CN1162654A - Metal coating on thermoplastic - Google Patents
Metal coating on thermoplastic Download PDFInfo
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- CN1162654A CN1162654A CN 97102153 CN97102153A CN1162654A CN 1162654 A CN1162654 A CN 1162654A CN 97102153 CN97102153 CN 97102153 CN 97102153 A CN97102153 A CN 97102153A CN 1162654 A CN1162654 A CN 1162654A
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000002184 metal Substances 0.000 title claims description 17
- 239000011248 coating agent Substances 0.000 title claims description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000004642 Polyimide Substances 0.000 claims abstract description 13
- 229920001721 polyimide Polymers 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 238000010101 extrusion blow moulding Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229920000412 polyarylene Polymers 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 1
- 229920013745 polyesteretherketone Polymers 0.000 abstract 1
- 229920002959 polymer blend Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 25
- 229920006360 Hostaflon Polymers 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 11
- 229920002530 polyetherether ketone Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000004696 Poly ether ether ketone Substances 0.000 description 10
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 9
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004963 Torlon Substances 0.000 description 4
- 229920003997 Torlon® Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920012287 polyphenylene sulfone Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- 229920013633 Fortron Polymers 0.000 description 3
- 239000004738 Fortron® Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229920004738 ULTEM® Polymers 0.000 description 3
- 229920003291 Ultrason® E Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229920003289 Ultrason® S Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 229920004704 VICTREX® PEEK 150XF Polymers 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 238000004164 analytical calibration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009996 mechanical pre-treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003210 poly(4-hydroxy benzoic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000000438 stratum basale Anatomy 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Metallized moldings of polymer mixtures comprise a thermoplastic and a filler selected from oxidized polyarylene sulfide, polyarylene sulfide, polyimide, aromatic polyester, or polyether ketone and mixture thereof. Said metallised plastics components have excellent metallic coatings adhesion.
Description
The present invention relates to the shaping workpiece of metallizing, this workpiece by contain at least a thermoplastic polymer heterogeneous, the biphase mixed polymer is made at least, and the production technique of this workpiece.
Common plastic-metal coating method is to adopt electrochemical method that metal deposition is arrived frosting.The first step is handled frosting earlier with chemistry or mechanical means, second step was coated with one deck agent of the discontinuous end, the 3rd step was put into chemical enhanced pond coating one deck continuous metal layer as thin as a wafer of metal-containing salt and reductive agent, the workpiece that to the handle aqueous solution of putting into metal-salt is electroplated metallizing at last, makes the thicker metal level of acquisition.The coating of stratum basale is that pretreated workpiece is put into the acidic zinc salts solution for instance, puts into precious metal aqueous solution metallizing then.Also can pressurize in two ponds.
Aforesaid method is very complicated, and step is many, and processing condition are complicated.The process of chemistry and mechanical pretreatment is often destroyed substrate, because frosting is poor to end agent solution wetting property, often goes wrong when the metallizing bottom.The bottom layer quality that this method generates is poor, discontinuous, and stability is poor.These class methods and other special metallizing technology see US-A4, in 590,115.
Also reported a kind of wet chemical technology of producing the electrolysis metallizing of the used nonmetal blank of printed circuit board (PCB) among the EP-A 0 414 097.This article is spoken of the simplification of production process and the raising of circuit card finished product quality.Yet this technology still shows system's limitation of wet chemical technology.
EP-A 0 417 037 has reported the example of another wet chemical technology, a kind of plastics part coating skim precious metal, these plastics contain a kind of weighting agent, can improve the adhesion strength of waiting to be coated with noble metal granule on the plastics workpiece surface, and the metal loss that causes owing to deposition in the pond is reduced.Metal oxide as weighting agent has MnO, NiO, Cu
2O, SnO and Bi
2O
3The shortcoming of these weighting agents is chemically stable inadequately and weight has problem.
An essence shortcoming of above-mentioned known wet chemical technology is: for reaching the firm degree of expectation, needed to formulate a cover than the complicated pretreatment step before metallizing.
These shortcomings can overcome with a kind of technology, wherein by making organometallics decompose to come applied plastic in plasma zone, and fluoropolymer (EP-A 0,321 734) especially.Its shortcoming is that ion energy, pressure of ambient gas, substrate humidity etc. are difficult to accurate control.Influence to energy emission also is difficult to abundant control equally.Another shortcoming is need use high pressure (about 133Pa) for the assurance continuous discharge.Because pressure is too big, to such an extent as to the evaporation of metallics can not continue to carry out.
These shortcomings can overcome with a kind of technology, i.e. the employing particles at low energies of describing among the EP-A 0,206 145.Shortcoming is to use some organic workpiece, and metal coat is insecure during as fluoropolymer.
The objective of the invention is the material of high yield forming polymer is improved, adopt sputter or method of evaporation metallizing, thereby the adhesion strength of the metal level on the polymeric substrates is improved with respect to starting polymer.
It is shocking: use heterogeneous, heterogenetic mixed polymer, promptly except containing a kind of thermoplastic polymer, the mixed polymer that also contains at least a poly arylidene thio-ester, a kind of oxidation poly arylidene thio-ester, a kind of polyimide, a kind of aromatic polyester or a kind of polyetherketone, can produce the metallizing plastic component of better performance, especially improve the adhesion strength of metallic coating on the plastic-substrates.
Therefore, the present invention relates to the metallizing plastic component made by heterogeneous mixed polymer, comprise A) a kind of thermoplastics and B) a kind of weighting agent.Its characteristic indication is: it contains at least a poly arylidene thio-ester, a kind of oxidation poly arylidene thio-ester, a kind of polyimide, a kind of aromatic polyester, a kind of polyetherketone or their mixture as weighting agent.
The invention still further relates to the strong metallizing plastic component of production tack, the heterogeneous mixed polymer of above-mentioned composition is made workpiece by moulding process earlier, then with workpiece gas phase sputtering process or sputtering method metallizing.
According to the present invention, the fusing point of suitable thermoplastic polymer should should be high temperature resistant or the high yield polymkeric substance more than 100 ℃ for example.The high yield polymkeric substance has fluoropolymer, polymeric amide, polycarbonate, polyester, polyimide, liquid crystalline polymers (LCP), polymethylmethacrylate, polyphenylene oxides, polysulfones, urethane and silicone.Preferred thermoplastics is a fluoropolymer, special preferably polytetrafluoroethylene (PTFE).
The plastic component metallizing is preferably used gas phase spraying plating processing or sputtering method.The metal that uses is unrestricted.The metal level that generates can be copper, silver, aluminium, gold, titanium, iron, chromium or nickel etc.
High-efficiency polymer refers to such plastics, and its fusing point is higher than 100 ℃, preferably is higher than 200 ℃.These polymkeric substance for example see the 5th edition (Encyclopedia of Industrial Chemistry of industrial chemistry encyclopaedia of Ullman, 5.Auflage), VCH publishes company limited, Weinheim-New York 1992: organic fluorine polymers, A11 volume 393-430 page or leaf; Polymeric amide, A21 volume 179-206 page or leaf; Polycarbonate, A21 volume 207-216 page or leaf; Polyester, A21 volume 227-252 page or leaf; Polyimide, A21 volume 253-273 page or leaf; Polymeric blend, A21 volume 274-305 page or leaf; High-temperature polymer, A21 volume 449-472 page or leaf; Polymethylmethacrylate, A21 volume 473-486 page or leaf; Polyphenylene oxides, A21 volume 605-614 page or leaf; Urethane, A21 volume 665-716 page or leaf and silicone, A24 volume 57-95 page or leaf, these contents will be merged in herein.
Polyarylphosphorus is also referred to as poly arylidene thio-ester and is meant such polymkeric substance, and it contains an arylene sulfide unit (A-S at least; The A=arylidene, S=sulphur).Arylidene such as phenylene, diphenylene (C
6H
4-C
6H
4-), naphthylidene, but one or many replaces.Substituting group can be C straight chain, cyclic or side chain
1-C
20Alkyl is as C
1-C
10Alkyl: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl or n-hexyl, or C
6-C
14Aryl: phenyl or naphthyl; Halogen, sulfonic group, amino, nitro, cyano group, hydroxyl or carbonyl.Particularly suitable is that polyphenylene sulfide (PPS) is as mixing composition B).
Polyarylphosphorus, particularly polyphenylene sulphur are pressed EDMONDS and the preparation of HILL method on the basis of dihalo aromatic compound and sodium sulphite reaction.Polyarylphosphorus and preparation technology thereof see " industrial chemistry encyclopaedia of Ullmann " A21 volume, B.Elvers.S.Hawkins and G.Schulz (Eds) work, and VCH, Weinheim-New York 1992, the 463-472 page or leaf is incorporated it into this paper.Contain among the synthetic Chimia of seeing 28 (9), (1974) 567 of polyarylphosphorus of sulfuryl, incorporate it into this paper equally.
The polyarylphosphorus of oxidation is the polyarylene of straight chain and side chain, and its sulfenyl partly or wholly is converted into sulfoxide group or sulfuryl.Oxidation polyarylphosphorus and preparation thereof see German patent application DE 4314737 and DE 4,314 738.The example of oxidation polyarylphosphorus has: polyarylsulfoxide, polyarylsulphone, polyarylphosphorus-sulfoxide, polyarylphosphorus-sulfoxide-sulfone, polyarylphosphorus-sulfone and polyarylsulfoxide-sulfone.Particularly preferred polyarylsulphone or polyarylphosphorus-sulfoxide-sulfone is the oxidation polyarylphosphorus: wherein at least 40%, and preferred at least 60% sulphur bridge is converted into sulfuryl.Preferred polyarylsulphone is a Polyphenylene Sulfone, particularly contains at least 40%, the Polyphenylene Sulfone of best 60% sulfuryl.The polyarylphosphorus of oxidation is heat-resisting especially, and very stable under the thermoplasticity processing conditions.This oxidation polyarylphosphorus is useed weighting agent as in thermoplastics.
The example of polyimide sees Ullmann industrial chemistry encyclopaedia A21 volume VCH and publishes company limited, and Weinheim-Ney York 1992, the 253-272 pages or leaves are incorporated it into this paper.This polyimide comprises thermoplastic polyimide and by polycondensation or add the polyimide that collecting process obtains.
Particularly suitable a kind of polyimide has following constitutional features:
This polyimide is to be made by the Lenzing AG company of Austrian Lenzing, and commodity are called P84.
The example of line style aromatic polyester is seen Ullmann industrial chemistry encyclopaedia A21 volume, and VCH publishes company limited, and Weinheim-New York 1992, the 227-251 pages or leaves are incorporated this paper at this.
Particularly suitable a kind of polyester contains oxygen benzoyl unit-O-C
6H
4-CO-.Sumitomo chemistry (the Sumitomo Chemical Co. of company limited by the Tokyo, Ltd) commodity of this polyester of Zhi Zaoing Sumika Super E101S by name, the commodity Ekonol by name of this polyester of making by the Carborundum company of USA New York.
It is the thin material polyether etherketone (Polyether etherketon) of Victrex PEEK 150XF that the suitable example of polyetherketone has code name, by the Victrax Germany Co., Ltd production of German Hofheim, the about 30 μ m of mean particle size.
Blending ingredients B) working what improve the metal coat mass action in is the oxidation poly arylidene thio-ester, because it has not only improved the metal coat effect, and shows significant chemical resistance.Fluoropolymer is by adding the performance of the permanent chemically-resistant widely of oxidation polyphenylene sulfide (particularly Polyphenylene Sulfone) maintenance.
Mix composition B) preferably use with powder-form.Mean particle size (the D of this powder
50Value) usually 0.3 * 10
-6To 500 * 10
-6Rice, preferred 1 * 10
-6To 100 * 10
-6Rice, preferred especially 5 * 10
-6To 50 * 10
-6Rice.For guaranteeing that metal level at the fabulous sticking power of workpiece surface, requires granularity as far as possible little, particularly make to mix composition B) granularity that is not melted in case of necessity.
Mix composition B) content be 1-99% weight, preferred 1-30% weight, preferred especially 1-20% weight, weight percentage are based on the polyblend gross weight.The preferred especially 5-15% weight according to the present invention.
Can contain typical additives according to polyblend of the present invention, as thermo-stabilizer, UV stablizer, static inhibitor, fireproofing agent, tinting material, pigment, inorganic and/or organic filler and as the lubricant of molybdenumdisulphide or graphite.
Usually in the mixing tank that is fit to, prepare one by one according to mixture of the present invention by single respective components, then according to already known processes (as injection moulding, pressure sintering, extrude, blowing, clinkering) put into relevant device under 150 ℃-450 ℃, preferred 200-400 ℃ add right one-tenth die body (workpiece), metallizing then.
The plastics part of metallizing is used for different industrial circles according to the present invention, needs the applied metal surfacing in these fields, as automotive industry, as advertising equipment, wireless, door handle, window glass rise and fall crank, heating installation frame, dashboard button, searchlight reflective mirror, taillight etc.In this external wireless, TV and the electronic industry, particularly printed circuit board (PCB), and multilayer-even sophisticated circuitry plate, chip carrier and the part in the EMI-protection screen, installed; In aircraft industry, in dentistry and medical industries, in the optics industry as the system mirror, and household goods.
Embodiment: Polyphenylene Sulfone (PPSO
2) preparation:
63 kilograms of polyphenylene sulfide powder (d
50Value: 20 μ m), Tg is that 94 ℃ and Tm are 290 ℃, adds in 219 liters of Glacial acetic acid of 50 ℃, adds 1.2 liters of vitriol oils, splashes into 91 kilograms of hydrogen peroxide (50%) in 3 hours, is warming up to 60-65 ℃ simultaneously.Stirred 2 hours down at 65 ℃ then, stirred 1 hour down at 80 ℃, with the reaction solution cooling, at 50 ℃ of suction strainers, washing is also dry.Yield: 70 kilograms; 352 ℃ of DSC data: Tg, Tm:520 (decomposition) ultimate analysis: (C
6H
4SO
2)
nC:55.6%, H3.2%, S:24.6%, O16.0%.This is 65% corresponding to the sulphur oxidisability in the polymkeric substance, calculates with theoretical oxygen uptake rate 100%.Also use following polymers among the embodiment:
Sumika Super E 101S is a kind of line style aromatic polyester (product appearance: powder) that Tokyo Sumitomo chemistry company limited produces.Product property and working method are seen the data loose-leaf " Sumika Super " that Sumitomo chemistry company limited provides.
P84 is a kind of polyimide (product appearance: powder) that the Lenzing AG of Austrian Lenzing produces.Product property and working method are seen the data loose-leaf " Lenzing P84 " that Lenzing AG company provides.
Fortron 0205 B4/20 is a kind of polyphenylene sulfide (product appearance: powder) that the Hoechst AG of Frankfurt, Germany produces.Product property and working method are seen the data loose-leaf " Fortron " that Hoechst AG company provides.
Unsized textile fibreglass through rolling is formed (mean length: 60 μ m, Fibre diameter: 14 μ m) by the monofilament of different lengths.
Hostaflon TF 1750 is a kind of tetrafluoroethylene (product appearances: powder) that the Hoechst AG of Frankfurt, Germany produces.Product property and working method are seen the data loose-leaf " Hostaflon " that Hoechst AG company provides.
Hostanon PFA 6515 is a kind of fluorinated thermoplastic plastics (product appearances: powder) that the Hoechst AG of Frankfurt, Germany produces.Product property and working method are seen the data loose-leaf " Hostaflon " that Hoechst AG company provides.
The MVI of Polybutylene Terephthalate (PBT) is 38cm
3/ 10 minutes (250 ℃/2.16kg).Product appearance: granular.
Vectra A950 is a kind of liquid crystal type polymkeric substance (product appearance: granular) that the Hoechst AG of Frankfurt, Germany produces.Product property and working method are seen the data loose-leaf " Vectra " that Hoechst AG company provides.
Ultem 1000 is a kind of polyetherimides (product appearance: granular) that the universal electric plastics company limited of German Ruesselsheim produces.Product property and working method are seen the data loose-leaf " Ultem " that universal electric plastics company limited provides.
Udel P-1700 is a kind of polysulfones (product appearance: granular) that the chemical company limited of Amoco Germany of Dusseldorf ,Germany produces.Product property and working method are seen the data loose-leaf " Amoco Performance Produets " that Amoco company provides.
PEEK 450G is a kind of polyether etherketone (product appearance: granular) that the Victrex Germany Co., Ltd of German Hofheim produces.Product property and working method are seen the brochure of Britain Middlesbrough: ICI material " Victrex PEEK ".
Torlon 4203L is a kind of polyamidoimide (product appearance: granular) that the chemical company limited of Amoco Germany of Dusseldorf ,Germany produces.Product property and working method are seen the data loose-leaf " Amoco Performance Products " that Amoco company provides.
Ultrason S is a kind of polysulfones (product appearance: granular) that the BASF AG of Ludwigshafen, Germany produces.Product property and working method are seen the brochure " Ultrason S, Ultrason E " that BASF AG provides.
Ultrason E is a kind of polyethersulfone (product appearance: granular) that the BASF AG of Ludwigshafen, Germany produces.Product property and working method are seen the brochure " UltrasonS, Ultrason E " that BASF AG provides.
PEEK 150 XF are polyether etherketones of a kind of porphyrize of producing of the Victrex Germany Co., Ltd of German Hofheim, and mean particle size is about 30 μ m.The manufacturing of compound:
These product particles are put into the ZM1 type experiment mill that German Haan Fa.Retsch company produces and are ground.Prescription by table 1 and 2 mixes product then.Mixture is dried, and is processed into sample (sample outward appearance: circular piece, diameter: 60mm, thickness: 4mm in the Polystat 200S type extrusion machine that the Fa.Schwabenthan of Berlin produces.The extrusion time unification is 15 minutes, in the extrusion temperature tabulation table).
The sample metallizing:
The sample that generates is put into Fa.Leyhold Heraeus and is produced Z700 spraying equipment metallizing.For the metallize sample is installed on the support in the equipment to spray 5 centimetres of targets apart, under same test parameter, handle in order to guarantee all samples.The copper that is used to apply is that electrochemistry is pure.Container is pumped into about 10
-5The mbar vacuum, then being pressurized to oxygen with oxygen is pressurized to 5 * 10
-3Mbar keeps discharge in 15 minutes.The voltage that apply on the sample this moment is 45V, and plasma power is 1kw.Sample applies the copper layer at once after the discharge, and Ar gas is spraying gas.Power is 1KwDC (direct current).For making coating even, the sample that is fixed on the support rotates with 1/3 rev/min of speed in container.The copper bed thickness 240nm of coating.Apply the vacuum that finishes and take out sample, measure adhesion strength.
The mensuration of adhesion strength is to carry out in a special instrument, and its structure is seen Fig. 1.Fig. 1 shows that at length the plane of a plunger 1 pastes mutually with the matel coated plane of sample 2.The adhesion strength of tackiness agent is known, always greater than the adhesive force of metal layer value of Instrument measuring in table 1 and the table 2.Apply power with 3 pairs of plungers 1 of stepper-motor, this power passes to dynamometry jar 4 (Burster, the Fa.Burster Technology of Precision Measurement company of German Gernsbach makes) by lever 5 and measures.A kind of signal voltage of dynamometry jar 4 outputs is by an electronic indicator device 6 (Keithley 197 multifunction instruments) record data.In case plunger 1 is torn the metallic coating of sample 2, voltage gets back to zero at once, can be calculated by peak voltage and pull component.The calibration of instrument is adopted and has been measured the known sample that pulls component through independent experiment.The component absolute value that pulls of following column data does not have decisive significance, importantly with pure thermoplastic polymer A) with contain the B that combined group is divided accordingly) the compound relative value of comparing.Comparative Example V 1, embodiment 1-9:
Following table 1 is that the detailed composition of above-mentioned polymkeric substance reaches the component that pulls to its mensuration.PPSO wherein
2Be that oxidisability is 65% polymkeric substance, its preparation method as previously mentioned.The extrusion forming temperature of sample is 375 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V1 | ?Hostaflon ?TF?1750 | ?240nm?Cu | ?89 | ?96 | ?92 |
| ?1 | ?90％Hostaflon ?TF?1750 ?10％Glasfaser | ?240nm?Cu | ?231 | ?97 | ?237 |
| ?2 | ??90％Hostaflon ??TF?1750 ??10％PPSO 2 | ??240nm?Cu | ?564 | ??94 | ??603 |
| ?3 | ??90％Hostaflon ??TF?1750 ??10％PPSO 2 | ??100nm?Ti ??240nm?Cu | ?480 | ??77 | ??637 |
| ?4 | ??90％Hostaflon ??TF?1750 ??10％PPSO 2 | ??10nm?TiO ??100nm?Ti ??240nm?Cu | ?411 | ??97 | ??426 |
| ?5 | ??90％Hostaflon ??TF?1750 ??10％P?84 | ??200nm?Cu | ?595 | ??96 | ??616 |
| ?6 | ??90％Hostaflon ??TF?1750 ??10％Sumika?Super ??E?101?S | ??200nm?Cu | ?519 | ??99 | ??521 |
| ??7 | ??90％Hostaflon ??TF?1750 ??10％Fortron?0205 ??B4/20 | ??240nm?Cu | ?488 | ??96 | ??508 |
| ??8 | ??90％Hostaflon ??TF?1750 ??5％PPSO 2??5％P?84 | ??240nm?Cu | ?581 | ??97 | ??599 |
| ??9 | ??90％Hostaflon ??TF?1750 ??5％PPSO 2??5％Sumika?Super ??E?101?S | ??240nm?Cu | ?543 | ??98 | ??554 |
Table 1 Comparative Example V 2, embodiment 10:
Table 2 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 375 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V2 | ?Hostaflon ?PFA?6516 | ?240nm?Cu | ?90 | ?95 | ?95 |
| ?10 | ?90％Hostaflon ?PFA?6516 ?10％PPSO 2 | ?240nm?Cu | ?622 | ?97 | ?642 |
Table 2 Comparative Example V 3, embodiment 11 and 12:
Table 3 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 250 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V3 | ?PBT | ?240nm?Cu | ?3139 | ?92 | ?3414 |
| ?11 | ?95％PBT ?5％PPSO 2 | ?240nm?Cu | ?3438 | ?94 | ?3656 |
| ?12 | ?90％PBT ?10％PPSO 2 | ?240nm?Cu | ?3620 | ?95 | ?3834 |
Table 3 Comparative Example V 4, embodiment 13:
Table 4 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 300 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| V4 | ?Vectra?A950 | ?240nm?Cu | ?532 | ?92 | ?570 |
| 13 | ?90％Vectra?A950 ?10％PPSO 2 | ?240nm?Cu | ?852 | ?97 | ?878 |
Table 4 Comparative Example V 5, embodiment 14 and 15:
Table 5 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 380 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| V5 | ?Ulterm?1000 | ?240nm?Cu | ?1976 | ?97 | ?2025 |
| 14 | ?90％Ultem?1000 ?10％PPSO 2 | ?240nm?Cu | ?2180 | ?100 | ?2180 |
| 15 | ?90％Ultem?1000 ?10％P84 | ?240nm?Cu | ?2903 | ?98 | ?2965 |
Table 5 Comparative Example V 6, embodiment 16:
Table 6 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 360 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V6 | ?Udel?P-1700 | ?240nm?Cu | ?1825 | ?95 | ?1913 |
| ?16 | ?90％Udel?P-1700 ?10％PPSO 2 | ?240nm?Cu | ?2485 | ?87 | ?2979 |
Table 6 Comparative Example V 7, embodiment 17 and 18:
Table 7 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 380 ℃.
(table 7)
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| V7 | ?Victrex?PEEK?450G | ?240nm?Cu | ?2340 | ?87 | ?2613 |
| 17 | ?90％Victrex?PEEK ?450G ?10％PPSO 2 | ?240nm?Cu | ?4194 | ?100 | ?4194 |
| 18 | ?90％Victrex?PPEK ?450G ?10％?P84 | ?240nm?Cu | ?2917 | ?97 | ?3010 |
Table 7 Comparative Example V 8, embodiment 19 and 20:
Table 8 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 260 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V8 | ?Torlon?4203L | ?240nm?Cu | ?1419 | ?80 | ?1725 |
| ?19 | ?90％Torlon?4203L ?10％PPSO 2 | ?240nm?Cu | ?2782 | ?99 | ?2799 |
| ?20 | ?90％Torlon?4203L ?10％P84 | ?240nm?Cu | ?2221 | ?99 | ?2261 |
Table 8 Comparative Example V 9 and V10, embodiment 21 and 22:
Table 9 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 360 ℃.
Table 9
Comparative Example V 11, embodiment 23,24 and 25:
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ?V9 | ?Ultrason?S | ?240nm?Cu | ?1402 | ?83 | ?1661 |
| ?21 | ?90％Ultrason?S ?10％PPSO 2 | ?240nm?Cu | ?3231 | ?90 | ?3640 |
| ?V10 | ?Ultrason?E | ?240nm?Cu | ?1620 | ?96 | ?1683 |
| ?22 | ?90％Ultrason?E ?10％PPSO 2 | ?140nm?Cu | ?2912 | ?91 | ?3231 |
Table 10 is another detailed component that pulls that reaches its mensuration of forming of polymkeric substance.The extrusion forming temperature of sample is 375 ℃.
| Embodiment | Polyblend | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| ??V11 | ??Hostaflon?TF?1750 | ??240nm?Cu | ??89 | ??96 | ??92 |
| ??23 | ??90％Hostaflon ??TF?1750 ??5％Victrex?PEEK ??150XF ??5％PPSO 2 | ??240nm?Cu | ??406 | ??100 | ??406 |
| ??24 | ??90％Hostaflon ??TF?1750 ??10％Victrex?PEEK ??150XF | ??240nm?Cu | ??693 | ??100 | ??693 |
| ??25 | ??80％Hostaflon ??TF?1750 ??20％Victrex?PEEK ??150XF | ??240nm?Cu | ??977 | ??100 | ??977 |
Table 10 embodiment 26-29:
In the table of embodiment 26-29, show the influence of pre-treatment to sample.With after the oxygen treatments applied, copper is very little in the influence that the adhesion strength of specimen surface is subjected to Comparative Example V 1-V10 and embodiment 1-25.Table 11 is PTFE/PPSO
2Different adhesion strengths with copper after the gas with various pre-treatment.Experimental detail is identical with embodiment 1.Sample extrusion forming temperature is 375 ℃.
| Embodiment | Polyblend | Pretreatment gas | The spraying medium | Pull component [N/cm 2] | Pull branch area [%] | Sticking power [N/cm 2] |
| 26 | ?90％ ?Hostaflon ?TF?1750 ?10％ ?PPSO 2 | ?Luft | ?240nm?Cu | ?525 | ?93 | ?565 |
| ?27 | ?90％ ?Hostaflon ?TF?1750 ?10％ ?PPSO 2 | ?O 2 | ?240nm?Cu | ?564 | ?94 | ?603 |
| ?28 | ?90％ ?Hostaflon ?TF?1750 ?10％ ?PPSO 2 | ?NH 3 | ?240nm?Cu | ?501 | ?96 | ?522 |
| ?29 | ?90％ ?Hostaflon ?TF?1750 ?10％ ?PPSO 2 | ?CF 4 | ?240nm?Cu | ?551 | ?94 | ?584 |
Table 11
Claims (10)
1. the plastic component of metallizing is made up of the heterophase polymerization mixture, and mixture contains A) a kind of thermoplastics and B) a kind of weighting agent, it is characterized in that, as the weighting agent minimum polyarylphosphorus that contains a kind of polyarylphosphorus, a kind of oxidation, a kind of polyimide, a kind of aromatic polyester or a kind of polyetherketone.
2. the plastic component of the metallizing in the claim 1 is characterized in that, the component A that contains) this thermoplastic polymer should have the fusing point more than 100 ℃.
3. the plastic component of claim 1 or 2 metallizing is characterized in that the component A that contains) this thermoplastic polymer is fluoropolymer, polymeric amide, polycarbonate, polyester, polyimide, liquid crystalline polymers (LCP), polymethylmethacrylate, polyphenylene oxides, polysulfones, urethane or silicone.
4. the plastic component of the metallizing of one of claim 1-3 is characterized in that, the A that contains) this thermoplastic polymer preferably polytetrafluoroethylene (PTFE).
5. the plastic component of the metallizing of one of claim 1 to 4 is characterized in that, as the B component of weighting agent) be the poly arylidene thio-ester of oxidation.
6. the plastic component of the metallizing of one of claim 1 to 5 is characterized in that, the metal of coating has copper, silver, aluminium, gold, titanium, iron, chromium or nickel and composition thereof or alloy.
7. the plastic component technology for preparing the metallizing of one of claim 1 to 6, it is characterized in that, generate mixture by each component, and then use injection moulding or pressure sintering or extrusion molding or blow moulding or sintering method under 150～450 ℃, preferred 200 ℃～400 ℃ with mixture machine-shaping, then with workpiece with gas phase spraying plating or sputtering method metallizing.
8. the technology of claim 7 is characterized in that, makes mixture by each component, wherein B component) account for the 1-99% weight of polyblend gross weight, preferred 1～30% weight, preferred especially 1～20% weight.
9. the technology of claim 8 is characterized in that, blending ingredients B) content be 5～15% weight.
10. the application of the workpiece of the metallizing of one of claim 1 to 5: automotive industry middle frame, display instrument and wireless manufacturing, door handle, window glass up-down handle, heating installation frame, dashboard button, searchlight reflective mirror; In wireless, TV and electronic industry, make printed circuit board (PCB), chip carrier; The installation parts of EM1-protection screen; In aircraft industry, make mirror in the optics industry, and production household goods and toy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97102153 CN1162654A (en) | 1996-01-26 | 1997-01-24 | Metal coating on thermoplastic |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19602659.8 | 1996-01-26 | ||
| CN 97102153 CN1162654A (en) | 1996-01-26 | 1997-01-24 | Metal coating on thermoplastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1162654A true CN1162654A (en) | 1997-10-22 |
Family
ID=5166176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97102153 Pending CN1162654A (en) | 1996-01-26 | 1997-01-24 | Metal coating on thermoplastic |
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|---|---|
| CN (1) | CN1162654A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101677575A (en) * | 2007-04-18 | 2010-03-24 | 巴斯夫欧洲公司 | antimicrobial plastics and coatings |
| CN103805209A (en) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | Modified LCP (Liquid Crystal Polymer) plastic |
| CN106380773A (en) * | 2016-08-30 | 2017-02-08 | 厦门建霖工业有限公司 | Organic composite material for physical deposition of metal film layer |
| CN111101095A (en) * | 2020-01-10 | 2020-05-05 | 广州三孚新材料科技股份有限公司 | Chromium-free metallization method for plastic substrate |
| CN111726938A (en) * | 2020-06-15 | 2020-09-29 | 江苏百旭电子新材料科技有限公司 | A kind of FCCL flexible copper clad laminate and its manufacturing method |
-
1997
- 1997-01-24 CN CN 97102153 patent/CN1162654A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101677575A (en) * | 2007-04-18 | 2010-03-24 | 巴斯夫欧洲公司 | antimicrobial plastics and coatings |
| CN101677575B (en) * | 2007-04-18 | 2014-04-16 | 巴斯夫欧洲公司 | Antimicrobial plastics and coatings |
| CN103805209A (en) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | Modified LCP (Liquid Crystal Polymer) plastic |
| CN106380773A (en) * | 2016-08-30 | 2017-02-08 | 厦门建霖工业有限公司 | Organic composite material for physical deposition of metal film layer |
| CN106380773B (en) * | 2016-08-30 | 2019-06-14 | 厦门建霖健康家居股份有限公司 | A kind of organic composite material for physical deposition metallic diaphragm |
| CN111101095A (en) * | 2020-01-10 | 2020-05-05 | 广州三孚新材料科技股份有限公司 | Chromium-free metallization method for plastic substrate |
| CN111726938A (en) * | 2020-06-15 | 2020-09-29 | 江苏百旭电子新材料科技有限公司 | A kind of FCCL flexible copper clad laminate and its manufacturing method |
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