CN104176769A - Doped tin oxide, preparing method thereof, polymer product, preparing method of the polymer product, ink composition and surface selective metallization method - Google Patents
Doped tin oxide, preparing method thereof, polymer product, preparing method of the polymer product, ink composition and surface selective metallization method Download PDFInfo
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Abstract
Doped tin oxide and a preparing method thereof are provided. The doping elements in the doped tin oxide relate to vanadium and/or molybdenum. Based on the amount of the doped tin oxide, the content of tin oxide is 90-99 mol%, and the total amount of the doping elements based on oxides is 1-10 mol%. A polymer product containing the dope tin oxide, a preparing method of the polymer product, an ink composition containing the doped tin oxide and a substrate surface selective metallization method are also provided. The doped tin oxide is light-colored. In addition, the doped tin oxide is high in absorption capability of energy beams, and a substrate surface irradiated by the energy beams can be gasified and peeled even though only a small amount of the doped tin oxide is added into the substrate, thus forming a metal layer on the irradiated surface through chemical plating. The surface of the polymer product can be subjected to selective metallization through chemical plating by selectively coating the surface to be metalized of the substrate with the ink containing the doped tin oxide.
Description
Technical field
The present invention relates to stannic oxide of a kind of doping and preparation method thereof, the invention still further relates to polymer product of a kind of stannic oxide that contains described doping and preparation method thereof, the present invention relates to again a kind of ink composite of the stannic oxide that contains described doping, the invention further relates to the method for substrate surface selective metallization.
Background technology
In the insulativity substrate surface selectivity as plastics, form metal level, using it as electromagnetic signal, the path of conduction, is widely used in the fields such as automobile, computer and communication.Can adopt several different methods to form metal level at the insulativity substrate surface as plastics.
For example, US5599592 discloses a kind of by the method for the plastics composite slice surface metal that contains plastics and metal oxide particle, and the method comprises: (1) uses the light being produced by excimer laser to irradiate the surface of composite material sheet; (2) composite material sheet through irradiating is placed in to chemical plating fluid and carries out electroless plating, with the forming metal layer on surface through irradiating; (3) composite material sheet that surface is formed with to metal level is heat-treated, so that the metal diffusing in coating enters in composite material sheet.Described metal oxide can be for the oxide compound of antimony, the oxide compound of the oxide compound of aluminium, iron, the oxide compound of the oxide compound of zinc or tin.Although US5599592 disclose described metal oxide particle content can for the 1-30%(of whole plastic composite tablet by weight or by volume), but from the disclosed embodiment of US5599592, more than the content of the metal oxide in matrix material is 4 volume %.
Summary of the invention
Metal oxide is preset at as in the insulativity matrix of plastics, after laser radiation, carries out electroless plating, thereby during by insulativity substrate surface selective metallization, when the color of metal oxide is darker, can affect the color of insulativity base material.But, when metal oxide as more shallow in the color of stannic oxide is preset in insulativity base material, because the photo absorption performance of the more shallow metal oxide of color is bad, the abundant energy of absorbing laser, can not make insulativity substrate surface peel off fast on the one hand, form porous surface; The electroless plating active centre quantity not sufficient that metal oxide activation forms on the other hand, is difficult to meet the requirement of electroless plating.Therefore, must be under higher metal oxide addition, or use high-octane laser beam, just can make substrate surface peel off and make base material there is the ability of electroless plating.
The present inventor conducts in-depth research for the problems referred to above, find: in stannic oxide, adulterate the oxide compound of molybdenum and/or the oxide compound of vanadium and the stannic oxide of the doping that obtains, not only of light color, and there is the light absorptive more much higher than stannic oxide, even under lower addition, or use low-energy laser beam to irradiate, the substrate surface of the stannic oxide that also can make to contain this doping is peeled off; The more important thing is, even if the stannic oxide of above-mentioned doping activates without energy-beam, also can, as electroless plating promotor, make base material there is the ability of electroless plating.Completed on this basis the present invention.
According to a first aspect of the invention, the invention provides a kind of stannic oxide of doping, doped element in the stannic oxide of this doping is vanadium and/or molybdenum, the total amount of stannic oxide of this doping of take is benchmark, the content of stannic oxide is 90-99 % by mole, and the total amount of described doped element of oxide compound of take is 1-10 % by mole.
According to a second aspect of the invention, the invention provides a kind of preparation method of stannic oxide of doping, the method comprises carries out roasting by a kind of powder mixture, described powder mixture contains stannic oxide and at least one compound containing doped element, the total amount of described powder mixture of take is benchmark, the content of described stannic oxide is 90-99 % by mole, the content of described doped element of oxide compound of take is 1-10 % by mole, described doped element is vanadium and/or molybdenum, described compound is the oxide compound of described doped element and/or the precursor that can form described oxide compound under roasting condition.
According to a third aspect of the present invention, the invention provides a kind of stannic oxide of the doping of being prepared by method of the present invention.
According to a fourth aspect of the present invention, the invention provides a kind of polymer product, this polymer product contains polymeric matrix and at least one metallic compound, described metallic compound is dispersed in described polymeric matrix, wherein, the stannic oxide that described metallic compound is doping provided by the invention.
According to a fifth aspect of the present invention, the invention provides a kind of preparation method of described polymer product, the method comprises each component of a kind of polymer composition is mixed, and by the mixture forming obtaining, described polymer composition contains polymer matrix component and at least one metallic compound.
According to a sixth aspect of the invention, the invention provides a kind of surfaces of polymeric articles selective metallization method, the method comprises:
With energy-beam irradiated polymer goods need to carry out metallized surface, make irradiated surface gasification; And
Postradiation polymer product is carried out to electroless plating,
Wherein, described polymer product is polymer product provided by the invention.
According to a seventh aspect of the present invention, the invention provides a kind of ink composite, said composition contains at least one metallic compound and at least one binder, wherein, and the stannic oxide that described metallic compound is doping provided by the invention.
According to an eighth aspect of the present invention, the invention provides a kind of insulativity substrate surface selective metallization method, the method comprises:
Each component in ink composite provided by the invention is mixed, and what the mixture obtaining was applied to insulativity base material need to carry out metallized surface, to form ink layer; And
The insulativity base material with described ink layer is carried out to electroless plating, with one deck metal level at least of plating on described ink layer.
Of light color according to the stannic oxide of doping of the present invention, in the time of in adding base material to, can or substantially can not exert an influence to the body color of base material, when being applied to substrate surface, can or substantially can not cover the body color of base material.And, strong to the receptivity of energy-beam according to the stannic oxide of doping of the present invention, even add in base material with lower addition, be also enough to make the substrate surface gasification of being irradiated by energy-beam to be peeled off.
According to the stannic oxide of doping of the present invention, without restoring metal simple-substance, can be used as electroless plating promotor, therefore, the polymer product of the stannic oxide that contains described doping only need be by surfaces of polymeric articles selectivity roughening, can be by electroless plating by surfaces of polymeric articles selective metallization; Or the stannic oxide of described doping is made to ink, ink Selective coating is needed to metallized surface at base material, can be by electroless plating by surfaces of polymeric articles selective metallization.And, when adopting energy-beam elective irradiation surfaces of polymeric articles to realize surface roughening, without too high energy, the stannic oxide of doping is reduced into metal simple-substance, and only need make polymer gasification expose the stannic oxide of doping, can directly carry out electroless plating, realize surfaces of polymeric articles selective metallization, technique is simple, low to energy requirement.
In addition, simple according to the preparation method of the stannic oxide of doping of the present invention, easy to implement.
Embodiment
According to a first aspect of the invention, the invention provides a kind of stannic oxide of doping, the doped element in the stannic oxide of this doping is vanadium and/or molybdenum.
In the stannic oxide of this doping, the total amount of doped element is 1-10 % by mole, is preferably 2-8 % by mole, and the content of stannic oxide is 90-99 % by mole, is preferably 92-98 % by mole.The content of described doped element is in oxide compound.When described doped element is vanadium and molybdenum, the present invention is not particularly limited for the ratio between described vanadium and molybdenum, as long as the total amount of vanadium and molybdenum meets aforementioned requirement.
According to the particle diameter of the stannic oxide of doping of the present invention, can carry out appropriate selection according to its concrete application scenario.Usually, the volume average particle size of the stannic oxide of described doping can be 50nm to 10 μ m, is preferably 300nm to 5 μ m, more preferably 1-3.5 μ m.Described volume average particle size is to adopt laser particle analyzer to measure.
Of light color according to the stannic oxide of doping of the present invention, is generally white.
Can be by using the oxide compound of vanadium and/or the oxide compound of molybdenum to obtain as hotchpotch according to the stannic oxide of doping of the present invention.The oxide compound of described vanadium refers to the compound being formed by v element and oxygen element, is generally Vanadium Pentoxide in FLAKES; The oxide compound of described molybdenum refers to the compound being formed by molybdenum element and oxygen element, is generally molybdic oxide.
According to a second aspect of the invention, the invention provides a kind of preparation method of stannic oxide of doping, the method comprises carries out roasting by a kind of powder mixture, described powder mixture contains stannic oxide and contains the compound of doped element, described doped element is vanadium and/or molybdenum, the oxide compound that described compound is described doped element and/or can form the precursor of described oxide compound under roasting condition.
When doped element contains vanadium, the oxide compound of described doped element contains the oxide compound of vanadium, as Vanadium Pentoxide in FLAKES; When doped element contains molybdenum, the oxide compound of described doped element contains the oxide compound of molybdenum, as molybdic oxide.
The precursor that can form described oxide compound under roasting condition can be the various compounds that can be transformed into oxide compound under roasting condition.For example, when described doped element contains vanadium, the described precursor that can form described oxide compound under roasting condition can contain the oxyhydroxide of vanadium and/or the gel of vanadium; When described doped element contains molybdenum, the described precursor that can form described oxide compound under roasting condition can contain the oxyhydroxide of molybdenum and/or the gel of molybdenum.
The total amount of described powder mixture of take is benchmark, and the content of described stannic oxide is 90-99 % by mole, is preferably 92-98 % by mole; The content of described doped element of oxide compound of take is 1-10 % by mole, is preferably 2-8 % by mole.The content of described doped element, in oxide compound, when the compound containing doped element is described precursor, is converted to the amount of this precursor the amount of corresponding oxide compound.When described doped element is vanadium and molybdenum, the relative proportion between described vanadium and molybdenum is not particularly limited, as long as the total amount of vanadium and molybdenum meets aforementioned requirement.
Method of the present invention is not particularly limited for the method for the described powder mixture of preparation, can select for routine.For example: can grind by stannic oxide with containing the compound of doped element, thereby obtain described powder mixture.Described grinding can be dry grinding, can be also wet grinding, can also grind for semidrying.The dispersion agent of described wet grinding can be various dispersion agents conventional in grinding technics.Particularly, described dispersion agent can be water and/or C
1-C
5alcohol (as ethanol).The consumption of dispersion agent can be selected for routine, is not particularly limited.When adopting wet grinding or semidrying to grind, also comprise that the mixture that grinding is obtained is dried, to obtain described powder mixture.Described dry can selection for routine.Particularly, described dry temperature can be 40-120 ℃, can in oxygen-containing atmosphere, carry out, and also can in nonactive atmosphere, carry out.Herein, described oxygen-containing atmosphere can be for example air atmosphere, or the atmosphere that oxygen and non-active gas are mixed to form.Described nonactive atmosphere refer to not with powder mixture in each component or the metallic compound of generation there is chemically interactive gas, can be for example neutral element gas or nitrogen, described neutral element gas can be argon gas.
The particle diameter of described powder mixture is not particularly limited, and can select for routine.Usually, the volume average particle size of described powder mixture can be 50nm to 10 μ m.
The method according to this invention, the temperature of described roasting can be 800-1000 ℃, is preferably 850-950 ℃.The condition of described roasting can be carried out appropriate selection according to the temperature of roasting, can be generally 1-6 hour.Described roasting can be carried out in oxygen-containing atmosphere, also can in nonactive atmosphere, carry out.But, at the described compound containing doped element, be that in the time of can forming the precursor of described oxide compound under roasting condition, described roasting is carried out in oxygen-containing atmosphere.
The method according to this invention, the product that roasting obtains can further grind, so that its particle diameter meets the requirement of concrete use occasion.Usually, it is 50nm to 10 μ m that the condition of described grinding makes the volume average particle size of the product of roasting after grinding, is preferably 300nm to 5 μ m, more preferably 1-3.5 μ m.Described grinding can be dry grinding, can be also wet grinding, can also grind for semidrying.The dispersion agent of described wet grinding can be various dispersion agents conventional in grinding technics.Particularly, described dispersion agent can be water and/or C
1-C
5alcohol (as ethanol).The consumption of dispersion agent can be selected for routine, is not particularly limited.
According to a third aspect of the present invention, the invention provides a kind of stannic oxide of the doping of being prepared by method of the present invention.
According to a fourth aspect of the present invention, the invention provides a kind of polymer product, this polymer product contains polymeric matrix and at least one metallic compound, described metallic compound is dispersed in described polymeric matrix, wherein, the stannic oxide that described metallic compound is doping provided by the invention.
Stannic oxide of described doping and preparation method thereof is described in detail above, repeats no more herein.
In described polymer product, the content of metallic compound can carry out appropriate selection according to the concrete function of metallic compound in polymer product.Particularly, when the metallic compound in described polymer product is used as electroless plating promotor, the gross weight of described polymer product of take is benchmark, the content of described metallic compound can be 1-10 % by weight, be preferably 1-5 % by weight, the content of described polymeric matrix can be 90-99 % by weight, is preferably 95-99 % by weight.The stannic oxide that is doping provided by the invention according to the metallic compound in polymer product of the present invention, it has better receptivity to energy-beam, even if also can absorb abundant energy under lower addition, makes surface of polymer substrates gasification.Therefore, the gross weight of described polymer product of take is benchmark, and the content of described metallic compound is 1-3 % by weight more preferably, and the content of described polymeric matrix is 97-99 % by weight more preferably.When the content of described metallic compound is 1-3 % by weight, when being enough to make surfaces of polymeric articles gasification to be peeled off under energy-beam irradiates to expose metallic compound and be enough to carry out electroless plating, described polymer product also has better mechanical property (as higher shock strength).
Described polymeric matrix can be the various formed bodys by polymer formation.Described polymkeric substance can carry out appropriate selection according to the concrete application scenario of this polymer product, can be thermoplastic polymer, can be also thermosetting polymer.Described polymkeric substance can be plastics, can be also rubber, can also be fiber.The specific examples of described polymkeric substance can include but not limited to: polyolefine is (as polystyrene, polypropylene, polymethylmethacrylate and poly-(acrylonitrile-butadiene-styrene (ABS))), polycarbonate, polyester is (if poly terephthalic acid hexanaphthene is to diformazan alcohol ester, PDAIP, poly terephthalic acid diallyl, PBN, polyethylene terephthalate and polybutylene terephthalate), polymeric amide is (as polyhexamethylene adipamide, poly-azelaoyl hexanediamine, poly-succinyl hexanediamine, nylon 612, polyhexamethylene sebacamide, nylon 1010, nylon 11, poly-lauramide, poly-decoylamide, poly-9 aminononanoic acid, polycaprolactam, poly-paraphenylene terephthalamide's phenylenediamine, poly-6I hexamethylene isoterephalamide, poly-hexamethylene terephthalamide and poly-paraphenylene terephthalamide's nonamethylene diamine), polyarylether, polyetherimide, polycarbonate/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene oxide, polyphenylene sulfide, polyimide, polysulfones, polyether-ether-ketone, polybenzimidazole, resol, urea-formaldehyde resin, melamine formaldehyde resin, epoxy resin, one or more in Synolac and urethane.
Described polymer product can also contain at least one auxiliary agent as required, and as filler, oxidation inhibitor and photostabilizer, to improve the performance of polymer product or to give polymer product with new performance, but described auxiliary agent should be light-colored auxiliary agent.The content of described auxiliary agent can carry out appropriate selection according to its kind and concrete service requirements, is not particularly limited.
Described filler can be laser not to be played to the filler of any physics or chemical action, for example, and talcum powder and calcium carbonate.Although glass fibre is insensitive to laser, add glass fibre can greatly deepen the degree of depth of plastic substrate depression after laser activation, be conducive to the adhesion of copper in electroless copper.Described mineral filler can also be the mineral filler that laser is played a role, for example, described filler can also be one or more in glass microballon, calcium sulfate, barium sulfate, titanium dioxide, pearlescence, wollastonite, diatomite, kaolin, potter's clay, mica, kerosene shale ash, pure aluminium silicate, aluminum oxide, silicon-dioxide and zinc oxide.
Described oxidation inhibitor can improve the antioxidant property of polymer product of the present invention, thereby improves the work-ing life of goods.Described oxidation inhibitor can for various oxidation inhibitor conventional in polymer arts, for example, can contain primary antioxidant and auxiliary antioxidant.Described primary antioxidant can carry out appropriate selection according to kind with the relative consumption between described auxiliary antioxidant.Usually, the weight ratio of described primary antioxidant and described auxiliary antioxidant can be 1:1-4.Described primary antioxidant can be hindered phenol type antioxidant; its specific examples can include but not limited to oxidation inhibitor 1098 and antioxidant 1010; wherein; the main component of oxidation inhibitor 1098 is N; N '-bis--(3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, the main component of antioxidant 1010 is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane.Described auxiliary antioxidant can be phosphite type oxidation inhibitor, and its specific examples can include but not limited to irgasfos 168, and its main component is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.
Described photostabilizer can be known various photostabilizers, hindered amine type light stabilizer for example, and its specific examples can include but not limited to two (2,2,6,6-tetramethyl--4-piperidyl) sebates.
The content of described auxiliary agent can carry out appropriate selection according to the function of auxiliary agent and kind.Usually, the total amount of described polymer product of take is benchmark, and the content of described filler can be 1-40 weight part, and the content of described oxidation inhibitor can be 0.01-1 weight part, the content of described photostabilizer can be 0.01-1 weight part, and the content of described lubricant can be 0.01-1 weight part.
According to a fifth aspect of the present invention, the invention provides a kind of preparation method of described polymer product, the method comprises each component of a kind of polymer composition is mixed, and by the mixture forming obtaining, described polymer composition contains polymer matrix component and at least one metallic compound.
Kind and the content of described metallic compound are described in detail above, repeat no more herein.
Described polymer matrix component refers to the component that is used to form polymeric matrix, comprises previously described polymkeric substance and various auxiliary agent.Described auxiliary agent for improving the performance of polymeric matrix or giving the auxiliary agent of polymeric matrix with new performance, can also comprise the various auxiliary agents that can improve the processing characteristics of polymeric matrix, as lubricant except previously described.Described lubricant can be the various materials that can improve the mobility of polymer melt, for example can be for being selected from one or more in copolymerization wax (EVA wax), polyethylene wax (PE wax) and the stearate of ethylene/vinyl acetate.
The present invention is not particularly limited for the method for moulding, can be the conventional various forming methods in forming polymer field, for example: injection moulding, extrusion moulding.
According to a sixth aspect of the invention, the invention provides a kind of surfaces of polymeric articles selective metallization method, the method comprises:
With energy-beam irradiated polymer goods need to carry out metallized surface, make irradiated surface gasification; And
Postradiation polymer product is carried out to electroless plating,
Wherein, described polymer product is polymer product provided by the invention.
Described energy-beam can, for laser, electron beam or ionic fluid, be preferably laser.The method according to this invention, the condition that described energy-beam irradiates, can make irradiated surfaces of polymeric articles gasification, exposes metallic compound and is as the criterion.Particularly, when described energy-beam is laser, described sharp light wavelength can be 157-10600nm, and power can be 1-100W; When described energy-beam is electron beam, the power density of described electron beam can be 10-10
11w/cm
2; When described energy-beam is ionic fluid, the energy of described ionic fluid can be 10-10
6eV.The angle of the precision of the pattern forming from further raising product surface, described energy-beam is preferably laser.The stannic oxide that contains doping provided by the invention due to described polymer product, the stannic oxide of this doping has higher receptivity to energy-beam, even if therefore use the lower energy-beam of energy to irradiate, also can make surface of polymer substrates gasification peel off, for example to be preferably wavelength be the laser that 1064-10600nm and power are 3-50W to described energy-beam, and more preferably wavelength is that 1064nm and power are more preferably 5-20W of 3-40W() laser.
The method that postradiation polymer product is carried out to electroless plating is for conventionally known to one of skill in the art.For example, while carrying out electroless copper, the method can comprise postradiation polymer product is contacted with copper electrolyte, described copper electrolyte contains mantoquita and reductive agent, pH value is 12-13, described reductive agent can be reduced to copper simple substance by cupric ion in mantoquita, and for example described reductive agent can be one or more in oxoethanoic acid, hydrazine and inferior sodium phosphate.
After carrying out electroless plating, can also then electroplate or carry out again one or many electroless plating, further to increase the thickness of coating or form other metal plating on chemical plating.For example, after electroless copper finishes, electroless plating one deck nickel prevents that copper coating surface is oxidized again.
According to a seventh aspect of the present invention, the invention provides a kind of ink composite, said composition contains at least one metallic compound and at least one binder, wherein, and the stannic oxide that described metallic compound is doping provided by the invention.
Stannic oxide of described doping and preparation method thereof is described in detail above, repeats no more herein.
When described ink composite is applied to insulativity substrate surface, described binder can play the surface that metallic compound is dispersed in to described insulativity base material, and forms on the surface of described insulativity base material the effect that has some strength and described insulativity base material is had to the rete of certain sticking power.
The present invention is not particularly limited for the kind of described binder, as long as selected binder can function as described above.Preferably, described binder is organic binder bond.More preferably, described binder is that rhodia, polyacrylic ester are one or more in resin, vinyl-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate (PVA), polyvinylpyrrolidone and polyphosphonic acid.
According to ink composite of the present invention, described binder for example can for example, for being purchased CAB series butylacetate Mierocrystalline cellulose (: the trade mark is the butylacetate Mierocrystalline cellulose of CAB381-0.5, CAB381-20, CAB551-0.2 and CAB381-2) from U.S. Yi Shi Man, be purchased the Mowital series polyvinyl butyral acetal (for example: the trade mark is Mowital B60T, Mowital B75H and Mowital B60H polyvinyl butyral acetal) from Japanese Kuraray company.
According to ink composite of the present invention, relative proportion between described binder metallizing thing is can be dispersed in described metallic compound the surface of described insulativity base material, formation has some strength and described insulativity base material is had to the ink layer of certain sticking power, and can be on described ink layer metal plating layer.Usually, according to ink composite of the present invention, with respect to 100 weight part metallic compounds, the amount of described binder can be 1-60 weight part, is preferably 30-60 weight part.
According to ink composite of the present invention, the dispersing uniformity from the described metallic compound of further raising described binder also forms the angle of more uniform rete on the surface of described insulativity base material, and described ink composite preferably also contains solvent.Ink composite of the present invention is not particularly limited for the kind of described solvent, can select for the routine of this area.Preferably, described solvent is water, C
1-C
12alcohol, C
3-C
12ketone, C
6-C
12aromatic hydrocarbons, C
1-C
12halogenated alkane and C
2-C
12haloolefin in one or more.Particularly, described solvent can be methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, acetone, the positive pentanone of 2-, the positive butanone of 2-, 3-methyl-2 pentanone, 2,3-dimethyl diketone, 2,3-diacetylmethane, 2, one or more in 5-hexanedione, hydroresorcinol, toluene, dimethylbenzene and trieline.
Ink composite of the present invention is not particularly limited for the consumption of described solvent, can be the conventional amount used of this area.Guarantee described metallic compound can be scattered in equably described binder in and under prerequisite at the surface uniform landform film forming layer of described insulativity base material, from reducing the angle of solvent load, with respect to 100 weight part metallic compounds, described solvent can be 20-250 weight part.
Ink composite according to the present invention can also contain according to its concrete application scenario the auxiliary agent that various ink areas are conventional, to give ink composite of the present invention with specific performance or function.Preferably, described auxiliary agent contains and is selected from one or more in dispersion agent, defoamer, flow agent and viscosity modifier.The consumption of described auxiliary agent can be selected for the routine of this area.Preferably, with respect to 100 weight part metallic compounds, the total amount of described auxiliary agent can be 0.1-20 weight part, is preferably 0.5-10 weight part.
According to ink composite of the present invention, described dispersion agent is for shortening the time that metallic compound is dispersed in to binder and optional solvent, and improves the dispersion stabilization of metallic compound in described binder and optional solvent.Described dispersion agent can be the conventional various materials that can realize above-mentioned functions in this area.For example, described dispersion agent can be the conventional organic dispersing agent in this area, for example: fatty amine is that dispersion agent, hydramine are that dispersion agent, ring-type unsaturated amine are that dispersion agent, fatty acid series dispersion agent, aliphatic amide are that dispersion agent, ester are that dispersion agent, paraffin series dispersion agent, phosphoric acid ester are that dispersion agent, polymer system dispersion agent (for example: polyacrylic ester is that dispersion agent and polyester are dispersion agent) and organic phosphine are dispersion agent.
According to ink composite of the present invention, described dispersion agent can be the conventional various dispersion agents that can be commercially available in this area.Particularly, described dispersion agent can be one or more in following dispersion agent: the trade mark being purchased from German BYK company is ANTI-TERRA-U, ANTI-TERRA-U80, ANTI-TERRA-U100, DISPERBYK-101, DISPERBYK-130, BYK-220S, LACTIMON, LACTIMON-WS, BYK-W966, DISPERBYK, BYK-154, BYK-9076, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-102, DISPERBYK-111, DISPERBYK-180, DISPERBYK-106, DISPERBYK-187, DISPERBYK-181, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-167, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-168, DISPERBYK-169, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-190, DISPERBYK-2150, BYK-9077, DISPERBYK-112, DISPERBYK-116, DISPERBYK-191, DISPERBYK-192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2020, DISPERBYK-2025, the dispersion agent of DISPERBYK-2050 and DISPERBYK-2070, the trade mark being purchased from Dutch Akzo Nobel company is the dispersion agent of PHOSPHOLAN PS-236, be purchased the dispersion agent that the trade mark from U.S. Witco chemical company is PS-21A, be purchased Hypermer KD Series Dispersant and Zephrym PD Series Dispersant from Britain Croda company.
According to ink composite of the present invention, described dispersion agent can be the conventional amount used of this area.Usually, with respect to 100 weight part metallic compounds, the content of described dispersion agent can be 0.1-4 weight part.
According to ink composite of the present invention, described defoamer can suppress formation of foam, destroy the foam forming or the material that the foam of formation is deviate from from system for conventional various in this area.For example, described defoamer can be that defoamer, polyethers are that defoamer and higher alcohols are defoamer for organopolysiloxane.Preferably, described defoamer is that organopolysiloxane is defoamer.
According to ink composite of the present invention, described defoamer can be the conventional various defoamers that can be commercially available in this area.Particularly, described defoamer can be BYK-051 for the trade mark being purchased from German BYK company, BYK-052, BYK-053, BYK-055, BYK-057, BYK-020, BYK-065, BYK-066N, BYK-067A, BYK-070, BYK-080A, BYK-088, BYK-141, BYK-019, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028, BYK-011, BYK-031, BYK-032, BYK-033, BYK-034, BYK-035, BYK-036, BYK-037, BYK-038, BYK-045, BYK-A530, BYK-A555, BYK-071, BYK-060, BYK-018, one or more in the defoamer of BYK-044 and BYK-094.
According to ink composite of the present invention, the amount of described defoamer can be the conventional amount used of this area.Preferably, with respect to 100 weight part metallic compounds, described defoamer is 0.1-3 weight part.
According to ink composite of the present invention, described flow agent is used for impelling ink to form more smooth, a smooth and uniform rete in drying and forming-film process.The present invention is not particularly limited for the kind of described flow agent, can be the conventional material that can realize above-mentioned functions in this area.For example, described flow agent can be that flow agent, polydimethylsiloxane are that flow agent, PSI are one or more in flow agent and fluorochemical surfactant for polyacrylic ester.
According to ink composite of the present invention, described flow agent can be the conventional various flow agents that can be commercially available in this area.For example, described flow agent can be one or more in BYK-333, BYK-306, BYK-358N, BYK-310, BYK-354 and BYK-356 flow agent for being purchased the trade mark from German BYK company.
According to ink composite of the present invention, the consumption of described flow agent can, for the conventional amount used of this area, be not particularly limited.Preferably, with respect to 100 weight part metallic compounds, described flow agent is 0.3-4 weight part.
According to ink composite of the present invention, described viscous regulator is for regulating the viscosity of ink composite.The present invention is not particularly limited for the kind of described viscous regulator, can select for the routine of this area.For example, described viscous regulator can be one or more in aerosil, polyamide wax, organobentonite, hydrogenated castor oil, metallic soap, hydroxy alkyl cellulose and derivative thereof, polyvinyl alcohol and polyacrylate.
According to ink composite of the present invention, the amount of viscous regulator can be selected for the routine of this area.Preferably, with respect to 100 weight part metallic compounds, described viscous regulator is 0.3-3 weight part.
Of the present invention a kind of preferred embodiment in, described ink composite contains described metallic compound, binder, solvent, dispersion agent, defoamer, flow agent and viscous regulator, with respect to 100 weight part metallic compounds, described binder is 1-60 weight part, described solvent is 20-250 weight part, and described dispersion agent is 0.4-4 weight part, and described defoamer is 0.1-3 weight part, described flow agent is 0.3-4 weight part, and described viscous regulator is 0.3-3 weight part.
According to the preparation method of ink composite of the present invention, be not particularly limited, as long as described metallic compound and binder and optional solvent and auxiliary agent can be mixed.For example, can be by mixing tank (as planetary ball mill), described metallic compound and binder and optional solvent and auxiliary agent are mixed, thereby obtain according to ink composite of the present invention.The method in mixing tank, each component being mixed and condition are known in the field, repeat no more herein.
According to ink composite of the present invention, can be applied in the surface of insulativity (that is, non-conductive) base material, and carry out electroless plating on the surface of described insulativity base material, with by the surface selective metallization of described insulativity base material.
According to an eighth aspect of the present invention, the invention provides a kind of edge substrate surface selective metallization method, the method comprises:
Each component in ink composite provided by the invention is mixed, and what the mixture obtaining was applied to insulativity base material need to carry out metallized surface, to form ink layer; And
The insulativity base material with described ink layer is carried out to electroless plating, with one deck metal level at least of plating on described ink layer.
The composition of described ink composite is described in detail above, repeats no more herein.
Can adopt the conventional the whole bag of tricks in this area ink composite provided by the invention to be applied to for example, on the surface of insulativity base material: can the ink being formed by ink composite according to the present invention is applied to and need to be carried out on the surface of metallized insulativity base material by being selected from silk screen printing, spraying, Laser Printing, spray ink Printing, transfer printing, intaglio printing, letterpress and lithographic method.Above-mentioned silk screen printing, spraying, Laser Printing, spray ink Printing, transfer printing, intaglio printing, letterpress and lithographic concrete operation method and condition are known in the field, repeat no more herein.Ink composite according to the present invention is particularly suitable for being applied to by the mode of spray ink Printing or Laser Printing the surface of insulativity substrate to metalization.
The method according to this invention can also comprise ink composite is applied to behind the surface of described insulativity base material, and the base material with described ink composite is dried.The present invention is not particularly limited for described dry method, can carry out appropriate selection according to the kind of the binder in ink composite and optional solvent, and for example: described dry temperature can be 40-150 ℃, the time can be 0.5-5 hour.Described dry can carrying out under normal pressure also can carry out under the condition of decompression.
The thickness of described ink layer can carry out appropriate selection according to the composition of described ink composite, carrying out electroless plating on the surface of described insulativity base material, and then the surface selective metallization of described insulativity base material is as the criterion.Preferably, the thickness of described ink layer is 8-50 μ m.More preferably, the thickness of described ink layer is 12-40 μ m.Further preferably, the thickness of described ink layer is 12-25 μ m.
The method of described electroless plating has been also conventionally known to one of skill in the art.For example, while carrying out electroless copper, the method can comprise the insulativity base material with ink layer is contacted with copper electrolyte, described copper electrolyte contains mantoquita and reductive agent, pH value is 12-13, described reductive agent can be reduced to copper simple substance by cupric ion in mantoquita, and for example described reductive agent can be one or more in oxoethanoic acid, hydrazine and inferior sodium phosphate.
After carrying out electroless plating, can also then electroplate or carry out again one or many electroless plating, further to increase the thickness of coating or form other metal plating on chemical plating.For example, after electroless copper finishes, electroless plating one deck nickel prevents that copper coating surface is oxidized again.
The sticking power of metal level and the angle of plating speed that from further raising electroless plating, form, method is according to an eighth aspect of the invention preferably before carrying out electroless plating by the insulativity base material with described ink layer, with energy-beam, the surface of described ink layer is irradiated, so that the gasification of the surface of ink layer.
Described energy-beam can, for laser, electron beam or ionic fluid, be preferably laser.The method according to this invention, the condition that described energy-beam irradiates is can make the surface gasification of ink layer be as the criterion.Particularly, when described energy-beam is laser, described sharp light wavelength can be 157-10600nm, and power can be 5-100W; When described energy-beam is electron beam, the power density of described electron beam can be 10-10
11w/cm
2; When described energy-beam is ionic fluid, the energy of described ionic fluid can be 10-10
6eV.Preferably, described energy-beam is laser.Due to the stannic oxide that described polymer product contains doping provided by the invention, the stannic oxide of this doping has higher receptivity to energy-beam, even if therefore use the lower energy-beam of energy to irradiate, also can make the gasification of ink layer surface peel off.It is the laser that 1064-10600nm and power are 3-50W that described energy-beam is preferably wavelength, and more preferably wavelength is that 1064nm and power are more preferably 5-20W of 3-40W() laser.
The method according to this invention can be carried out selective metallization to multiple insulativity base material, and described insulativity base material can be for example coating, ceramic base material, glass baseplate, wood substrates, cement matrix or the paper of plastic basis material, rubber substrate, fiber base material, coating formation.Preferably, described insulativity base material is plastic basis material or ceramic base material.For example, when described insulativity base material is flexiplast base material (: polyethylene terephthalate, polyimide, polycarbonate, polyetherketone, polyether-ether-ketone or liquid crystal polymer), ink composite of the present invention is applied to the surface of base material, and the goods that obtain after base material selective metallization are particularly suitable for making flexible circuit board.
In following examples, adopt inductively coupled plasma emission spectrography (ICP) to measure the composition of metallic compound.
In following examples, volume average particle size is to adopt the laser particle analyzer being purchased from the Chengdu new powder testing apparatus of essence company limited to measure.
In following examples, adopt the hundred lattice skill in using a kitchen knife in cookery to be determined at the sticking power of the metal level of substrate surface formation.Concrete testing method is: with hundred lattice cuttves, on testing sample surface, draw the little grid of 10 * 10 1mm * 1mm, the lowest layer of each rule dark and metal level, after the fragment of test zone being cleaned down with hairbrush, with adhesive tape (3M600 gummed paper), cling tested little grid, with hand, catch adhesive tape one end, shut down rapidly in the vertical direction gummed paper, at same position, carry out same test 2 times, according to following standard sticking power grade:
5B: scribing edge is smooth, all comes off without metal level at edge and the place, point of crossing of line;
4B: the place, point of crossing in line has the metal level of small pieces to come off, and the total area that comes off is less than 5%;
3B: edge and place, point of crossing in line have the metal level of small pieces to come off, and come off the total area between 5-15%;
2B: edge and place, point of crossing in line have metal level in blocks to come off, and come off the total area between 15-35%;
1B: edge and place, point of crossing in line have metal level in blocks to come off, and come off the total area between 35-65%;
0B: edge and place, point of crossing in line have metal level in blocks to come off, and the total area that comes off is greater than 65%.
In following examples and comparative example, adopt the method for stipulating in ASTM D256 to measure notched Izod impact strength, the notched Izod impact strength of same source sample is the mean value of 5 Validity Test data.
Embodiment 1-13 is used for illustrating the present invention.
Embodiment 1
(1) by SnO
2be placed in the ball grinder of ball mill, then add V
2o
5and ethanol, carry out the grinding of 4 hours.Wherein, with respect to 100 weight part solid matters, the consumption of ethanol is 300 weight parts; With SnO
2and V
2o
5total amount be benchmark, V
2o
5consumption be 10 % by mole.The mixture that ball milling is obtained is dried 2 hours at 80 ℃ in air atmosphere, obtains the powder mixture that volume average particle size is 1 μ m.By described powder mixture, 900 ℃ of roastings 5 hours in air atmosphere, it is 1.5 μ m that product of roasting is ground to form to volume average particle size, thereby obtains the stannic oxide of doping, and color be white.After measured, in the stannic oxide of doping, V
2o
5content be 10 % by mole.
(2) stannic oxide addition of doping step (1) being obtained, in polycarbonate, after mixing, is sent into the mixture obtaining in forcing machine, carries out extruding pelletization.The pellet obtaining is sent in injection moulding machine to injection moulding, the polymer plate of the stannic oxide that obtains containing doping.Wherein, take the stannic oxide that adulterates and the total amount of polycarbonate is benchmark, and the content of the stannic oxide of doping is 3 % by weight.Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) surface of the polymer plate with the laser that YAG laser apparatus produces, step (2) being obtained is irradiated, and usings and forms the pattern as the antenna of receiving apparatus at plate surface.Wherein, the condition of laser radiation comprises: optical maser wavelength is 1064nm, and power is 5W, and frequency is 30kHz, and Trace speed is 1000mm/s, and filling spacing is 30 μ m.
(4) polymer plate step (3) being obtained is placed in plating solution, carries out electroless plating, forms the metal plating of antenna pattern.Consisting of of plating solution: CuSO
45H
2o0.12mol/L, Na
2eDTA2H
2o0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid 0.10mol/L, and with NaOH and H
2sO
4regulating the pH value of plating solution is 12.5-13, the temperature 50 C of plating solution.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Comparative example 1
(1) using in embodiment 1 step (1) as the stannic oxide addition of raw material in polycarbonate, under the condition identical with embodiment 1 step (2), carry out extruding pelletization and injection moulding, obtain the polymer plate that contains stannic oxide.Wherein, the total amount of stannic oxide and polycarbonate of take is benchmark, and the content of stannic oxide is 3 % by weight.
(2) surface of the polymer plate that the employing method identical with embodiment 1 step (3) obtains comparative example 1 step (1) with laser is irradiated.
(3) polymer plate comparative example 1 step (2) being obtained adopts the method identical with embodiment 1 step (4) to carry out electroless plating.
Result cannot form circuit.
Comparative example 2
(1) using in embodiment 1 step (1) as the stannic oxide addition of raw material in polycarbonate, under the condition identical with embodiment 1 step (2), carry out extruding pelletization and injection moulding, obtain the polymer plate that contains stannic oxide.Wherein, the total amount of stannic oxide and polycarbonate of take is benchmark, and the content of stannic oxide is 10 % by weight (that is, 1.85 volume %).Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(2) surface of the polymer plate that the employing method identical with embodiment 1 step (3) obtains comparative example 2 steps (1) with laser is irradiated.
(3) polymer plate comparative example 2 steps (2) being obtained adopts the method identical with embodiment 1 step (4) to carry out electroless plating, forms line layer.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Embodiment 2
(1) by SnO
2be placed in the ball grinder of ball mill, then add MoO
3and ethanol, carry out the grinding of 2 hours.Wherein, with respect to 100 weight part solid matters, the consumption of ethanol is 300 weight parts; With SnO
2and MoO
3total amount be benchmark, MoO
3content be 10 % by mole.The mixture that ball milling is obtained is dried 3 hours at 80 ℃ in air atmosphere, obtains the powder mixture that volume average particle size is 2.6 μ m.By described powder mixture, 950 ℃ of roastings 5 hours in air atmosphere, it is 1.6 μ m that product of roasting is ground to form to volume average particle size, thereby obtains the stannic oxide of doping, and color be white.After measured, in the stannic oxide of doping, MoO
3content be 10 % by mole.
(2) stannic oxide addition of doping step (1) being obtained, in polycarbonate, after mixing, is sent into the mixture obtaining in forcing machine, carries out extruding pelletization.The pellet obtaining is sent in injection moulding machine to injection moulding, the polymer plate of the stannic oxide that obtains containing doping.Wherein, take the stannic oxide that adulterates and the total amount of polycarbonate is benchmark, and the content of the stannic oxide of doping is 3 % by weight.Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) surface of the polymer plate with laser, step (2) being obtained is irradiated.Wherein, the condition of laser radiation is with embodiment 1.
(4) polymer plate step (3) being obtained is placed in plating solution, carries out electroless plating, forms metal plating.The composition of plating solution and the condition of electroless plating are with embodiment 1.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Comparative example 3
Adopt the stannic oxide, polymer plate of the method identical with embodiment 2 preparation doping and by polymer plate surface metalation, different, in step (1) with the Ga of equivalent
2o
3replace MoO
3.
Through visual observations, discovery cannot form complete circuit.
Embodiment 3
(1) adopt the stannic oxide of the method preparation doping identical with embodiment 2, different, MoO
3addition be 8 % by mole.The color of the stannic oxide of the doping obtaining is white.After measured, in the stannic oxide of doping, MoO
3content be 8 % by mole.
(2) adopt the method identical with embodiment 2 steps (2) to prepare polymer plate, different, the stannic oxide of doping is the stannic oxide of the doping prepared of embodiment 3 steps (1).Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) adopt the method identical with embodiment 2 steps (3) to irradiate with laser, different, polymer plate is the polymer plate that embodiment 3 steps (2) obtain.
(4) adopt the method identical with embodiment 2 steps (4) to carry out electroless plating, different, polymer plate is the polymer plate that embodiment 3 steps (3) obtain.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Embodiment 4
(1) by SnO
2be placed in the ball grinder of ball mill, then add V
2o
5and ethanol, carry out the grinding of 5 hours.Wherein, with respect to 100 weight part solid matters, the consumption of ethanol is 300 weight parts; With SnO
2and V
2o
5total amount be benchmark, V
2o
5content be 1 % by mole.The mixture that ball milling is obtained is dried 6 hours at 100 ℃ in air atmosphere, obtains the powder mixture that volume average particle size is 1.8 μ m.By the dry mixture obtaining, 850 ℃ of roastings 6 hours in air atmosphere, it is 1.2 μ m that product of roasting is ground to form to volume average particle size, thereby obtains the stannic oxide of doping, and color be white.After measured, in the stannic oxide of doping, V
2o
5content be 1 % by mole.
(2) stannic oxide addition of doping step (1) being obtained, in polycarbonate, after mixing, is sent into the mixture obtaining in forcing machine, carries out extruding pelletization.The pellet obtaining is sent in injection moulding machine to injection moulding, the polymer plate of the stannic oxide that obtains containing doping.Wherein, take the stannic oxide that adulterates and the total amount of polycarbonate is benchmark, and the content of the stannic oxide of doping is 3 % by weight.Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) surface of the polymer plate with the laser that YAG laser apparatus produces, step (2) being obtained is irradiated, and usings and forms the pattern as the antenna of receiving apparatus at plate surface.Wherein, the condition of laser radiation comprises: optical maser wavelength is 1064nm, and power is 20W, and frequency is 30kHz, and Trace speed is 800mm/s, and filling spacing is 25 μ m.
(4) polymer plate step (3) being obtained is placed in plating solution, carries out electroless plating, forms the metal plating of antenna pattern.The composition of plating solution and the condition of electroless plating are with embodiment 1.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Embodiment 5
(1) adopt the stannic oxide of the method preparation doping identical with embodiment 4, different, V
2o
5addition be 2 % by mole.The color of the stannic oxide of the doping obtaining is white.After measured, in the stannic oxide of doping, V
2o
5content be 2 % by mole.
(2) adopt the method identical with embodiment 4 steps (2) to prepare polymer plate, different, the stannic oxide of doping is the stannic oxide of the doping prepared of embodiment 5 steps (1).Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) adopt the method identical with embodiment 4 steps (3) to irradiate with laser, different, polymer plate is the polymer plate that embodiment 5 steps (2) obtain.
(4) adopt the method identical with embodiment 4 steps (4) to carry out electroless plating, different, polymer plate is the polymer plate that embodiment 5 steps (3) obtain.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Embodiment 6
(1) by SnO
2be placed in the ball grinder of ball mill, then add MoO
3, V
2o
5and ethanol, carry out the grinding of 4 hours.Wherein, with respect to 100 weight part solid matters, the consumption of ethanol is 200 weight parts; With SnO
2, MoO
3and V
2o
5total amount be benchmark, MoO
3content be 1.8 % by mole, V
2o
5content be 2.5 % by mole.The mixture that ball milling is obtained is dried 4 hours at 120 ℃ in air atmosphere, obtains the powder mixture that volume average particle size is 3.8 μ m.By described powder mixture, 920 ℃ of roastings 4 hours in air atmosphere, it is 3.2 μ m that product of roasting is ground to form to volume average particle size, thereby obtains the stannic oxide of doping, and color be white.After measured, in the stannic oxide of doping, MoO
3content be 1.8 % by mole, V
2o
5content be 2.5 % by mole.
(2) stannic oxide and the TiO of doping step (1) being obtained
2(volume average particle size is 2.1 μ m) adds in polycarbonate, after mixing, the mixture obtaining sent in forcing machine, carries out extruding pelletization.The pellet obtaining is sent in injection moulding machine to injection moulding, the polymer plate of the stannic oxide that obtains containing doping.Wherein, stannic oxide, the TiO to adulterate
2with the total amount of polycarbonate be benchmark, the content of the stannic oxide of doping is 1.8 % by weight, TiO
2content be 2 % by weight.Shock strength to the polymer plate obtaining is tested, and result provides in table 1.
(3) surface of the polymer plate with laser, step (2) being obtained is irradiated.Wherein, the condition of laser radiation is with embodiment 1.
(4) polymer plate step (3) being obtained is placed in plating solution, carries out electroless plating, forms metal plating.The composition of plating solution and plating condition are with embodiment 1.
Through visual observations, find that the circuit forming is complete.The sticking power of plating speed and metal level is listed in table 1.
Embodiment 7
Adopt the stannic oxide that adulterates to the identical method preparation of step (4) with embodiment 1 step (1), polymer plate and by the surface metalation of polymer plate, different, the content of the stannic oxide adulterating in the polymer plate that step (2) obtains is 5 % by weight.
Through visual observations, find that the circuit forming is complete.Plating speed, sticking power and shock strength are listed in table 1.
Table 1
| ? | Plating speed (μ m/h) | Sticking power | Shock strength (J/m) |
| Embodiment 1 | 5.1 | 5B | 673.8 |
| Comparative example 1 | - | - | - |
| Comparative example 2 | 6.0 | 5B | 483.0 |
| Embodiment 2 | 5.2 | 5B | 650.2 |
| Comparative example 3 | - | - | - |
| Embodiment 3 | 5.1 | 5B | 649.3 |
| Embodiment 4 | 2.7 | 3B | 676.4 |
| Embodiment 5 | 4.5 | 4B | 679.3 |
| Embodiment 6 | 4.7 | 5B | 642.3 |
| Embodiment 7 | 5.6 | 5B | 548.4 |
Embodiment 8
(1) stannic oxide, the 20g binder of the doping of 50g embodiment 1 preparation (are purchased to the Yi Shi Man from the U.S., the trade mark is CAB381-0.5), 100g n-Heptyl alcohol, 2g dispersion agent (be purchased the company from German BYK, the trade mark is DISPERBYK-165), 0.2g defoamer (is purchased the company from German BYK, the trade mark is BYK-051), 0.4g flow agent (is purchased the company from German BYK, the trade mark is BYK-333) and 0.5g hydrogenated castor oil (being purchased from Wuhan Jin Nuo Chemical Co., Ltd.) mix, thereby obtain according to ink composite of the present invention.
(2) with the ink composite that the method for spray ink Printing is prepared step (1), be applied to Al
2o
3the surface of ceramic base material, and at the temperature of 120 ℃ dry 3 hours, thus on the surface of described base material, form the ink layer of pattern of the antenna of receiving apparatus, with the thickness of scanning electron microscope (SEM) mensuration ink layer, be 12 μ m.
(3) with the ink layer that laser forms step (2), irradiate.Wherein, the condition of laser radiation comprises: optical maser wavelength is 1064nm, and power is 5W, and frequency is 20kHz, and Trace speed is 800mm/s, and filling spacing is 20 μ m.
(4) base material step (3) being obtained is placed in plating solution, carries out electroless plating.Consisting of of plating solution: CuSO
45H
2o0.12mol/L, Na
2eDTA2H
2o0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid 0.10mol/L, and with NaOH and H
2sO
4regulating the pH value of plating solution is 12.5-13, the temperature 50 C of plating solution.
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Embodiment 9
Adopt the method identical with embodiment 8 to prepare ink composite and for by Al
2o
3the surface metalation of ceramic base material, different, do not carry out step (3), the base material directly step (2) being obtained is placed in plating solution and carries out electroless plating.
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Comparative example 4
Adopt the method identical with embodiment 8 to prepare ink composite and be applied to Al
2o
3behind the surface of ceramic base material, with laser radiation and carry out electroless plating, different, in step (1), with stannic oxide (for the raw material of the stannic oxide of the described doping of preparation), replace the stannic oxide of doping.
Result cannot form circuit.
Embodiment 10
(1) stannic oxide of the doping of 50g embodiment 2 preparation, 15g polyvinyl butyral acetal (be purchased the company from Japanese Kuraray, the trade mark is Mowital) and 20g toluene are mixed, thereby obtain according to ink composite of the present invention.
(2) with the ink composite that inkjet printing methods is prepared step (2), be applied to the surface of polyether-ether-ketone (PEEK) base material, and be dried 4 hours at the temperature of 150 ℃, thereby on the surface of described base material, form the ink layer of pattern of the antenna of receiving apparatus, the thickness of measuring ink layer by scanning electron microscope (SEM) is 25 μ m.
(3) with the ink layer that laser forms step (2), irradiate.Wherein, the condition of laser radiation comprises: optical maser wavelength is 1064nm, and power is 5W, and frequency is 20kHz, and Trace speed is 1000mm/s, and filling spacing is 20 μ m.
(4) base material step (3) being obtained is placed in plating solution and carries out electroless plating, obtains the coating that thickness is 4 μ m.Consisting of of plating solution: CuSO
45H
2o0.12mol/L, Na
2eDTA2H
2o0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid 0.10mol/L, and with NaOH and H
2sO
4regulating the pH value of plating solution is 12.5-13, the temperature 50 C of plating solution.
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Embodiment 11
Adopt prepare ink composite and be applied to Al identical with embodiment 10
2o
3behind the surface of ceramic base material, with laser radiation and carry out electroless plating, different, the stannic oxide of doping is the stannic oxide of the doping prepared of embodiment 3 steps (1).
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Embodiment 12
(1) stannic oxide of the doping of 50g embodiment 4 preparation, 30gEVA binder (being purchased the Yi Shi Man from the U.S.), 110g toluene, 3g dispersion agent (are purchased to the company from German BYK, the trade mark is ANTI-TERRA-U80), 0.5g defoamer (is purchased the company from German BYK, the trade mark is BYK-065), 0.5g flow agent (is purchased the company from German BYK, the trade mark is BYK-306) and 0.4g Natvosol (being purchased from Luzhou north great Dong chemical company) mix, thereby obtain according to ink composite of the present invention.
(2) with the ink composite that inkjet printing methods is prepared step (2), be applied to the surface of glass baseplate, and be dried 4 hours at the temperature of 150 ℃, thereby on the surface of described base material, form the ink layer of pattern of the antenna of receiving apparatus, by scanning electron microscope (SEM), measuring ink film thickness is 18 μ m.
(3) with the ink layer that laser forms step (2), irradiate.Wherein, the condition of laser radiation is with embodiment 10.
(4) base material step (3) being obtained is placed in plating solution and carries out electroless plating, obtains the coating that thickness is 3 μ m.Consisting of of plating solution: CuSO
45H
2o0.12mol/L, Na
2eDTA2H
2o0.14mol/L, yellow prussiate of potash 10mg/L, 2,2 '-dipyridyl 10mg/L, oxoethanoic acid 0.10mol/L, and with NaOH and H
2sO
4regulating the pH value of plating solution is 12.5-13, the temperature 50 C of plating solution.
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Embodiment 13
Adopt prepare ink composite and be applied to the surface of glass baseplate after identical with embodiment 12, with laser radiation and carry out electroless plating, different, the stannic oxide of doping is the stannic oxide of the doping prepared of embodiment 5 steps (1).
Through visual observations, find that the circuit forming is complete.The sticking power of the coating of plating rate and formation is listed in table 2.
Table 2
| ? | Plating speed (μ m/h) | Sticking power |
| Embodiment 8 | 12.0 | 5B |
| Comparative example 4 | - | - |
| Embodiment 9 | 8.0 | 3B |
| Embodiment 10 | 11.0 | 5B |
| Embodiment 11 | 10.8 | 5B |
| Embodiment 12 | 9.2 | 4B |
| Embodiment 13 | 10.0 | 4B |
Claims (20)
1. a stannic oxide for doping, the doped element in the stannic oxide of this doping is vanadium and/or molybdenum, and the total amount of stannic oxide of this doping of take is benchmark, and the content of stannic oxide is 90-99 % by mole, and the total amount of described doped element of oxide compound of take is 1-10 % by mole.
2. the stannic oxide of doping according to claim 1, wherein, the total amount of stannic oxide of this doping of take is benchmark, and the content of stannic oxide is 92-98 % by mole, and the total amount of described doped element of oxide compound of take is 2-8 % by mole.
3. the stannic oxide of doping according to claim 1 and 2, wherein, the volume average particle size of the stannic oxide of this doping is 50nm to 10 μ m.
4. the preparation method of the stannic oxide of a doping, the method comprises carries out roasting by a kind of powder mixture, described powder mixture contains stannic oxide and at least one compound containing doped element, the total amount of described powder mixture of take is benchmark, the content of described stannic oxide is 90-99 % by mole, the content of described doped element of oxide compound of take is 1-10 % by mole, described doped element is vanadium and/or molybdenum, the oxide compound that described compound is described doped element and/or can form the precursor of described oxide compound under roasting condition.
5. method according to claim 4, wherein, the total amount of described powder mixture of take is benchmark, and the content of described stannic oxide is 92-98 % by mole, and the content of described doped element of oxide compound of take is 2-8 % by mole.
6. method according to claim 4, wherein, the temperature of described roasting is 800-1000 ℃.
7. method according to claim 4, wherein, the method also comprises that the solid matter that roasting is obtained grinds, the volume average particle size of the solid matter after the condition of described grinding makes to grind is 50nm to 10 μ m.
8. the stannic oxide of the doping that in claim 4-7 prepared by the method described in any one.
9. a polymer product, this polymer product contains polymeric matrix and at least one metallic compound, described metallic compound is dispersed in described polymeric matrix, it is characterized in that, described metallic compound is the stannic oxide of the doping described in any one in claim 1-3 and 8.
10. polymer product according to claim 9, wherein, the total amount of described polymer product of take is benchmark, and the content of described metallic compound is 1-3 % by weight, and the content of described polymeric matrix is 97-99 % by weight.
The preparation method of 11. 1 kinds of polymer products claimed in claim 9, the method comprises each component of a kind of polymer composition is mixed, and by the mixture forming obtaining, described polymer composition contains polymer matrix component and at least one metallic compound.
12. methods according to claim 11, wherein, the total amount of polymer composition of take is benchmark, and the content of described metallic compound is 1-3 % by weight, and the content of described polymer matrix component is 97-99 % by weight.
13. 1 kinds of ink composites, said composition contains at least one metallic compound and at least one binder, it is characterized in that, and described metallic compound is the stannic oxide of the doping described in any one in claim 1-3 and 8.
14. ink composites according to claim 13, wherein, with respect to metallic compound described in 100 weight parts, the amount of described binder is 1-60 weight part.
15. according to the ink composite described in claim 13 or 14, wherein, to be selected from rhodia, polyacrylic ester be one or more in resin, vinyl-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate (PVA), polyvinylpyrrolidone and polyphosphonic acid to described binder.
16. 1 kinds of surfaces of polymeric articles selective metallization methods, the method comprises:
With energy-beam irradiated polymer goods need to carry out metallized surface, make irradiated surface gasification; And
Postradiation polymer product is carried out to electroless plating,
It is characterized in that, described polymer product is the polymer product described in claim 9 or 10.
17. 1 kinds of insulativity substrate surface selective metallization methods, the method comprises:
Each component in ink composite described in any one in claim 13-15 is mixed, and what the mixture obtaining was applied to insulativity base material need to carry out metallized surface, to form ink layer; And
The insulativity base material with described ink layer is carried out to electroless plating, with one deck metal level at least of plating on described ink layer.
18. methods according to claim 17, wherein, before the insulativity base material with described ink layer is carried out to electroless plating, the method also comprises with energy-beam irradiates the surface of described ink layer, so that the gasification of the surface of ink layer.
19. according to the method described in claim 16 or 18, and wherein, described energy-beam is laser.
20. methods according to claim 19, wherein, described energy-beam is that wavelength is the laser that 1064nm and power are 3-40W.
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| CN201310195129.8A CN104176769B (en) | 2013-05-23 | 2013-05-23 | The stannum oxide of doping and preparation method and polymer product and preparation method and ink composite and surface selective metallization method |
| TW103113873A TW201445006A (en) | 2013-05-23 | 2014-04-16 | A method of selective metallizing a surface of a polymer article and a polymer article obtained thereof |
| PCT/CN2014/078151 WO2014187340A1 (en) | 2013-05-23 | 2014-05-22 | Polymer article and method for selective metallization of the same |
| US14/285,322 US20140349030A1 (en) | 2013-05-23 | 2014-05-22 | Polymer article and method for selective metallization of the same |
| PCT/CN2014/078305 WO2014187360A1 (en) | 2013-05-23 | 2014-05-23 | Doped tin oxide and method for selective metallization of insulating substrate |
| EP14801718.9A EP2999665B1 (en) | 2013-05-23 | 2014-05-23 | Polymer comprising doped tin oxide and method for selective metallization of insulating substrate |
| US14/943,861 US9869025B2 (en) | 2013-05-23 | 2015-11-17 | Doped tin oxide and method for selective metallization of insulating substrate |
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| CN109880499A (en) * | 2017-12-06 | 2019-06-14 | 比亚迪股份有限公司 | The explosion-proof coating that can be metallized and preparation and application, the explosion-proof layer with antenna and preparation and 3D glass or ceramic cover |
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| E. BONTEMPI ET AL: ""Structural Characterization of Tin and Molybdenum Oxides Thin Films Deposited by RGTO"", 《CHEM. MATER.》, vol. 13, 17 July 2001 (2001-07-17), pages 2608 - 2612 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880499A (en) * | 2017-12-06 | 2019-06-14 | 比亚迪股份有限公司 | The explosion-proof coating that can be metallized and preparation and application, the explosion-proof layer with antenna and preparation and 3D glass or ceramic cover |
| CN109880499B (en) * | 2017-12-06 | 2020-11-20 | 比亚迪股份有限公司 | Metallizable explosion-proof coating, preparation and application thereof, explosion-proof layer with antenna, preparation thereof, and 3D glass or ceramic cover |
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