CN1175287A - Ornamental member - Google Patents
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- CN1175287A CN1175287A CN 95197559 CN95197559A CN1175287A CN 1175287 A CN1175287 A CN 1175287A CN 95197559 CN95197559 CN 95197559 CN 95197559 A CN95197559 A CN 95197559A CN 1175287 A CN1175287 A CN 1175287A
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Abstract
A white ornamental member comprising a base material, an undercoat plating layer formed on the base material in a thickness of 1 'mu'm or above and comprising copper (or its alloy), an Sn-Cu-Pd alloy plating layer formed on the undercoat plating layer in a thickness of 0.2 'mu'm or above and comprising 10-20 wt.% Sn, 10-80 wt.% Cu and 10-50 wt.% Pd as the essential components, and a finish plating layer formed on the alloy plating layer in a thickness of 0.2-5 'mu'm and comprising at least one member selected from among Pd, Rh and Pt. As this member does not contain any Ni component, it does not cause nickel allergy even when worn. Also it cna be provided in a single color of white, gold or black and in the combination of these colors at a low cost.
Description
Technical field
The present invention relates to decoration.More particularly, the present invention relates to have the polychrome of white, gold, black or above-mentioned color combination and when damaged, can not cause Ni decoration hypersensitive.Background technology
The decoration that can directly contact with skin when the external parts of all tables such as wristwatch case framework, back of the body lid and watchband, decoration such as necklace, bangle, ear stud, ring and earrings and spectacle frame are breakage.Great majority in them have tone as white, gold or black glossy etc.
When these decorations of industrial production, method commonly used be with dry plating or wet method plating technology at base material, for example form on the metal base and have the coating of above-mentioned tone.
For example, when production has white glossy watchcase, method commonly used is to form the Ni coating as bottom that thickness is about 2-3 μ m on the substrate surface of brass or copper-nickel alloy, on Ni coating, form the Pd-Ni alloy layer that thickness is about 2-3 μ m then, can at random and then on above-mentioned Pd-Ni alloy layer, carry out Rh or Pt flash as finish coat.
When production has golden glossy decoration, method commonly used is to form the Ni coating that thickness is about 2-3 μ m on the substrate surface of for example brass or copper-nickel alloy, on Ni coating, form the Pd-Ni alloy layer that thickness is about 2-3 μ m then, at last, on the Pd-Ni alloy layer, form 22 carats of Au-Ni alloy layers or the Au coating that thickness is about 1-2 μ m.In addition, the production decision of the golden decoration that had proposed already also has: form Ni coating and Pd-Ni alloy layer with wet method plating technology successively continuously at substrate surface, then with dry plating technology such as (cathode) sputtering method or vacuum evaporation coating embrane method continuous successively thick TiN layer and Au or Au-Ni alloy layer of about 0.1-10 μ m that form on Pd-Ni coating.
When production has the decoration of black glossy, method commonly used is to form thick Ni coating or the Cu-Ni-Cr alloy layer of about 2-3 μ m on the substrate surface of for example brass or copper-nickel alloy, forms thick black Ni coating or the black Cr coating of about 0.5-3 μ m more thereon.In addition, the production decision of the black decoration that had proposed already also has: form above-mentioned Ni coating or Cu-Ni-Cr alloy layer with wet method plating technology at substrate surface, form the thick TaC layer of about 0.1-2 μ m with PVD technology such as ion plating or (cathode) sputtering method thereon again.
Yet the decoration of all above-mentioned existing whites, gold and black contains Ni, and like this, they have the danger that causes dermatitis, because Ni can directly contact as free Ni dissolving and with skin in the sweat that for example skin is discharged.
Recently, the scheme of decoration that existing production does not contain white, gold and the black of Ni proposes, to suppress above-mentioned Ni allergy.
For example, the white in finish part that known useful following method is produced: at Cu coating or the Sn-Cu alloy layer of the thick Sn that contains 30-35 weight % of the substrate surface formation at least 2 μ m of for example brass, the Pd coating that forms thick about 0.1-5 μ m more thereon is as finish coat.In addition, also know on above-mentioned Pd coating the white in finish part that forms Rh or Pt flash layer and make.
The golden decoration that the following method of known usefulness is produced: the coating that forms Cu coating or Cu alloy such as above-mentioned Sn-Cu alloy earlier at the substrate surface of for example brass, then form Pd coating thereon, on Pd coating, form Au coating then or do not contain the Au alloy layer of Ni, as the Au-Fe alloy layer.
In addition, also know the golden decoration of producing with following method: with dry plating technology TiN layer and Au coating of the thick about 0.1-10 μ m of formation or do not contain the Au alloy layer of Ni continuously successively on above-mentioned Pd coating.
Knownly directly on above-mentioned Pd coating, form above-mentioned TaC layer and the black decoration that does not contain any Ni composition that makes with the dry plating technology.
All above-mentioned decorations do not contain any Ni composition, therefore, and when because damaged and during with skin contact, they can not cause Ni allergy.
Yet these decorations have Pd coating bar none, and Pd is expensive precious metal, and therefore, their production cost is very high inevitably.
Like this, people are just making great efforts to use the Pd alloy layer to replace the relative content of Pd coating with the Pd in the minimizing coating, thereby reduce the whole production cost.
A known example of above-mentioned Pd alloy layer is the Sn-Cu-Pd alloy layer.Yet this Sn-Cu-Pd coating on reducing cost is and is unsatisfactory, because Pd content wherein is significantly up to about 50-99 weight %.
In these cases, the present inventor studies the Sn-Cu-Pd alloy layer with low Pd content, and develops the method for the Sn-Cu-Pd ternary alloy that plating is made up of the Pd of the Cu of Sn, the 10-80 weight % of 10-20 weight % and 10-50 weight % and the plating bath that is used for this method.They are seen and are set forth in Japanese patent application No.5 (1993)-80844.
Compare with pure Pd coating, wherein the density of the Sn-Cu-Pd alloy layer of Ti Chuing is low, and for example, with the coating of same thickness relatively the time, it is about 60% that the Pd content of Sn-Cu-Pd alloy layer reduces, and like this, can reduce production costs.Sn-Cu-Pd coating has excellent erosion resistance and has excellent specular gloss.
The objective of the invention is to, the polychrome that can have white, gold, black or above-mentioned color combination is provided and can cause Ni decoration irritated and that can produce at low cost by the above-mentioned excellent properties that uses Sn-Cu-Pd coating.Disclosure of an invention
White in finish part of the present invention comprises base material; The prime coat on the covering substrates surface that at least 1 μ m is thick, above-mentioned prime coat is made up of Cu coating or Cu alloy layer; The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, above-mentioned Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; With the cover coating of the thick covering Sn-Cu-Pd alloy layer of 0.2-5 μ m, above-mentioned cover coating is selected from the elementary composition of Pd, Rh and Pt by at least one.
Golden decoration of the present invention (to call " the first golden decoration " in the following text) comprises base material; The prime coat on the covering substrates surface that at least 1 μ m is thick, above-mentioned prime coat is made up of Cu coating or Cu alloy layer; The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, above-mentioned Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; With the cover coating of the thick covering Sn-Cu-Pd alloy layer of 0.2-5 μ m, above-mentioned cover coating is made up of Au coating or the Au alloy layer that do not contain Ni.
Golden decoration of the present invention (to call " the second golden decoration " in the following text) comprises base material; The prime coat on the covering substrates surface that at least 1 μ m is thick, above-mentioned prime coat is made up of Cu coating or Cu alloy layer; The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, above-mentioned Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; 0.1-10 the TiN coating on the covering Sn-Cu-Pd alloy layer surface that μ m is thick; With the cover coating of the thick covering TiN layer of 0.05-0.5 μ m, above-mentioned cover coating is made up of Au coating or the Au alloy layer that do not contain Ni.
Black decoration of the present invention comprises base material; The prime coat on the covering substrates surface that at least 1 μ m is thick, above-mentioned prime coat is made up of Cu coating or Cu alloy layer; The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, above-mentioned Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; 0.2-1.0 the Ti layer on the covering Sn-Cu-Pd alloy layer surface that μ m is thick; With the cover coating of the thick covering Ti layer of 0.5-2.0 μ m, above-mentioned cover coating is made up of TiNCO.
Polychrome decoration of the present invention comprises base material; The prime coat on the covering substrates surface that at least 1 μ m is thick, above-mentioned prime coat is made up of Cu coating or Cu alloy layer; The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, above-mentioned Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; 0.2-5.0 the cover coating on the covering Sn-Cu-Pd alloy layer surface that μ m is thick, above-mentioned cover coating is made up of the material that is selected from Pd, Rh, Pt, Au, Au alloy and TiNCO; With cover surface layer part surface part finish coat, above-mentioned part finish coat is made up of the material that is different from finish coat, and has the tone that is different from finish coat.
In decoration of the present invention, their composition material does not all contain Ni, and like this, they can not run into the problems of dissolution of free Ni, and when because damaged and during with skin contact, decoration can not cause Ni allergy.The simple declaration of accompanying drawing
Fig. 1 is the layer section of structure of white in finish part A of the present invention;
Fig. 2 is the layer section of structure of golden decoration B of the present invention;
Fig. 3 is the layer section of structure of another golden decoration B ' of the present invention;
Fig. 4 is the layer section of structure of another golden decoration C of the present invention;
Fig. 5 is the layer section of structure of another golden decoration C ' more of the present invention;
Fig. 6 is the layer section of structure of black decoration D of the present invention;
Fig. 7 is the layer section of structure of polychrome decoration E1 of the present invention;
Fig. 8 is the state profile that shows the white in finish part A of the Fig. 1 with the Au that forms in its surface or Au alloy layer;
Fig. 9 is the state profile that shows the coating of the Fig. 8 with the patterned mask that forms in the above;
Figure 10 is presented among Fig. 9 except that the zone that is formed with patterned mask, the state profile of the coating that all the other zones have been removed; With
Figure 11 is the layer section of structure of another polychrome decoration E2 of the present invention.
In the drawings, numeral 1 expression base material (brass), numeral 2 expression prime coats (Cu or Cu alloy), numeral 3 expression Sn-Cu-Pd alloy layers, numeral 4 expression cover coating (Pd, Rh and Pt), numeral 5 expression cover coating (Au or Au alloy), numeral 6 expression Pd coating, the TiN coating that numeral 7 expressions form with the dry plating method, Au finish coat or Au alloy cap surface layer that numeral 8 expressions form with the dry plating method, the Ti layer that numeral 9 expressions form with the dry plating method, the TiNCO finish coat that numeral 10 expressions form with the dry plating method, numeral 11 expression patterned mask.Preferred forms of the present invention
At first, with reference to Fig. 1, white in finish part A of the present invention is described.
With reference to Fig. 1, base material 1 is made up of brass, and the surface of this base material is by the thick prime coat covering of being made up of Cu coating or Cu alloy layer of at least 1 μ m.Prime coat 2 has the sticking power guaranteed between base material 1 surface and the following Sn-Cu-Pd alloy layer to prevent coating and peel off and levelling property by contained Cu improves base material glossy function.This prime coat 2 is to form with wet method plating technology.
The material of base material 1 is not limited to brass.It can be for example copper, copper alloy (for example, red brass or phosphor bronze), zinc or zinc alloy (for example, Zn-Al alloy or Zn-Al-Cu alloy).
If the thickness of prime coat 2 is less than 1 μ m, then when the wet method plating, can the brittle intermetallics of formation between prime coat 2 and base material 1 (brass), like this, loss of adhesion between prime coat 2 and base material 1 surface.On the other hand, if above-mentioned thickness is too big, then not only unhelpful to prime coat, and, electroplate Strain Accumulation to high degree, phenomenon can appear peeling off in its result.The thickness of this prime coat 2 is preferably between the 1-5 μ m.
When prime coat 2 is formed by the Cu alloy, for example can use Cu-Sn alloy, Cu-Sn-Zn alloy, Cu-Sn-Pb alloy or Cu-Sn-Cd alloy as the Cu alloy.In these alloys, preferably use the Zn of the Sn, the 1-10 weight % that comprise 20-40 weight % and surplus Cu-Sn-Zn alloy as Cu.
When base material 1 was made up of brass, the prime coat 2 that is formed by above-mentioned Cu alloy can be guaranteed the sticking power between base material 1 and the following Sn-Cu-Pd alloy layer, because the Zn composition of 2 pairs of base materials 1 of prime coat and Sn-Cu-Pd alloy layer have high-affinity.
In this structure, if the Sn content in the Cu alloy is less than 20 weight %, the then corrosion-resistant of prime coat.On the other hand, greater than 40 weight %, then prime coat 2 has the intensive strain as if Sn content, and like this, it is very big from the tendency of base material 1 sur-face peeling.When attempting to produce by wherein Zn content less than the prime coat of the Cu alloy composition of 1 weight %, Zn content during plating bath is formed is so low, so that the effect of dwindling the sedimentation potential difference when electroplating between Cu and the Sn weakens, its result is difficult in low current operation or the high current practice process and obtains ideal gloss.And, when the Zn content in the Cu alloy during greater than 10 weight %, the corrosion-resistant of prime coat.When attempting to produce wherein Zn content greater than the prime coat of 10 weight %, when electroplating sedimentary Cu quantitative change big so that the rough sledding of whole prime coat jaundice appears.
Above-mentioned alloy composition can easily obtain by the composition of adjusting the plating bath of using in the wet method plating.
Then, form Sn-Cu-Pd alloy layer 3 with wet method plating technology on the surface of this prime coat 2.
This Sn-Cu-Pd alloy layer forms with the method described in Japanese patent application 5 (1993)-80844, and its composition comprises the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component.
If the Sn content in the above-mentioned Sn-Cu-Pd alloy layer is lower than 10 weight %, then not only the surface luster of Sn-Cu-Pd alloy layer is taken off change, and also variation of its erosion resistance.And if Sn content wherein surpasses 20 weight %, then the surface luster of Sn-Cu-Pd alloy layer 3 is also poor.Therefore, Sn content is set in the above-mentioned scope.This Sn content in the Sn-Cu-Pd alloy layer 3 should be preferably between the 16-18 weight % between 13-19 weight %.
If Cu content is less than 10 weight %, then the surface luster of Sn-Cu-Pd alloy layer 3 is poor.And if the Cu content in the Sn-Cu-Pd alloy layer greater than 80 weight %, then surface luster is also poor, and the erosion resistance of coating is degenerated.Therefore, Cu content is set in the above-mentioned scope.Cu content in the Sn-Cu-Pd alloy layer 3 should be preferably between the 43-45 weight % between 3-65 weight %.
If Pd content is less than 10 weight %, then the surface luster of Sn-Cu-Pd alloy layer 3 is poor.And if the Pd content in the Sn-Cu-Pd alloy layer greater than 50 weight %, then surface luster is also poor, in addition, the not only erosion resistance variation of coating, and production cost rises.Therefore, Pd content is set in the above-mentioned scope.Pd content in the Sn-Cu-Pd alloy layer 3 should be preferably between the 37-40 weight % between 25-45 weight %.
Especially, the Sn-Cu-Pd alloy layer of Pd that comprises the Cu of Sn, 43-45 weight % of 16-18 weight % and 37-40 weight % is highly beneficial, because Pd content expensive in the coating is low as can to reduce production cost, and surface luster and excellent corrosion resistance, and the effect of the sticking power between above-mentioned prime coat 2 and the following cover coating that is enhanced, and thermotolerance height.
The thickness setting of this Sn-Cu-Pd alloy layer 3 is more than 0.2 μ m.Its reason is, if this thickness less than 0.2 μ m, the zone of throwing power difference then can occur when electroplating, and these regional erosion resistance variation.The thickness of this Sn-Cu-Pd alloy layer 3 is preferably 0.2-10 μ m.
At last, form by one or at least two elementary composition cover coating 4 that is selected from Pd, Rh and Pt covering Sn-Cu-Pd alloy layer 3 with wet method plating technology, thereby obtain white in finish part A of the present invention.
The thickness setting of this cover coating 4 is 0.2-5 μ m.Its reason is, if this thickness is less than 0.2 μ m, then as the white glossy tone defectiveness of decoration, and if thickness greater than 5 μ m, then the improvement of tone reaches capacity, the expensive precious metal of waste just, thereby cause the rising of production cost.From guaranteeing the angle of ideal white glossy tone economically, the thickness of cover coating is preferably in the scope of 0.2-3 μ m.
Above-mentioned Sn-Cu-Pd alloy layer 3 is adjusted to the big thickness of 4-5 μ m, can reduces the thickness of this cover coating 4, its result can show ideal white gloss tone on its surface.Like this, obtain economically benefit.
In this white in finish part A, base material 1 and each coating all do not contain Ni, and therefore, when the sweat with the skin discharge contacted, white in finish part A can not run into free Ni dissolved problem, thereby can not cause Ni allergy.Whole Sn-Cu-Pd alloy layer 3 possesses white gloss and have excellent erosion resistance.Therefore, for example, even outmost cover coating 4 is impaired, display white gloss tone for a long time can be continued in the surface of decoration A.
The hardness of Sn-Cu-Pd alloy layer 3 (Hv) like this, for example, even cover coating 4 is impaired, can detect the damaged condition of base material 1 thus effectively up to about 250-350.
Below, with reference to Fig. 2 the of the present invention first golden decoration B is described.
This gold decoration B has the layer structure identical with white in finish part A, and difference is, the cover coating 4 of white in finish part A as shown in Figure 1 is by by Au coating or not contain the golden glossy cover of the band coating 5 that the Au alloy layer of Ni forms alternative.
Form above-mentioned cover coating 5 with wet method plating technology, its thickness setting is 0.2-5 μ m.
Its reason is, if the thickness of cover coating 5 is less than 0.2 μ m, the white color that then is positioned at the Sn-Cu-Pd alloy layer 3 of sublevel exposes, thereby cause defective occurring as the golden glossy tone of golden decoration, and if thickness greater than 5 μ m, the improvement of then golden gloss tone reaches capacity, and just wastes expensive Au, thereby causes the rising of production cost.
When forming this cover coating 5, can use Au-Fe, the Au-Pd, Au-Pt, Au-Sn, Au-Ag, Au-In, Au-Cu, Au-Pd-Fe and the Au-In-Fe alloy that for example do not contain Ni as the Au alloy with the Au alloy.
This gold decoration can have layer structure B ' shown in Figure 3, wherein, sandwiches Pd coating 6 with wet method plating technology between Sn-Cu-Pd alloy layer 3 and cover coating 5.
This layer structure B ' is gratifying, because compare with the layer structure of Fig. 2, the sticking power between Sn-Cu-Pd alloy layer 3 and the cover coating 5 is enhanced.
If Pd coating 6 is too thick, then can cause production cost to rise.On the other hand, if thickness is too little, the effect of then above-mentioned enhancing sticking power can not be brought into play fully.The thickness of Pd coating 6 is preferably between the 0.2-1 μ m.
Below with reference to Fig. 4 the of the present invention second golden decoration C is described.
This gold decoration C has the layer structure identical with golden decoration B, difference is, the golden cover coating 5 of golden decoration B as shown in Figure 2 is by by Au coating or not contain cover coating that the Au alloy layer of Ni forms 8 alternative and be clipped between this cover coating 8 and the Sn-Cu-Pd alloy layer 3 with the TiN layer 7 that the dry plating technology forms.
This TiN layer 7 has golden gloss and excellent abrasive, therefore, even when the cover coating above being formed on TiN layer 78 can not show golden gloss owing to breakage, the TiN layer alternatively showed golden gloss, thereby plays to guarantee for a long time golden decoration function.And even will be cut down widely by the thickness of the finish coat 8 of Au or Au alloy composition, the gained decoration can guarantee that still the gold on its surface decorates, thereby can reduce production cost.
The thickness setting of TiN layer 7 is 0.1-10 μ m.If this thickness less than 0.1 μ m, then can not keep gratifying wear resistance, its result, the white gloss that is positioned at the Sn-Cu-Pd alloy layer 3 under it exposes at short notice.On the other hand, if this thickness is greater than 10 μ m, then TiN layer 7 self can run into the blushing problem, its result, and its degraded appearance not only, and can cause production cost to rise.This thickness is preferably between the 0.2-0.3 μ m.
The thickness setting that is formed on the finish coat 8 above the TiN layer 7 is 0.05-0.5 μ m.If this thickness is less than 0.05 μ m, then throwing power can not be satisfactory, and feasible TiN layer 7 as sublevel exposes.On the other hand, greater than 0.5 μ m, the improvement of then golden gloss tone reaches capacity as if thickness, just the expensive Au of waste.The thickness of cover coating 8 is preferably in 0.2-0.3 μ m.
TiN layer 7 and finish coat 8 all form with habitual dry plating technology.The dry plating example of technology that can use aptly comprises (cathode) sputtering technology, ion plating technology or vacuum evaporation coating membrane technique.
In this gold decoration C, moiety does not all contain Ni, therefore, when golden decoration C contacts with the sweat of skin discharge, free Ni dissolving can't take place, and wears the Ni problem hypersensitive that can not run into per capita of this decoration.
When owing to wearing golden decoration C softish finish coat 8 being worn, thereby when the golden gloss that causes finish coat 8 disappeared, the TiN layer 7 that is positioned at the high-wearing feature under it can continue to show for a long time golden gloss.
And, even when and sweat that cause for example skin discharge impaired when finish coat 8 and TiN layer 7 infiltrates golden decoration C, golden decoration C since be positioned at the Sn-Cu-Pd alloy layer 3 under it excellence erosion resistance and guarantee erosion resistance for a long time.
This gold decoration can have layer structure C shown in Figure 5 ', wherein, between Sn-Cu-Pd alloy layer 3 and TiN layer 7, sandwich Pd coating 6 with wet method plating technology.
This layer structure C ' be gratifying, because compare with the layer structure of Fig. 4, the sticking power between Sn-Cu-Pd alloy layer 3 and the TiN layer 7 is enhanced.
If the thickness of Pd coating 6 is too big, then can cause production cost to rise.On the other hand, if thickness is too little, the effect of then above-mentioned enhancing sticking power can not be brought into play fully.The thickness of Pd coating 6 is preferably between the 0.2-1 μ m.
Below with reference to Fig. 6 black decoration D of the present invention is described.
This black decoration D has the layer structure identical with white in finish part A shown in Figure 1, difference is that the cover coating 4 of white in finish part A is clipped between finish coat 10 and the Sn-Cu-Pd alloy layer 3 by the Ti layer 9 that the finish coat 10 of the TiNCO that forms with the dry plating technology substitutes and forms with the dry plating technology.
Finish coat 10 has black glossy, and its hardness (Hv) is between 1000-1500.The wear resistance of finish coat 10 is so high, makes that the function of black decoration is continued to guarantee for a long time.
Being formed on finish coat 10 following Ti layers 9 can be combined in finish coat 10 on the Sn-Cu-Pd alloy layer 3 securely.Since the insertion of this Ti layer 9, the problem that black decoration D peels off from Sn-Cu-Pd alloy layer 3 completely without black finish coat 10.
As long as use under normal operation, even there is not Ti layer 9, that is, though when finish coat 10 be formed directly into Sn-Cu-Pd alloy layer 3 above the time, black decoration D does not have the problem that finish coat 10 is peeled off yet.
The thickness setting of this finish coat 10 is 0.5-2.0 μ m.If this thickness is greater than 0.5 μ m, then finish coat 10 is subjected to being positioned at the influence of the tone of Ti layer 9 under it and Sn-Cu-Pd alloy layer 3 (being white), is difficult to obtain black glossy clearly.On the other hand, if the thickness of finish coat 10 is greater than 0.2 μ m, then when finish coat 10 formed, the Strain Accumulation amount was very big, and its result finish coat 10 may occur and break, and the processing characteristics that layer forms descends.The thickness of finish coat 10 is preferably between the 0.8-1.5 μ m.
The thickness setting of the Ti layer 9 that forms below finish coat 10 is 0.2-1.0 μ m.If this thickness is greater than 0.2 μ m, then the sticking power between finish coat 10 and the Sn-Cu-Pd alloy layer 3 easily descends.On the other hand, if the thickness of TiN layer 9 is greater than 1.0 μ m, then the effect of not only above-mentioned enhancing sticking power does not become, and the processing characteristics that layer forms descends.The thickness of TiN layer 9 is preferably between the 0.4-0.8 μ m.
Finish coat 10 and Ti layer 9 all form with the dry plating technology.The dry plating example of technology that can use aptly comprises (cathode) sputtering technology, ion plating technology or vacuum evaporation coating membrane technique.In the formation of the finish coat 10 of being with black glossy, can use the method for describing among the open communique No.63 (1988)-161158 of Japanese Patent aptly.
Above-mentioned explanation relates to the decoration that the surface has white, gold and black glossy respectively.In the present invention, can produce the polychrome decoration that the surface has at least two kinds of glossy combinations by multiple gloss is made up.
Promptly, have with the surface of the tone of different tone mixing finish coats can be by following method production: on Sn-Cu-Pd alloy layer 3, form by in Pd, Rh and Pt (being white) layer, Au and the Au alloy (being gold) any layer or the layer of TiNCO (black) forms layer, then form and cover this finish coat part surface, have the layer (for example, the layer of the layer of Pd, Rh or Pt, Au or Au alloy or the layer of TiNCO) of the tone different with finish coat.
In the kind of polychrome decoration of the present invention,, illustrate the decoration E1 that the surface has white and these two kinds of colors of golden gloss below with reference to Fig. 7.
The pattern 5a of this decoration E1 by forming Au coating or Au alloy layer obtains with the part surface of the cover coating 4 that covers white in finish part A shown in Figure 1.
In the production of this decoration E1, at first, form Au or Au alloy layer 5 whole surface with the cover coating 4 of white in finish part A shown in the coverage diagram 1 (referring to Fig. 8).
Then, with reference to Fig. 9,, shelter pattern 11 in the intact zone formation of the plan on coating 5 surfaces by habitual printing process such as silk screen printing, inking roller or offset printing and brushing or photoetching.Then, the decoration of Fig. 9 is immersed in the prussiate type Au stripping liquid, dissolves with zone that above-mentioned masked pattern 11 is covered coating 5 with outside part.Like this, with reference to Figure 10, still stayed by the coating 5 of sheltering the zone that pattern 11 covers of preselected pattern and to be with on the white glossy coating 4.
Then, peel off and shelter pattern 11, obtain the band white shown in Figure 7 and the decoration E1 of golden these two kinds of colors thus.
Figure 11 is the sectional view of another double-colored decoration E2.In this double-colored decoration E2, use the method identical on the finish coat 10 of the black decoration D of Fig. 6, to form the pattern 5a of golden coating with above-mentioned decoration E1.Like this, this decoration E2 has the band black of the lip-deep golden patterns that is formed on the band black glossy and the decoration of golden these two kinds of colors.EXAMPLE Example 1
Form coating on the surface of brass watch case with following method, obtain having the white in finish part of the layer structure of Fig. 1 thus.
(1) formation of prime coat 2
The composition of plating bath: Na
2SnO
33H
2O 60g/l
CuCN 20g/l
K
2SO
3H 10g/l
KCN (dissociating) 30g/l
KOH 60g/l
Zn(CN)
2 5g/l
The plating condition:
Bathe 50 ℃ of temperature
Current density 2.4A/dm
2
pH 12.5
Sedimentation rate 0.33 μ m/min
Time 10min
On the watchcase surface, formed the Cu-Sn-Zn alloy layer 2 of thick about 3 μ m.
(2) formation of Sn-Cu-Pd alloy layer
On Cu-Sn-Zn alloy layer 2, form Sn-Cu-Pd alloy layer 3 under the following conditions.
The composition of plating bath: Na
2SnO
33H
2O 60g/l
(, being 26.7g/l) in Sn
CuCN 20g/l
(, being 14.2g/l) in Cu
K
2SO
3H 10g/l
KCN (dissociating) 30g/l
KOH 60g/l
K
2Pd(CN)
4·3H
2O 30g/l
(, being 9.3g/l) in Pd
The plating condition:
Bathe warm 50-55 ℃
Current density 2.0A/dm
2
Current efficiency 47.8%
pH 12.5-13
Sedimentation rate 0.33 μ m/min
Time 9min
Formed that thick about 3 μ m, hardness (Hv) are about 300, density is about 9.6g/cm
3Coating.Use scanning electron microscope and X-ray microanalysis instrument that the composition of this coating is carried out simple quantitative analysis, found that, coating is made up of the ternary alloy that the Pd of the Cu of Sn, the 44.22 weight % of 17.12 weight % and 38.66 weight % constitutes.
(3) formation of cover coating 4
On Sn-Cu-Pd alloy layer 3, form coating 4 under the following conditions.
Plating bath: Pallabright-SSS (ProductName)
Japan Pure Chemical Co., Ltd. produces
The plating condition:
Bathe 50 ℃ of temperature
Current density 1.5A/dm
2
pH 7.6
Sedimentation rate 0.33 μ m/min
Time 6min
Formed the band white glossy Pd coating 4 of thick about 2 μ m.
The band white glossy watchcase (white in finish part) that obtains was thus flooded 24 hours in the emulation sweat that contains 9.9g/l sodium-chlor, 0.8g/l sodium sulphite, 7.1g/l urea, 0.19ml/l ammoniacal liquor, 0.2g/l sucrose and 0.8ml/l lactic acid (50%).
Any fading do not seen on the surface, proves that thus it has excellent erosion resistance.
In addition, be with white glossy watchcase to carry out oven test, be allowed to condition at 200 ℃ and left standstill 5 hours this.Do not observe plating exfoliation.Embodiment 2
Form coating on the surface of brass watch case with following method, obtain having the golden decoration of the layer structure of Fig. 2 thus.
Form prime coat 2 and Sn-Cu-Pd alloy layer 3 with the method identical with embodiment 1.
Preparation contains the plating bath of the pH4.0 of Au10g/l, Pt0.3g/l, citric acid 100g/l and Trisodium Citrate 50g/l, is bathing temperature 40 ℃, current density 1.0A/dm
2Condition under wet method plating 15 minutes.On above-mentioned Sn-Cu-Pd alloy layer 3, formed the Au-Pt alloy layer 5 of thick 3.6 μ m thus.
The golden glossy watchcase of gained band (golden decoration) shows essentially identical erosion resistance and the thermotolerance with embodiment 1.Embodiment 3
Form coating on the surface of brass watch case with following method, obtain having the golden decoration of the layer structure B ' of Fig. 3 thus.
At first, under the condition identical, form prime coat 2 with embodiment 1.Again thereon in identical with embodiment 1, the difference part only is that electroplating time is the Sn-Cu-Pd alloy layer 3 that forms thick 2.5 μ m under 7.5 minutes the condition.Then, more thereon in identical with the formation of the cover coating of embodiment 1, the difference part only is that electroplating time is the Pd coating 6 that forms thick 0.5 μ m under 1 minute the condition.At last, under the condition identical, on Pd coating 6, form Au-Pt alloy layer 5 with embodiment 2.
The golden glossy watchcase of gained band (golden decoration) shows essentially identical erosion resistance and the thermotolerance with embodiment 1.Embodiment 4
Under the condition identical, form prime coat 2 and Sn-Cu-Pd alloy layer 3 successively on the surface of brass watch case with embodiment 1.Then, on Sn-Cu-Pd alloy layer 3, form TiN layer 7 and finish coat 8 under the following conditions, obtain having the golden decoration of the layer structure C of Fig. 4 thus.
The decoration that will have the Sn-Cu-Pd alloy layer 3 of formation is placed in the ion plating device.The inside of device is evacuated, imports argon gas then, the vacuum tightness that makes device is 1.0 * 10
-3Torr.
Then, start the thermion filament and the plasma electrode that are installed on the device, produce the Ar plasma body.Icon bombardment cleaning was made 10 minutes in the surface of Sn-Cu-Pd alloy layer 3.
Then, in device, import nitrogen, make the vacuum tightness of device remain on 2.0 * 10
-3Torr.Be placed in plasma gun on the device with when forming plasma body in startup, evaporate Ti10 minute, thus the thick TiN layer 7 of formation 0.5 μ m on above-mentioned Sn-Cu-Pd alloy layer 3.
Stop the evaporation of Ti and the importing of nitrogen.With the Au-Fe alloy evaporation coating of the Fe that contains 60 weight %, like this, on above-mentioned TiN layer 7, form the thick Au-Fe alloy layer 8 of 0.3 μ m.
The golden glossy watchcase of the band that obtains thus (golden decoration) has the golden tone of the unified regulation that satisfies Switzerland's gold-plated color standard 1N-14 item color requirement, and the tone that records with color difference meter is L
*80, a
*1.0, b
*15.0.
With the emulation sweat identical watchcase is carried out anti-corrosion test in 24 hours with embodiment 1.Do not observe the corrosion and fade.
In addition, with the gauze wiping watchcase of the alcoholic solution that has soaked into dimethylglyoxime, carry out the test of Ni reaction detection.The appearance of red coloration phenomenon is not arranged and do not measure free Ni.Embodiment 5
Form Sn-Cu-Pd alloy layer 3 with the method identical with embodiment 4, its thickness is identical with embodiment 3, is 2.5 μ m.Then, under the condition identical, form the thick Pd coating 6 of 0.5 μ m in the above with embodiment 3.On above-mentioned Pd coating 6, form thick TiN layer 7 of 0.5 μ m and the thick Au-Fe alloy layer 8 of 0.3 μ m successively by the method identical again with embodiment 4.Like this, make have Fig. 5 the layer structure C ' golden decoration.
With the emulation sweat identical watchcase is carried out anti-corrosion test in 24 hours with embodiment 1.Do not observe the corrosion and fade.Embodiment 6
Under the condition identical, form prime coat 2 and Sn-Cu-Pd alloy layer 3 successively on the surface of brass watch case with embodiment 1.Then, on Sn-Cu-Pd alloy layer 3, form Ti layer 9 and TiNCO finish coat 10 under the following conditions, obtain having the black decoration D of the layer structure of Fig. 6 thus.
The decoration that will have the Sn-Cu-Pd alloy layer 3 of formation is placed in the bell jar of ion plating device.The inside of bell jar is evacuated, imports argon gas then, the vacuum tightness that makes bell jar is 5 * 10
-4To 1 * 10
-2Between the Torr.
Then, start the thermion filament and the plasma electrode that are installed on the device, produce the Ar plasma body.Icon bombardment cleaning was made about 10 minutes in the surface of Sn-Cu-Pd alloy layer 3.
Then, the vacuum tightness with bell jar is adjusted in 3 * 10
-4To 1 * 10
-2In the scope of Torr, with the metal Ti of the electron beam irradiation that is installed in the plasma gun generation in the device as vapour source.Make the ionization and be that the acceleration voltage of 50-200V is applied on the decoration in plasma zone of the Ti steam of generation and argon gas with negative potential.On Sn-Cu-Pd alloy layer 3, form the thick TiN layer 9 of 0.5 μ m thus
The O that then, will contain 0.1-5.0 volume %
2Import in the bell jar with the nitrogen of the CO of 0.1-2.0 volume % and the mixed gas of argon gas, air inlet/exhaust is regulated and control, make the vacuum tightness of bell jar remain on 5 * 10
-5Torr.
Electron beam irradiation metal Ti with plasma gun produces produces Ti steam thus, meanwhile, the 50V volts DS is applied to as between anodal metal Ti and the decoration as negative pole about 30 minutes of the ion(ic)current of feeding 5A.
Like this, on Ti layer 9, form the TiNCO black finish coat 10 of thick about 1 μ m.
The surface of gained watchcase (black decoration) has band glossy black tone, and demonstration erosion resistance and the thermotolerance identical with the white in finish part of embodiment 1.This decoration 90 ° of pliability tests have been carried out.There is any peeling off on the surface of not observing the black finish coat, and proves to have excellent sticking power between itself and the base material.Embodiment 7
Under the condition identical, form prime coat 2 and Sn-Cu-Pd alloy layer 3 successively on the surface of brass watch case with embodiment 1.Then, on Sn-Cu-Pd alloy layer 3, form the cover coating 4 of Rh,, obtain having the polychrome decoration of the layer structure of Fig. 7 thus more thereon with the part cover coating 5 of following method formation Au-Pt alloy.
Under the following conditions the wet method plating is carried out on the surface of decoration with Sn-Cu-Pd alloy layer 3:
The Rh of the composition of plating bath: 2g/l and the H of 38ml/l
2SO
4
Bathe temperature: 40 ℃
Current density: 1A/dm
2Like this, formed the cover coating 4 of the thick 1.5 μ m that form by Rh.This cover coating 4 has dark white gloss, and hardness (Hv) is 850, excellent in abrasion resistance.
Under the condition identical, on cover coating 4, form the Au-Pt alloy layer 5 (referring to Fig. 8) of thick 2.5 μ m with embodiment 2.
The intact zone of plan that ink screen is printed on Au-Pt alloy layer 5 surfaces of sheltering with Resins, epoxy forms patterned mask shown in Figure 9 11 thus.Whole watchcase is immersed in the prussiate type Au stripping liquid, thereby the Au-Pt alloy layer of the above-mentioned zone that is covered by patterned mask 11 with outside part dissolved.
Whole watchcase is immersed in the stripping liquid of being made up of chlorinated hydrocarbons solvent, alcohol, nonionic surface active agent and paraffin, peels off patterned mask.
The watchcases (polychrome decoration) with white and golden these two kinds of colors of gained have the pattern 5a that is painted on the part cover coating of the golden tone of band on the part surface of the cover coating 4 of dark white color, the abundant decorative effect of performance design thus.In addition, this polychrome decoration has erosion resistance and the thermotolerance identical with the white in finish part of embodiment 1.
If want to enlarge on this polychrome decoration zone with the part cover coating of golden tone, suitable method comprises and forms with white glossy cover coating 4, forms patterned mask in the zone that stays white color of wanting of cover coating 4, meanwhile, at the part cover coating 5 of other zone formation, peel off patterned mask at last with golden tone.Embodiment 8
Under the condition identical, form the cover coating 10 of prime coat 2, Sn-Cu-Pd alloy layer 3, Ti layer 9 and TiNCO successively, obtain having the black decoration D of the layer structure of Fig. 6 thus on the surface of brass watch case with embodiment 6.Then, under the condition identical, on the black finish coat 10 of black decoration D, form pattern with the part cover coating of the Au-Pt alloy of golden tone with embodiment 7.
The watchcase (polychrome decoration) with black and golden these two kinds of colors of gained has the pattern of the band golden part cover coating on the part surface that is painted on the finish coat that has the glossy black tone, thus the whole meticulous decorative effect of performance.In addition, this polychrome decoration has the essentially identical erosion resistance of black decoration, thermotolerance and the sticking power with embodiment 6.
If want to enlarge on this polychrome decoration zone with the part cover coating of golden tone, suitable method comprises the cover coating that forms the band black glossy, forms patterned mask in the zone that stays black tone of wanting of cover coating, meanwhile, at the part cover coating 5 of other zone formation, peel off patterned mask at last with golden tone.
This polychrome decoration also can be by following method production.
That is, at first, produce the golden decoration of layer structure with Fig. 2.On the surface of its cover coating 5, form TiNCO cover coating.The remain untouched surface in zone of the plan that covers this finish coat with patterned mask.Whole decoration is flooded the given time in the 10-15% sodium hydroxide solution, and peel off with the TiNCO of outside part in the zone that will be covered by patterned mask thus.At last, whole decoration is immersed in the stripping liquid of being made up of chlorinated hydrocarbons solvent, alcohol, nonionic surface active agent and paraffin, optionally peels off patterned mask.The invention effect
Foregoing description shows that no free Ni dissolving from the white in finish part that comprises base material 1, prime coat 2, Sn-Cu-Pd alloy layer 3 and cover coating 4 is not because its constituent material all contains Ni.In addition, the ply adhesion between the coating is excellent, therefore, phenomenon do not occur peeling off in oven test.Also have, the white in finish part is owing to the effect of Sn-Cu-Pd alloy layer has excellent erosion resistance.
From the first golden decoration that comprises base material 1, prime coat 2, Sn-Cu-Pd alloy layer 3 and cover coating 5 and the second golden decoration that comprises base material 1, prime coat 2, Sn-Cu-Pd alloy layer 3, TiN layer 7 and finish coat 8, all there is not free Ni dissolving, because their constituent material does not all contain Ni.
No free Ni dissolving from the black decoration that comprises base material 1, prime coat 2, Sn-Cu-Pd alloy layer 3, Ti layer 9 and finish coat 10 is not because it contains Ni.Outmost TiNCO black finish coat has very high hardness and excellent abrasive.In addition, because the effect of Ti layer, outmost black finish coat and Sn-Cu-Pd alloy layer combine securely.Therefore, can bring into play the black decorative effect for a long time.
Finish coat that comprises base material 1, prime coat 2, Sn-Cu-Pd alloy layer 3, forms by the material that is selected from Pd, Rh, Pt, Au, Au alloy and TiNCO and the part surface that covers above-mentioned finish coat, form and polychrome decoration with part finish coat of the tone that is different from above-mentioned finish coat has for example white/gold, white/black or black/golden tone of band, thus the abundant decorative effect of performance design by the material that is different from above-mentioned finish coat.
Have the two the second golden decoration of Ti layer and finish coat because its constituent does not contain Ni with what the dry plating technology formed, therefore can not run into free Ni dissolved problem.In addition, owing between outmost golden layer that forms with the dry plating technology and Sn-Cu-Pd alloy layer, be used for the golden TiN layer that method plating technology has formed high-wearing feature, this second golden decoration is done as a whole, has the enhanced wear resistance, can guarantee work-ing life for a long time.
The second golden decoration that has the first golden decoration of the Pd coating that is clipped between Sn-Cu-Pd alloy layer 3 and the cover coating 5 and have the Pd coating that is clipped between Sn-Cu-Pd alloy layer 3 and the TiN layer 7 all shows the ply adhesion between the further enhanced coating.
Decoration of the present invention is very useful as the decoration of the tone of white, gold and black or their combination, and can not cause Ni allergy.
Claims (21)
1. white in finish part comprises:
Base material;
The prime coat on the covering substrates surface that at least 1 μ m is thick, described prime coat is made up of Cu coating or Cu alloy layer;
The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, described Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; With
0.2-5 the cover coating of the covering Sn-Cu-Pd alloy layer that μ m is thick, described cover coating is selected from the elementary composition of Pd, Rh and Pt by at least one.
2. decoration as claimed in claim 1 is characterized in that, described Cu alloy layer is by the alloy composition that is selected from Cu-Sn, Cu-Sn-Zn, Cu-Sn-Pb and Cu-Sn-Cd alloy.
3. decoration as claimed in claim 2 is characterized in that, described Cu alloy layer is the alloy composition of Cu by Zn and the surplus of the Sn that comprises 20-40 weight %, 1-10 weight %.
4. golden decoration comprises:
Base material;
The prime coat on the covering substrates surface that at least 1 μ m is thick, described prime coat is made up of Cu coating or Cu alloy layer;
The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, described Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component; With
0.2-5 the cover coating of the covering Sn-Cu-Pd alloy layer that μ m is thick, described cover coating is made up of Au coating or the Au alloy layer that do not contain Ni.
5. decoration as claimed in claim 4 is characterized in that, described Cu alloy layer is by the alloy composition that is selected from Cu-Sn, Cu-Sn-Zn, Cu-Sn-Pb and Cu-Sn-Cd alloy.
6. decoration as claimed in claim 5 is characterized in that, described Cu alloy layer is the alloy composition of Cu by Zn and the surplus of the Sn that comprises 20-40 weight %, 1-10 weight %.
7. golden decoration as claimed in claim 4 is characterized in that, Pd coating is clipped between Sn-Cu-Pd alloy layer and the cover coating.
8. golden decoration as claimed in claim 7 is characterized in that, described Pd coating forms with the wet method method for plating.
9. golden decoration comprises:
Base material;
The prime coat on the covering substrates surface that at least 1 μ m is thick, described prime coat is made up of Cu coating or Cu alloy layer;
The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, described Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component;
0.1-10 the TiN coating on the covering Sn-Cu-Pd alloy layer surface that μ m is thick; With
0.05-0.5 the cover coating of the covering TiN layer that μ m is thick, described cover coating is made up of Au coating or the Au alloy layer that do not contain Ni.
10. decoration as claimed in claim 9 is characterized in that, described Cu alloy layer is by the alloy composition that is selected from Cu-Sn, Cu-Sn-Zn, Cu-Sn-Pb and Cu-Sn-Cd alloy.
11. decoration as claimed in claim 10 is characterized in that, described Cu alloy layer is the alloy composition of Cu by Zn and the surplus of the Sn that comprises 20-40 weight %, 1-10 weight %.
12. golden decoration as claimed in claim 9 is characterized in that, Pd coating is clipped between Sn-Cu-Pd alloy layer and the TiN layer.
13. golden decoration as claimed in claim 12 is characterized in that, described Pd coating forms with the wet method method for plating.
14. golden decoration as claimed in claim 9 is characterized in that, TiN layer and finish coat all form with the dry plating method.
15. the black decoration comprises:
Base material;
The prime coat on the covering substrates surface that at least 1 μ m is thick, described prime coat is made up of Cu coating or Cu alloy layer;
The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, described Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component;
0.2-1.0 the Ti layer on the covering Sn-Cu-Pd alloy layer surface that μ m is thick; With
0.5-2.0 the cover coating of the covering Ti layer that μ m is thick, described cover coating is made up of TiNCO.
16. decoration as claimed in claim 15 is characterized in that, described Cu alloy layer is by the alloy composition that is selected from Cu-Sn, Cu-Sn-Zn, Cu-Sn-Pb and Cu-Sn-Cd alloy.
17. decoration as claimed in claim 16 is characterized in that, described Cu alloy layer is the alloy composition of Cu by Zn and the surplus of the Sn that comprises 20-40 weight %, 1-10 weight %.
18. black decoration as claimed in claim 14 is characterized in that, Ti layer and finish coat all form with the dry plating method.
19. the polychrome decoration comprises:
Base material;
The prime coat on the covering substrates surface that at least 1 μ m is thick, described prime coat is made up of Cu coating or Cu alloy layer;
The Sn-Cu-Pd alloy layer on the covering prime coat surface that at least 0.2 μ m is thick, described Sn-Cu-Pd alloy layer comprise the Pd of the Cu of Sn, 10-80 weight % of 10-20 weight % and 10-50 weight % as main component;
0.2-5.0 the cover coating on the covering Sn-Cu-Pd alloy layer surface that μ m is thick, described cover coating is made up of the material that is selected from Pd, Rh, Pt, Au, Au alloy and TiNCO; With
The part finish coat of the part surface of cover surface layer, described part finish coat is made up of the material that is different from finish coat, and has the tone that is different from finish coat.
20. decoration as claimed in claim 19 is characterized in that, described Cu alloy layer is by the alloy composition that is selected from Cu-Sn, Cu-Sn-Zn, Cu-Sn-Pb and Cu-Sn-Cd alloy.
21. decoration as claimed in claim 20 is characterized in that, described Cu alloy layer is the alloy composition of Cu by Zn and the surplus of the Sn that comprises 20-40 weight %, 1-10 weight %.
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| CN 95197559 CN1097644C (en) | 1995-12-07 | 1995-12-07 | Ornamental member |
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| CN 95197559 CN1097644C (en) | 1995-12-07 | 1995-12-07 | Ornamental member |
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| CN1175287A true CN1175287A (en) | 1998-03-04 |
| CN1097644C CN1097644C (en) | 2003-01-01 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008003216A1 (en) | 2006-06-26 | 2008-01-10 | Byd Company Limited | Electroplated product and preparation method thereof |
| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| EP3150744A1 (en) | 2015-09-30 | 2017-04-05 | COVENTYA S.p.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate |
| CN113106399A (en) * | 2020-12-29 | 2021-07-13 | 阳江市新辉科技有限公司 | Multicolor antibacterial film layer and preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768768B (en) | 2008-12-26 | 2012-01-25 | 比亚迪股份有限公司 | Aluminum alloy cyanide-free and nickel-free electroplating method and electroplating products thereof |
| ITUB20152876A1 (en) * | 2015-08-05 | 2017-02-05 | Bluclad S R L | Tin / copper alloys containing palladium, method for their preparation and use. |
-
1995
- 1995-12-07 CN CN 95197559 patent/CN1097644C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008003216A1 (en) | 2006-06-26 | 2008-01-10 | Byd Company Limited | Electroplated product and preparation method thereof |
| EP2035602A1 (en) * | 2006-06-26 | 2009-03-18 | Byd Company Limited | Electroplated product and preparation method thereof |
| EP2035602A4 (en) * | 2006-06-26 | 2009-07-15 | Byd Co Ltd | Electroplated product and preparation method thereof |
| CN102051648A (en) * | 2011-01-20 | 2011-05-11 | 广州市二轻工业科学技术研究所 | Cyanogen-free plating method of zinc alloy die casting |
| EP3150744A1 (en) | 2015-09-30 | 2017-04-05 | COVENTYA S.p.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate |
| CN113106399A (en) * | 2020-12-29 | 2021-07-13 | 阳江市新辉科技有限公司 | Multicolor antibacterial film layer and preparation method and application thereof |
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Address after: Japan Tokyo Tozai Tokyo city Tanashi town six chome 1 No. 12 Patentee after: Citizen Watch Co., Ltd. Address before: Japan Tokyo Tozai Tokyo city Tanashi town six chome 1 No. 12 Patentee before: Citizen Co., Ltd. |
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