TWI406975B - Method of plastic surface treatment - Google Patents
Method of plastic surface treatment Download PDFInfo
- Publication number
- TWI406975B TWI406975B TW97130322A TW97130322A TWI406975B TW I406975 B TWI406975 B TW I406975B TW 97130322 A TW97130322 A TW 97130322A TW 97130322 A TW97130322 A TW 97130322A TW I406975 B TWI406975 B TW I406975B
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- layer
- treatment method
- surface treatment
- plastic
- Prior art date
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 35
- 229920003023 plastic Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004381 surface treatment Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000009713 electroplating Methods 0.000 claims abstract description 8
- 238000010329 laser etching Methods 0.000 claims abstract description 8
- 238000007772 electroless plating Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 46
- 238000007747 plating Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003223 protective agent Substances 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 7
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000007788 roughening Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003595 mist Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 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 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本發明係關於一種塑膠表面處理方法，尤其係關於一種在塑膠表面產生亮啞雙色之表面處理方法。The invention relates to a plastic surface treatment method, in particular to a surface treatment method for producing bright and dull two colors on a plastic surface.
隨著人們對裝飾性外觀件之外觀品質及美觀性要求越來越高，多種表面裝飾技術應用於外觀件之製造。例如，為了獲得裝飾效果，手機、數位相機、個人數位助理等電子裝置之外觀件通常會進行電鍍或者烤漆等表面處理。其中，用電鍍方法處理後之外觀件產品金屬質感強，耐磨性能較好，因而受到人們青睞。With the increasing demand for the appearance quality and aesthetics of decorative appearance parts, various surface decoration techniques are applied to the manufacture of appearance parts. For example, in order to obtain a decorative effect, an appearance of an electronic device such as a mobile phone, a digital camera, or a personal digital assistant is usually subjected to surface treatment such as plating or baking. Among them, the appearance product treated by the electroplating method has strong metal texture and good wear resistance, and thus is favored by people.
目前，塑膠電鍍外觀件表面大多為同一光亮度表面，比如產品之整個電鍍表面均為亮面，或者均為啞光面，表面光亮度缺乏變化，視覺效果欠佳。At present, the surface of the plastic plating appearance parts are mostly the same brightness surface, for example, the entire plating surface of the product is a bright surface, or both are matte surfaces, the surface brightness is not changed, and the visual effect is not good.
有鑒於此，有必要提供一種可於塑膠表面獲得亮啞雙色之表面處理方法。In view of this, it is necessary to provide a surface treatment method which can obtain a bright and dull color on a plastic surface.
一種塑膠表面處理方法，其包括如下步驟：提供一塑膠基體；以無電解電鍍之方式於該基體表面形成至少一化學金屬層；以電解電鍍之方式於該化學金屬層表面形成一鍍銅層，使該化學金屬層位於該鍍銅層與該塑膠基體之間；用鐳射蝕刻方法於該鍍銅層表面進行蝕刻，以於該鍍銅層上形成一粗糙區； 以電解電鍍之方式於該基體之鍍銅層表面形成一電鍍表層。A plastic surface treatment method comprising the steps of: providing a plastic substrate; forming at least one chemical metal layer on the surface of the substrate by electroless plating; forming a copper plating layer on the surface of the chemical metal layer by electrolytic plating, The chemical metal layer is disposed between the copper plating layer and the plastic substrate; etching is performed on the surface of the copper plating layer by a laser etching method to form a rough region on the copper plating layer; An electroplated surface layer is formed on the surface of the copper plating layer of the substrate by electrolytic plating.
上述塑膠表面處理方法在塑膠基體上形成一電鍍銅層後用鐳射蝕刻之方法在該電鍍銅層之局部區域蝕刻出一粗糙面，然後再於該局部形成有粗糙面之鍍銅層上形成一電鍍表層，從而使該塑膠基體之表面與該粗糙面對應之區域呈啞光面，其餘表面呈亮面，整體表面呈現亮啞雙色，由此獲得較佳之視覺效果。The plastic surface treatment method forms a copper plating layer on the plastic substrate, and then etches a rough surface in a partial region of the electroplated copper layer by laser etching, and then forms a copper layer on the partially formed rough surface. The surface layer is plated so that the surface of the plastic substrate has a matte surface corresponding to the rough surface, and the remaining surfaces are bright, and the overall surface is bright and dull, thereby obtaining a better visual effect.
本發明較佳實施例塑膠表面處理方法包括如下步驟：首先，提供一塑膠基體。該基體之材料可以為丙烯腈－丁二烯－苯乙烯(Acrylonitrile－Butadiene－Styrene,ABS)、聚碳酸酯(polycarbonate,PC)、丙烯腈－丁二烯－苯乙烯與聚碳酸酯混合物及聚甲基丙烯酸甲酯(Polyethylmethacrylate,PMMA)等可進行電鍍之塑膠材料。The plastic surface treatment method of the preferred embodiment of the present invention comprises the following steps: First, a plastic substrate is provided. The material of the substrate may be Acrylonitrile-Butadiene-Styrene (ABS), polycarbonate (PC), acrylonitrile-butadiene-styrene and polycarbonate mixture and poly A plastic material that can be plated, such as polyethylmethacrylate (PMMA).
之後，採用常規方法對該基體表面進行前處理。Thereafter, the surface of the substrate is pretreated by a conventional method.
該前處理包括先對該基體表面進行脫脂，然後對其進行表面粗化處理，以使該基體表面具有良好之附著力，有利於後續金屬層之附著。該粗化處理可通過使用含有鉻酸、鉻酸－硫酸混合酸或者高錳酸鉀之化學腐蝕劑腐蝕該基體表面來實現，也可以採用等離子加工之方法處理該基體表面，使其表面粗化。若採用含有鉻酸之化學腐蝕劑對該基體進行腐蝕粗化，則可將粗化後之基體用含有鹽酸及鉻還原劑之溶液進行氧化－還原中和清洗，再用清水沖洗。接 下來進一步對上述清水沖洗後之基體浸漬於一含有膠態鈀之活化溶液中進行活化處理。然後，將該活化後之基體置於含有草酸及鹽酸之解膠處理液中進行解膠處理，使活性之鈀晶核充分暴露出來，從而使鈀晶核具有非常強而均勻之活性。The pretreatment comprises first degreasing the surface of the substrate and then subjecting it to a surface roughening treatment so that the surface of the substrate has good adhesion and facilitates adhesion of the subsequent metal layer. The roughening treatment can be carried out by etching the surface of the substrate with a chemical etchant containing chromic acid, a chromic acid-sulfuric acid mixed acid or potassium permanganate, or the surface of the substrate can be treated by plasma processing to roughen the surface. If the substrate is subjected to corrosion roughening using a chemical etchant containing chromic acid, the roughened substrate may be subjected to oxidation-reduction neutralization washing with a solution containing hydrochloric acid and a chromium reducing agent, followed by rinsing with water. Connect Further, the substrate after the rinsing of the water is further immersed in an activation solution containing colloidal palladium for activation treatment. Then, the activated substrate is subjected to a degumming treatment in a degumming treatment liquid containing oxalic acid and hydrochloric acid to sufficiently expose the active palladium crystal nucleus, so that the palladium crystal nucleus has a very strong and uniform activity.
其後，將經上述前處理後之基體以無電解電鍍之方式於該解膠後之基體表面至少形成一化學金屬層。例如，該經上述處理後之基體形成一化學銅層，還可以在該化學銅層上形成一化學鎳層。Thereafter, at least one chemical metal layer is formed on the surface of the de-geled substrate by electroless plating on the pre-treated substrate. For example, the substrate after the above treatment forms a chemical copper layer, and an electroless nickel layer may be formed on the chemical copper layer.
再以電解電鍍之方式形成一電鍍銅層於該化學金屬層之表面，使該化學金屬層位於該電鍍銅層與基體之間。形成該電鍍銅層時，可將所述基體浸漬於含有硫酸銅或焦磷酸銅之電鍍液中。將該塑膠基體連接於一電源之負極，同時，將一銅金屬塊與該電源之正極連接並置於所述電鍍液中，接通電源，電解即可獲得該電鍍銅層。Then, an electroplated copper layer is formed on the surface of the chemical metal layer by electrolytic plating so that the chemical metal layer is located between the electroplated copper layer and the substrate. When the electroplated copper layer is formed, the substrate may be immersed in a plating solution containing copper sulfate or copper pyrophosphate. The plastic substrate is connected to the negative electrode of a power source. At the same time, a copper metal block is connected to the positive electrode of the power source and placed in the plating solution, and the copper plating layer is obtained by electrolysis.
將上述電鍍銅層後之基體置於一保護劑溶液中浸置1~5分鐘，以防止該鍍銅層氧化後於表面生成一氧化膜而不利於後續鍍層附著。該保護劑溶液中含有20~120g/L之重鉻酸鉀。該基體浸置於該保護劑溶液中時，可同時以基體作為陰極，以石墨或碳板作陽極，以該保護劑溶液作電解液，用0.5~2A/dm2之電流密度進行電解，以此獲得更好之保護效果。The substrate after the electroplated copper layer is immersed in a protective agent solution for 1 to 5 minutes to prevent the copper plating layer from being oxidized to form an oxide film on the surface, which is unfavorable for subsequent adhesion of the plating layer. The protective agent solution contains 20 to 120 g/L of potassium dichromate. When the substrate is immersed in the protective agent solution, the substrate may be used as a cathode, graphite or carbon plate as an anode, and the protective agent solution as an electrolyte, and electrolysis is performed at a current density of 0.5 to 2 A/dm 2 . Get better protection.
之後，對該浸置過保護液之基體表面預形成啞光面之位置進行鐳射蝕刻，使被蝕刻區域形成一粗糙面。該粗糙面可以為任何圖形、標誌或文字。Thereafter, the position of the matte surface on which the surface of the substrate on which the protective liquid has been immersed is subjected to laser etching to form a rough surface. The rough surface can be any graphic, logo or text.
將該鐳射蝕刻後之基體置於含有氫氧化鈉及除油劑之溶液中進行除油，以除去基體表面在鐳射蝕刻過程中可能沾染之油污及雜質。該除油劑可以選用MAX60。The laser etched substrate is degreased in a solution containing sodium hydroxide and a degreaser to remove oil stains and impurities that may be contaminated on the surface of the substrate during the laser etching process. The degreaser can be used with the MAX60.
然後，用含有鹽酸及硫酸之溶液清洗上述除油後之基體，以中和除油後基體上殘餘之堿液。Then, the above degreased substrate is washed with a solution containing hydrochloric acid and sulfuric acid to neutralize the residual mash on the substrate after degreasing.
最後，以電解電鍍之方式於該電鍍銅層表面形成一電鍍表層。該電鍍表層可以為鉻、銅錫合金、鎳、鋅或錫等金屬層。Finally, an electroplated surface layer is formed on the surface of the electroplated copper layer by electrolytic plating. The plating surface layer may be a metal layer such as chromium, copper tin alloy, nickel, zinc or tin.
上述塑膠表面處理方法在塑膠基體上形成一電鍍銅層後用鐳射蝕刻之方法在該電鍍銅層之局部區域蝕刻出一粗糙面，然後再於該局部形成有粗糙面之鍍銅層上形成一電鍍表層，從而使該塑膠基體之表面與該粗糙面對應之區域呈啞光面，其餘表面呈亮面，整體表面呈現亮啞雙色，由此獲得較佳之視覺效果。The plastic surface treatment method forms a copper plating layer on the plastic substrate, and then etches a rough surface in a partial region of the electroplated copper layer by laser etching, and then forms a copper layer on the partially formed rough surface. The surface layer is plated so that the surface of the plastic substrate has a matte surface corresponding to the rough surface, and the remaining surfaces are bright, and the overall surface is bright and dull, thereby obtaining a better visual effect.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97130322A TWI406975B (en) | 2008-08-08 | 2008-08-08 | Method of plastic surface treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97130322A TWI406975B (en) | 2008-08-08 | 2008-08-08 | Method of plastic surface treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201006965A TW201006965A (en) | 2010-02-16 |
| TWI406975B true TWI406975B (en) | 2013-09-01 |
Family
ID=44826851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW97130322A TWI406975B (en) | 2008-08-08 | 2008-08-08 | Method of plastic surface treatment |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI406975B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4084968A (en) * | 1973-03-30 | 1978-04-18 | U.S. Philips Corporation | Method of manufacturing electrically conductive metal layers on substrates |
| US4089993A (en) * | 1975-10-21 | 1978-05-16 | Fuji Photo Film Co., Ltd. | Method of forming a metallic thin film by electroless plating on a vinylidene chloride undercoat |
| US5846665A (en) * | 1990-11-23 | 1998-12-08 | Lacks Industries, Inc. | Method for electroplating high-impact plastics |
-
2008
- 2008-08-08 TW TW97130322A patent/TWI406975B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4084968A (en) * | 1973-03-30 | 1978-04-18 | U.S. Philips Corporation | Method of manufacturing electrically conductive metal layers on substrates |
| US4089993A (en) * | 1975-10-21 | 1978-05-16 | Fuji Photo Film Co., Ltd. | Method of forming a metallic thin film by electroless plating on a vinylidene chloride undercoat |
| US5846665A (en) * | 1990-11-23 | 1998-12-08 | Lacks Industries, Inc. | Method for electroplating high-impact plastics |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201006965A (en) | 2010-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613862B (en) | Plastic surface processing method | |
| KR100629793B1 (en) | Copper plating layer formation method with good adhesion with magnesium alloy by electroplating | |
| CN101922010B (en) | Aluminum alloy surface treatment method | |
| CN102363884B (en) | Surface treatment process for zinc alloy die casting | |
| CN102649209B (en) | A kind of preparation method of aluminum alloy appearance part | |
| JP4458521B2 (en) | Surface-treated copper foil having a grayed surface, a method for producing the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil | |
| CN101555614B (en) | Plastic surface galvanizing method | |
| KR20060073941A (en) | Products made of magnesium or magnesium alloys and preparation method thereof | |
| CN105349971A (en) | Aluminum alloy surface modification technology | |
| TWI406975B (en) | Method of plastic surface treatment | |
| WO2005010241A1 (en) | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display | |
| WO2019045047A1 (en) | Plating pretreatment method for abs resin surface, plating treatment method for abs resin surface, and abs resin plated product | |
| JP4736084B2 (en) | Manufacturing method of product made of magnesium or magnesium alloy | |
| KR100453508B1 (en) | Plating method for lusterless metal layer and products coated by the method | |
| JP5292195B2 (en) | Method for tin plating on magnesium alloy and etching solution for magnesium alloy | |
| JPH1018055A (en) | Method for metallizing surface of plastic by plating | |
| JP2008166655A (en) | Copper foil for electromagnetic shielding material | |
| CN112251753A (en) | Electrolytic regeneration method for acidic etching waste liquid of printed circuit board | |
| TWI444416B (en) | Method of electroplating plastic surface | |
| JPS586800B2 (en) | Insatsu Kairo Youdou Hakuo Hiyou Menshiyo Risuru Hohou | |
| JP2009074146A (en) | Manufacturing method of black plating | |
| JP4609779B2 (en) | Magnesium alloy member and method for forming highly corrosion-resistant film thereof | |
| JP2007254866A (en) | Plating pretreatment method for aluminum or aluminum alloy raw material | |
| JP3869433B2 (en) | Method for producing blackened surface-treated copper foil for electromagnetic wave shielding | |
| GB2603003A (en) | Method of etching a plastic component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |