90° C., a thermoplastic crystalline polymer having a melting point of at least 110° C., and a thermosetting polymer, and
said organic particles and said organic component of said composite particles being corrosible by one of an acid or an alkali; and
wherein each of said composite particles comprise inorganic core particles coated with a thermosetting polymer layer.
7. A resin with resistance to alkali and acid comprising:
a resin matrix comprising an epoxy-acrylate having a fluorine skeleton and benzocyclobutene; and
at least one of insulative organic particles and insulative composite particles;
wherein not less than 90 percent by volume of said organic particles and said composite particles have a particle diameter in the range of 1-20 micrometers, and the volume of said at least one of said organic particles and said composite particles is in the range of 5-50 percent of the resin volume, said composite particles having an organic component and an inorganic component;
said organic particles and said organic component of said composite particles being selected from the group consisting of a thermoplastic amorphous polymer having a glass transition temperature of at least 90° C., a thermoplastic crystalline polymer having a melting point of at least 110° C., and a thermosetting polymer, and
said organic particles and said organic component of said composite particles being corrosible by one of an acid or an alkali;
wherein said organic particles and said composite particles comprise hollow particles;
wherein said hollow particles each have a coating of calcium carbonate, the weight of said coating being 25 percent or less of the weight of said hollow particle; and
wherein said organic particles and said organic component of said composite particles are at least one thermosetting polymer selected from the group consisting of epoxy resin, phenol resin, and diarylphthalate resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/815,059 US20010011111A1 (en) | 1996-12-05 | 2001-03-23 | Molded resin composition exhibiting good adhesion to conductive material on a surface |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8325301A JP3031272B2 (en) | 1996-12-05 | 1996-12-05 | Resin composition and method for forming conductor on molded article surface |
| JP08-325301 | 1996-12-05 | ||
| US08/986,104 US6232398B1 (en) | 1996-12-05 | 1997-12-05 | Alkali or acid corrodible organic or composite particles in resin matrix |
| US09/815,059 US20010011111A1 (en) | 1996-12-05 | 2001-03-23 | Molded resin composition exhibiting good adhesion to conductive material on a surface |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/986,104 Division US6232398B1 (en) | 1996-12-05 | 1997-12-05 | Alkali or acid corrodible organic or composite particles in resin matrix |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20010011111A1 true US20010011111A1 (en) | 2001-08-02 |
Family
ID=18175294
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/986,104 Expired - Lifetime US6232398B1 (en) | 1996-12-05 | 1997-12-05 | Alkali or acid corrodible organic or composite particles in resin matrix |
| US09/815,059 Abandoned US20010011111A1 (en) | 1996-12-05 | 2001-03-23 | Molded resin composition exhibiting good adhesion to conductive material on a surface |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/986,104 Expired - Lifetime US6232398B1 (en) | 1996-12-05 | 1997-12-05 | Alkali or acid corrodible organic or composite particles in resin matrix |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US6232398B1 (en) |
| JP (1) | JP3031272B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230611A1 (en) * | 2003-03-04 | 2006-10-19 | Zeon Corporation | Process for producing multilayer printed wiring board and multilayer printed wiring board |
| US20110257285A1 (en) * | 2008-10-28 | 2011-10-20 | Henkel Ag & Co., Kgaa | Epoxide-based structural foam having improved tenacity |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3119230B2 (en) * | 1998-03-03 | 2000-12-18 | 日本電気株式会社 | Resin film and method for connecting electronic components using the same |
| JP2002265762A (en) * | 2001-03-08 | 2002-09-18 | Nippon Kayaku Co Ltd | Benzocyclobutene resin composition, resin-bonded metallic molded part |
| US20070072425A1 (en) * | 2003-10-07 | 2007-03-29 | Neomax Materials Co., Ltd. | Substrate and method for producing same |
| JP4951924B2 (en) * | 2005-10-07 | 2012-06-13 | 学校法人早稲田大学 | Bipolar plate for solid polymer electrolyte fuel cell and solid polymer electrolyte fuel cell |
| US9201299B2 (en) * | 2007-10-01 | 2015-12-01 | San-Ei Kagaku Co., Ltd. | Inorganic filler and organic filler-containing curable resin composition, resist film coated printed wiring board, and method for producing the same |
| KR101114318B1 (en) * | 2009-04-16 | 2012-03-14 | 삼성전기주식회사 | Flame retardant resin composition for highly peel-strenghthened printed circuit board, printed circuit board using the same and manufacturing method thereof |
| US20110303644A1 (en) * | 2010-06-09 | 2011-12-15 | Arlington Plating Company | Methods for Plating Plastic Articles |
| CN108028194A (en) * | 2015-09-15 | 2018-05-11 | 日产化学工业株式会社 | Surface roughening method based on wet treatment |
| KR20240164882A (en) * | 2022-03-30 | 2024-11-21 | 니폰 제온 가부시키가이샤 | Hollow particles and their manufacturing method |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5618030B2 (en) | 1973-12-11 | 1981-04-25 | ||
| JPH066646B2 (en) | 1985-08-19 | 1994-01-26 | 三井東圧化学株式会社 | Polyolefin resin composition |
| JPH0649851B2 (en) | 1988-06-28 | 1994-06-29 | イビデン株式会社 | Adhesive for electroless plating |
| JP2612484B2 (en) | 1988-11-18 | 1997-05-21 | ディーエスエム・エヌヴィ | Optical three-dimensional molding resin composition |
| JPH0734505B2 (en) | 1989-01-18 | 1995-04-12 | イビデン株式会社 | Multilayer printed wiring board and manufacturing method thereof |
| JPH0570528A (en) | 1991-09-11 | 1993-03-23 | Nippon Steel Corp | Alkali-soluble photosensitive resin and alkaline-developable photosensitive resin composition using the same |
| JP3219827B2 (en) | 1992-03-02 | 2001-10-15 | イビデン株式会社 | Heat-resistant resin particles for anchor formation, adhesive for electroless plating, method for manufacturing printed wiring board using this adhesive, and printed wiring board |
| US5854302A (en) | 1993-04-29 | 1998-12-29 | The Dow Chemical Company | Partially polymerized divinylsiloxane linked bisbenzocyclobutene resins and methods for making said resins |
| JPH07179678A (en) | 1993-12-24 | 1995-07-18 | Sumitomo Chem Co Ltd | Polypropylene resin composition and film thereof |
| JP3398226B2 (en) | 1994-08-23 | 2003-04-21 | イビデン株式会社 | Metal film adherend |
| FR2724176B1 (en) | 1994-09-02 | 1997-01-03 | Rhone Poulenc Chimie | ORGANIC POLYMER-CALCIUM CARBONATE COMPOSITE PARTICLES, HOLLOW CALCIUM CARBONATE PARTICLES, PROCESSES FOR THEIR PREPARATION, THEIR USE AS FILLERS OR ADDITIVES IN PLASTICS AND ELASTOMERS. |
| JPH09214141A (en) | 1995-11-29 | 1997-08-15 | Nec Corp | Wiring construction |
| JPH1098271A (en) | 1996-03-29 | 1998-04-14 | Ibiden Co Ltd | Interlayer insulating agent and multilayered printed wiring board |
-
1996
- 1996-12-05 JP JP8325301A patent/JP3031272B2/en not_active Expired - Lifetime
-
1997
- 1997-12-05 US US08/986,104 patent/US6232398B1/en not_active Expired - Lifetime
-
2001
- 2001-03-23 US US09/815,059 patent/US20010011111A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060230611A1 (en) * | 2003-03-04 | 2006-10-19 | Zeon Corporation | Process for producing multilayer printed wiring board and multilayer printed wiring board |
| US7661190B2 (en) | 2003-03-04 | 2010-02-16 | Zeon Corporation | Process for producing multilayer printed wiring board |
| US20110257285A1 (en) * | 2008-10-28 | 2011-10-20 | Henkel Ag & Co., Kgaa | Epoxide-based structural foam having improved tenacity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3031272B2 (en) | 2000-04-10 |
| JPH10158526A (en) | 1998-06-16 |
| US6232398B1 (en) | 2001-05-15 |
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Legal Events
| Date | Code | Title | Description |
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| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |