CN104451615A - Surface treatment method for chemical plating activator, chemical plating activator, application thereof, polymer product and surface metallization method - Google Patents
Surface treatment method for chemical plating activator, chemical plating activator, application thereof, polymer product and surface metallization method Download PDFInfo
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- CN104451615A CN104451615A CN201310425960.8A CN201310425960A CN104451615A CN 104451615 A CN104451615 A CN 104451615A CN 201310425960 A CN201310425960 A CN 201310425960A CN 104451615 A CN104451615 A CN 104451615A
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- electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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Abstract
The invention provides a surface treatment method for a chemical plating activator. The method is as below: heating a chemical plating activator and a surface modifying agent in a dispersant agent, wherein the surface modifying agent is selected from A(OH)n, and can form A(OH)n substance and amorphous silica in the condition of hydrolysis and / or alcoholysis, and A represents B, Al or Si. The invention also provides the chemical plating activator subjected to surface treatment obtained by the method of the invention and its application. The invention further provides a polymer product containing the chemical plating activator subjected to surface treatment and a surface metallization method. The chemical plating activator is treated by the method of the invention, and then the chemical plating activator subjected to surface treatment is dispersed in a polymer matrix; and the probability of degradation of the polymer matrix can be significantly reduced, and the polymer matrix dispersed with the chemical plating activator subjected to surface treatment still has chemical plating activity.
Description
Technical field
The surface treated electroless plating activator that the present invention relates to a kind of electroless plating activator surface treatment method and obtained by the method and application thereof, the invention still further relates to a kind of polymer product being wherein dispersed with described surface treated electroless plating activator, the invention further relates to a kind of surfaces of polymeric articles method for metallising.
Background technology
Form metal level at surfaces of polymeric articles, as the path of electromagnetic signal conduction, be widely used in the fields such as automobile, industry, computer, communication.Optionally forming metal level at surfaces of polymeric articles is the core link that such polymer product manufactures.
US2004/0241422A1 reports the mineral compound powder adding spinel structure in polymeric matrix, these mineral compound contain the elements such as copper, nickel, cobalt, chromium, iron, then use Ultra-Violet Laser (wavelength is 248nm, 308nm, 355nm, 532nm) and infrared laser (wavelength is 1064nm and 10600nm) to activate.US2004/0241422A1 mentions the oxide compound with spinel structure especially can restore metal simple-substance under lasing, and using metal simple-substance as nucleus, induction-chemical deposition metal, forms metal level.The realization of this process needs strict technology controlling and process, and needing to irradiate higher laser energy could be metal simple-substance by the Reduction of Oxide of spinel structure, thus obtains the effect of the induction-chemical deposition metal of expection, all higher to the requirement of equipment and process.
CN101747650B discloses a kind of frosting selective metal method, and the method comprises: each component in a kind of plastics composite mixed and injection moulding, obtain plastic sample; By irradiation energy line, described plastic sample is etched, gasify to make partly plastic and peel off and expose catalyst component particles; Electroless copper is carried out to the plastic sample exposing catalyst component particles.Wherein, described plastics composite contains plastic basis material component and catalyst component, and described catalyst component is the ABO with delafossite structure
2one or more in type composite oxides, A is selected from the one in the periodic table of elements the 9th, 10 and 11 row metallic element, and B is Ni, Mn, Cr, Al or Fe, and A and B is different.The catalyst component used in CN101747650B directly can promote electroless copper, does not need, by induced with laser, the metal component in catalyst component is reduced to this complexity of simple substance and uppity process.
Summary of the invention
The present inventor finds in research process: under equal conditions, and as compared to the plastic sample not containing catalyst component (that is, electroless plating activator), the mechanical property of the plastic sample containing some catalyst components declines to some extent.
The present inventor is studied for this problem, finds: there occurs degraded containing the plastic substrate in the plastic sample of some catalyst components, thus make the mechanical properties decrease of the plastic sample containing described catalyst component.On this basis, through further studying discovery; If before these catalyst components are scattered in plastic substrate, with being selected from A (OH)
n, hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial and soft silica (wherein, A is B, Al or Si, n is the integer identical with the valency of A) heat treated is carried out to described catalyst component, obviously can reduce the degradation rate of plastic substrate, the more important thing is, the plastic substrate presetting this catalyst component does not still need, by induced with laser, the metal component in catalyst component is reduced to this complexity of simple substance and uppity process, directly can promote electroless copper.This completes the present invention.
According to a first aspect of the invention, the invention provides a kind of surface treatment method of electroless plating activator, the method comprises: electroless plating activator and at least one surface-modifying agent are carried out reacting by heating in dispersion agent, and described surface-modifying agent is selected from A (OH)
n, hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial and soft silica, wherein, A is B, Al or Si, and n is the integer identical with the valency of A.
According to a second aspect of the invention, the invention provides a kind of surface treated electroless plating activator obtained by method of the present invention.
According to a third aspect of the present invention, the invention provides the application of a kind of described surface treated electroless plating activator in insulativity substrate surface selective metallization.
According to a fourth aspect of the present invention, the invention provides a kind of polymer product, this polymer product comprises polymeric matrix and dispersion electroless plating activator in the polymer matrix, and wherein, described electroless plating activator is surface treated electroless plating activator provided by the invention.
According to a fifth aspect of the present invention, the invention provides a kind of surfaces of polymeric articles method for metallising, the method comprises the following steps:
(1) with energetic beam illumination polymer product need carry out metallized surface, make irradiated surface gasification; And
(2) postradiation polymer product is carried out electroless plating,
Wherein, described polymer product is polymer product provided by the invention.
Method of the present invention is adopted to process electroless plating activator, and then this surface treated electroless plating activator is dispersed in polymeric matrix, obviously can not only reduce the probability that degraded occurs polymeric matrix, and the polymeric matrix being dispersed with this surface treated electroless plating activator still has electroless plating activity.Its reason may be: electroless plating activator also has certain promoter action to polymer degradation, adopt method of the present invention to carry out process to electroless plating activator and can form one deck coating layer on electroless plating activator surface, polymeric matrix and electroless plating activator are separated, thus effectively reduces the probability that degraded occurs polymeric matrix; Further, in the irradiation of follow-up energy line and/or plating process, the material forming described coating layer can chemically plate activator sur-face peeling, makes electroless plating activator out exposed, gives polymeric matrix active with electroless plating.
Further, adopt method of the present invention to carry out to electroless plating activator the color burn that surface treatment can not make electroless plating activator, even can obtain more shallow color.
In addition, electroless plating activator surface treatment method of the present invention is easy and simple to handle, easy to implement.
Embodiment
According to a first aspect of the invention, the invention provides a kind of surface treatment method of electroless plating activator, the method comprises: electroless plating activator and at least one surface-modifying agent are carried out reacting by heating in dispersion agent.
In the present invention, described electroless plating activator refers to can the material of induction-chemical deposition metal, can for the conventional various materials that can realize above-mentioned functions.Preferably, one or more for being selected from the metallic compound shown in the metallic compound shown in the metallic compound shown in formula III, formula IV, formula V of described electroless plating activator.
Cu
ym
1 x(PO
4)
2(OH)
z(formula III)
In formula III, M
1for being selected from one or more elements in the 2nd row of the periodic table of elements, x+y=3,0≤x < 3, z is 0 or 1.
In formula III, M
1be preferably in Ca, Mg, Ba and Sr one or more.
CuM
2 2o
4(formula IV)
In formula IV, M
2for being selected from one or more elements in the 6th row of the periodic table of elements, the 8th row and the 13rd row, be preferably one or more in Al, B, Cr, Ga, Fe and In.
M
3 mcu
no (formula V)
In formula V, M
3for being selected from one or more elements in the 2nd row of the periodic table of elements, be preferably one or more in Ca, Mg, Ba and Sr; M+n=1.
Particularly, described electroless plating activator can for being selected from Cu
2.7mg
0.3(PO
4)
2, Cu
1.5mg
1.5(PO
4)
2, Cu
1.5ba
0.75sr
0.75(PO
4)
2, Cu
0.15mg
2.85(PO
4)
2, Cu
1.5ca
1.5(PO
4)
2, Cu
0.15ca
2.85(PO
4)
2, Cu
2ba (PO
4)
2, CuSr
2(PO
4)
2, Cu
0.4sr
2.6(PO
4)
2, CuCr
2o
4, CuB
2o
4, Mg
0.78cu
0.22o, Ca
0.5cu
0.5o, Sr
0.6cu
0.4o, Ba
0.25cu
0.75o, Cu
3(PO
4)
2and Cu
2(PO
4) one or more in (OH).
The granular size of described electroless plating activator can be conventional selection.Usually, the volume average particle size of described electroless plating activator can be 0.1-5 μm, is preferably 0.4-2 μm.
The color of the metallic compound shown in formula III is generally light green or light blue, and the goods of the polymkeric substance therefore containing this metallic compound also can present light color.
Described electroless plating activator can be commercially available, and known method also can be adopted to prepare.Such as: described electroless plating activator can be prepared by the method for sintering, namely the mixture in the component source containing described electroless plating activator be sintered, thus obtain described electroless plating activator.For succinct object, this paper is example with the compound (wherein, z is 0, x is not 0) shown in formula III, is described in detail the preparation method of electroless plating activator.
Metallic compound (wherein, z is 0, x is not 0) shown in formula III can by carrying out sintering obtaining containing Cu source, IIA race source metal and phosphatic mixture.
Described Cu source can be CuO and/or the material that can form CuO under sintering condition, the described material that can form CuO under sintering condition can be various mantoquita, as mantoquita and/or the organic acid mantoquita of mineral acid, its specific examples can include but not limited to: cupric oxalate and/or copper carbonate.
Described IIA race source metal can be the oxide compound of IIA race metal and/or can form the compound of oxide compound of IIA race metal under sintering condition.The described compound that can form the oxide compound of IIA race metal under sintering condition can be organic acid salt and/or the inorganic acid salt of IIA race metal, the IIA race metal-salt of such as carbonic acid and/or the IIA race metal-salt of oxalic acid.The specific examples of described IIA race source metal can include but not limited to: one or more in magnesium oxide, magnesiumcarbonate, magnesium oxalate, calcium oxide, calcium carbonate, caoxalate, strontium oxide, Strontium carbonate powder, barium oxide, barium carbonate and barium oxalate.
Described phosphoric acid salt can be the common metal-salt of various phosphoric acid and/or the ammonium salt of phosphoric acid, and its specific examples can include but not limited to: ammonium hydrogen phosphate and/or primary ammonium phosphate.
Relative proportion between described Cu source, IIA race source metal and phosphoric acid salt is as the criterion so that the content of various element in the metallic compound that finally obtains can be made can to meet previously described requirement.
Described sintering can adopt once sintered technique, also can adopt double sintering technique.Specifically, described once sintered technique comprises: will be incubated 10-20h containing Cu source, IIA race source metal and phosphatic mixture at 900-1000 DEG C, and grinds the sinter obtained; Described double sintering technique comprises: by Cu source, IIA race source metal and phosphatic mixture at 600-900 DEG C of insulation 2-10h, then grind the solid matter obtained, and then is incubated 10-20h by grinding the material obtained at 900-1000 DEG C.For at 900-1000 DEG C of insulation 10-20h, no matter being once sintered technique, or double sintering technique, when the mol ratio of IIA race metal and Cu is for being less than 1, being preferably incubated 10-20h at 900-950 DEG C.
Described Cu source, IIA race source metal and the phosphatic mixture of containing can obtain by Cu source, IIA race source metal and phosphoric acid salt being carried out grinding.
In the present invention, described grinding can be dry grinding, can be also wet grinding, can also grind for semidrying, is preferably wet grinding or semidrying grinding, is more preferably wet grinding.The dispersion agent of described wet grinding can for the conventional various dispersion agents be suitable for as metal oxide.Particularly, described dispersion agent can be water and/or dehydrated alcohol.The consumption of dispersion agent can be conventional selection, is not particularly limited.
Described surface-modifying agent is selected from A (OH)
n, hydrolysis and/alcoholysis conditions under can form A (OH)
nmaterial and soft silica, wherein, A is B, Al or Si, and n is the integer identical with the valency of A.
For A (OH)
n, its specific examples can include but not limited to: boric acid, Al (OH)
3with Si (OH)
4.
A (OH) can be formed under hydrolysis and/or alcoholysis conditions
nmaterial, can select according to the difference of A.
When A is Al, described hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial can be the aluminum alkoxide shown in formula I,
In formula I, R
1, R
2and R
3identical or different, be C separately
1-C
6alkyl.
In the present invention, C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyls and 2-ethyl-butyl.
When A is Si, described hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial can be various organo-siloxane, such as formula the siloxanes described in II,
In formula II, R
4, R
5, R
6and R
7identical or different, be C separately
1-C
6alkyl or
r
8for C
1-C
6alkyl.
A be B(namely, boron) time, described hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial can be various boric acid ester, the boric acid ester as shown in formula III,
In formula III, R
8, R
9and R
10identical or different, be C separately
1-C
6alkyl.
For soft silica, can be the amorphous silicon di-oxide in various source, containing-OH group in the molecular structure of this kind of silicon-dioxide, be reactive silicon dioxide.Such as: aerosil and silicon sol.The particle diameter of described aerosil can be conventional selection, and general volume average particle size can be below 100nm, as 20-60nm.
Particularly, described surface-modifying agent is one or more in boric acid, aluminum isopropylate, trimethyl carbinol aluminium, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyldimethoxysilane, Union carbide A-162, dimethyldiethoxysilane and aerosil.
Relative proportion between described surface-modifying agent and described electroless plating activator can carry out appropriate selection according to the kind of electroless plating activator.Usually, described surface-modifying agent is with A
2o
nmeter, relative to electroless plating activator described in 100 weight parts, the consumption of described surface-modifying agent can be 1-20 weight part, is preferably 1-15 weight part.
Described dispersion agent can be able to make described electroless plating activator disperse to form suspension for various, can dissolve or disperse again the material of described surface-modifying agent.Preferably, described dispersion agent contains water and/or alcohol, and described electroless plating activator can be made so on the one hand to disperse to form suspension, and contains at described surface-modifying agent can form A (OH) under hydrolysis and/or alcoholysis conditions
nmaterial time, for the hydrolysis of this material or alcoholysis provide water source or alcohol source.More preferably, described dispersion agent is water and/or C
1-C
5monohydroxy-alcohol.C
1-C
5monohydroxy-alcohol can be methyl alcohol, ethanol, n-propyl alcohol, 2-propyl alcohol, propyl carbinol, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propanol, Pentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 2-methyl-2-butanols, 3-methyl-2-butanols and 2, one or more in 2-dimethyl-1-propyl alcohol, are preferably ethanol.
The consumption of described dispersion agent is as the criterion can form uniform suspension.Usually, relative to electroless plating activator described in 100 weight parts, the consumption of described dispersion agent can be 100-1000 weight part.
Hydrolysis-condensation reaction can be there is or condensation reaction occurs to be as the criterion in the condition of described reacting by heating with described surface-modifying agent.Usually, described reacting by heating can be carried out under temperature is the condition of 20-90 DEG C.Preferably, described reacting by heating is carry out under the condition of 60-80 DEG C in temperature.
The time of described reacting by heating can be selected according to the temperature of reacting by heating.Usually, the time of described reacting by heating can be 1-8 hour, is preferably 1-3 hour.
Can also comprise according to surface treatment method of the present invention: isolate the solid matter in the mixture that reacting by heating obtains, and solid matter drying will be obtained.Described drying can be carried out under temperature is the condition of 80-150 DEG C.The time of described drying can be selected according to carrying out dry temperature, can be generally 1-24 hour.Described drying can be carried out (as carried out in air atmosphere) in oxygen-containing atmosphere, also can carry out in inert atmosphere.Described inert atmosphere refers to by the atmosphere chemically interactive gas does not occur with dried material being formed, such as can for the atmosphere (atmosphere as formed by argon gas) formed by nitrogen atmosphere and/or neutral element gas.
According to a second aspect of the invention, the invention provides a kind of surface treated electroless plating activator obtained by method of the present invention.When the surface treated electroless plating activator obtained by method of the present invention is dispersed in polymeric matrix, the degraded of polymeric matrix is little, and the polymeric matrix being thus wherein dispersed with electroless plating activator of the present invention still can have higher mechanical property; And the polymeric matrix being wherein dispersed with electroless plating activator of the present invention, in follow-up metallization processes, still has electroless plating activity.
According to a third aspect of the present invention, the invention provides surface treated electroless plating activator of the present invention by the application in insulativity substrate surface selective metallization.
Described insulativity base material can be the common various base materials without electroconductibility, such as: polymeric substrate, ceramic base material and glass baseplate etc.
Can electroless plating activator according to the present invention be dispersed in described insulativity base material, and by irradiation energy line by described insulativity base material need carry out metallized surface roughening, then carrying out electroless plating can by the surface selective metallization of insulativity base material.Also electroless plating activator of the present invention can be made ink, and ink is coated in insulativity base material need carry out metallized surface, and after making ink layer surface gasify optionally through irradiation energy line, carry out electroless plating, thus by insulativity substrate surface selective metallization.
According to a fourth aspect of the present invention, the invention provides a kind of polymer product, this polymer product comprises polymeric matrix and dispersion electroless plating activator in the polymer matrix, and wherein, described electroless plating activator is surface treated electroless plating activator provided by the invention.
Described surface treated electroless plating activator and preparation method thereof is described in detail above, repeats no more herein.
The content being dispersed in the surface treated electroless plating activator in described polymer product can carry out appropriate selection according to the concrete service requirements of polymer product.Usually, with the gross weight of described polymer product for benchmark, the content of described electroless plating activator can be 1-40 % by weight, is preferably 10-40 % by weight, is more preferably 20-40 % by weight.
Described polymer product can adopt conventional forming polymer method preparation.In one embodiment of the invention, can by by polymer matrix component and described surface treated electroless plating activator mix evenly, and the mixture forming that will obtain, thus obtain described polymer product.
Described polymer matrix component refers to the component for the formation of polymeric matrix, comprises polymkeric substance and optional auxiliary agent.
Described polymkeric substance can carry out appropriate selection according to the embody rule occasion of this polymer product.Usually, described polymer product can, for the goods formed by thermoplastic polymer, also can be the goods formed by thermosetting polymer.Described polymkeric substance can be plastics, also can be 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 polycyclohexylene is to diformazan alcohol ester, PDAIP, poly terephthalic acid diallyl, PBN, polyethylene terephthalate and polybutylene terephthalate), polymeric amide is (as polyhexamethylene adipamide, poly-hexamethylene azelamide, 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 auxiliary agent can such as, for can improving the performance of polymer product or giving polymer product with the material of new performance, filler, oxidation inhibitor and photostabilizer.The content of described auxiliary agent can carry out appropriate selection according to its kind and concrete service requirements, is not particularly limited.Usually, relative to polymkeric substance described in 100 weight parts, 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.
Described filler can be filler laser not being played to any physics or chemical action, such as, and talcum powder and calcium carbonate.Although glass fibre is insensitive to laser, adds the degree of depth that glass fibre can deepen plastic substrate depression after laser activation greatly, be conducive to the adhesion of copper in electroless copper.Described mineral filler can also be the mineral filler played a role to laser, and such as, stannic oxide especially nano tin dioxide can increase the capacity usage ratio of infrared laser when peeling off frosting; Functional filler also has carbon black, and it also can increase plastics to infrared absorption, increases the extent of exfoliation of plastics.Described filler can also be one or more in glass microballon, calcium sulfate, barium sulfate, titanium dioxide, pearlescence, wollastonite, diatomite, kaolin, coal dust, potter's clay, mica, kerosene shale ash, pure aluminium silicate, aluminum oxide, carbon fiber, silicon-dioxide and zinc oxide.
Described oxidation inhibitor can improve the antioxidant property of polymer product of the present invention, thus improves the work-ing life of goods.Described oxidation inhibitor can be various oxidation inhibitor conventional in polymer arts, such as, can contain primary antioxidant and auxiliary antioxidant.Relative usage between described primary antioxidant and described auxiliary antioxidant can carry out appropriate selection according to kind.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 photostabilizer, such as hindered amine type light stabilizer, and its specific examples can include but not limited to two (2,2,6,6-tetramethyl--4-piperidyl) sebate.
Described auxiliary agent can also comprise the various material that can improve the processing characteristics of polymeric matrix, as lubricant.Described lubricant can for the various material that can improve the mobility of polymer melt, such as can one or more for being selected from the copolymerization wax (EVA wax) of ethylene/vinyl acetate, polyethylene wax (PE wax) and stearate.
The various forming methods that described shaping method can be commonly used for polymer forming art, such as: injection moulding, extrusion moulding.
According to a fifth aspect of the present invention, the invention provides a kind of surfaces of polymeric articles method for metallising, the method comprises the following steps:
(1) with energetic beam illumination polymer product need carry out metallized surface, make irradiated surface gasification; And
(2) postradiation polymer product is carried out electroless plating,
Wherein, described polymer product is polymer product provided by the invention.
Described polymer product and preparation method thereof is described above, no longer describes in detail herein.
According to surfaces of polymeric articles method for metallising of the present invention, in cleaning process after irradiation energy bundle, irradiation energy bundle and plating process, the coating mass-energy being dispersed in the surface treated electroless plating activator surface in described polymer product enough chemically plates activator sur-face peeling, make electroless plating activator out exposed, thus it is active with electroless plating to give polymeric matrix.
Described energy-beam can be the various energy-beam that polymer gasification can be made to peel off, such as laser, electron beam or ionic fluid, is preferably laser.Described laser can be obtained by various known approach, obtains laser preferably by laser apparatus.
The condition of irradiation energy bundle is as the criterion so that the polymer gasification of surfaces of polymeric articles can be made to expose electroless plating activator, can select according to the difference of the type of the kind of polymkeric substance and energy-beam.According to method of the present invention, during with energy-beam elective irradiation surfaces of polymeric articles, without the need to too high energy, the metallic compound as electroless plating activator is reduced into metal simple-substance, and polymer gasification only need be made to expose metallic compound, directly can carry out electroless plating, realize surfaces of polymeric articles selective metallization, technique is simple, low to energy requirement.
Usually, when adopting laser as energy-beam, the wavelength of described laser can be 157nm to 10.6 μm, sweep velocity can be 500-8000mm/s, step-length can be 3-9 μm, and time delay can be 30-100 μ s, and frequency can be 30-40kHz, power can be 3-4kW, and filling spacing can be 10-50 μm.By irradiating such laser, the thickness of the polymkeric substance generally etched away is several microns to tens microns, thus the metallic compound as electroless plating activator be dispersed in polymer product is come out, at least part of surface of polymer product is formed on microcosmic as having the rough surface structure in rugged space; When follow-up electroless plating, metallic particles is just embedded in the hole of uneven surface, thus and forms very strong bonding force between plastic sample.
Through the polymer product of energetic beam illumination before carrying out electroless plating, preferably clean, with clean surface.Can clean the polymer product through energetic beam illumination with the clean-out system of such as water.
The method of electroless plating is carried out also for conventionally known to one of skill in the art to the polymer product exposing metallic compound.Such as, when carrying out electroless copper, the method can comprise the polymer product after by etching and contact with copper electrolyte, described copper electrolyte contains mantoquita and reductive agent, pH value is 12-13, cupric ion in mantoquita can be reduced to copper simple substance by described reductive agent, and such as described reductive agent can be one or more in oxoethanoic acid, hydrazine and inferior sodium phosphate.
After carrying out electroless plating, can also then carry out electroplating or carrying out one or many electroless plating again, to increase the thickness of coating further or form other metal plating on chemical plating.Such as, after electroless copper terminates, can copper coating surface be prevented oxidized by electroless plating one deck nickel again.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, inductively coupled plasma emission spectrography (ICP) is adopted to measure the composition of electroless plating activator.
In following examples and comparative example, adopting and be purchased from the laser particle analyzer of the new powder testing apparatus company limited of Chengdu essence to measure the median size of electroless plating activator, is volume average particle size.
In following examples and comparative example, cross-cut tester method is adopted to be determined at the sticking power of the metal level that substrate surface is formed.Concrete testing method is: the small grid drawing 10 × 10 1mm × 1mm with cross-cut tester on testing sample surface, each lowest layer that is dark and metal level of ruling, after the fragment of test zone being cleaned down with hairbrush, tested small grid is clung with adhesive tape (3M600 gummed paper), adhesive tape one end is caught with hand, shut down gummed paper rapidly in the vertical direction, carry out 2 same tests at same position, according to following standard determination sticking power grade:
ISO grade 0: scribing edge is smooth, line edge and point of crossing place all without peeling paint;
ISO grade 1: the peeling paint having small pieces at the point of crossing place of line, and the total area that comes off is less than 5%;
ISO grade 2: the peeling paint having small pieces at the edge of line and point of crossing place, and come off the total area between 5-15%;
ISO grade 3: have peeling paint in blocks at the edge of line and point of crossing place, and come off the total area between 15-35%;
ISO class 4: have peeling paint in blocks at the edge of line and point of crossing place, and come off the total area between 35-65%;
ISO class 5: have peeling paint in blocks at the edge of line and point of crossing place, and the total area that comes off is greater than 65%.
In following examples and comparative example, at the temperature of 300 DEG C, apply the load of 11.76N, measure the melt flow rate (MFR) of stock polymer and the polymer sheet containing electroless plating activator respectively, adopt the degree of degradation of following formulae discovery polymer product,
Degree of degradation (%)=[| MI
0-MI
1︱/MI
0] × 100%,
Wherein, MI
0for the melt flow rate (MFR) of stock polymer, in g/min,
MI
1for the melt flow rate (MFR) of the polymer sheet containing electroless plating activator, in g/min.
Embodiment 1-8 is for illustration of the present invention.
Embodiment 1
(1) by CuO and Cr
2o
3mix, wherein, Cu
2o and Cr
2o
3mol ratio be 1:1.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is water, and relative to 100 weight part mixtures, the consumption of water is 150 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 100 DEG C, and the time is 12 hours.
Dried powder is placed in retort furnace sinter, the temperature of sintering is 950 DEG C, and the time is 10 hours.Sinter is carried out dry grinding, obtains the ferrous metal compound that volume average particle size is 2 microns.After testing, the chemical formula of this metallic compound is CuCr
2o
4.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 100 weight parts), with being heated with stirring to 80 DEG C.Then, at 80 DEG C, the boric acid aqueous solution of 10 % by weight is dropped to and is dispersed with CuCr
2o
4water (with B
2o
3meter, relative to 100 part by weight of metal compounds, the consumption of boric acid is 15 weight parts) in.After being added dropwise to complete, continuing to stir after 1 hour at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in black), wherein, dry temperature is 100 DEG C, and the time is 12 hours.
(3) the surface treated metallic compound mixing prepared by polycarbonate, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 40 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, with water, plastic sample is cleaned, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 2 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 10.01%.
Comparative example 1
The method identical with embodiment 1 step (1) is adopted to prepare metallic compound, adopt the method identical with embodiment 1 step (3) to prepare polymer product, and adopt the method identical with embodiment 1 step (4) by the surface metalation of polymer product, unlike, do not carry out step (2) (namely, step (3) uses metallic compound prepared by step (1)).
After tested, plating rate is 7 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (3) obtains is 38.31%.
Embodiment 2
(1) by CuO, CaO and NH
4h
2pO
4mix, wherein, CuO, CaO and NH
4h
2pO
4mol ratio be 1.5:1.5:2.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is dehydrated alcohol, and relative to 100 weight part mixtures, the consumption of dehydrated alcohol is 150 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 80 DEG C, and the time is 12 hours.
Dried powder is placed in retort furnace sinter in air atmosphere, the temperature of sintering is 1000 DEG C, and the time is 20 hours.Sinter is carried out dry grinding; Obtain the metallic compound that volume average particle size is 2 microns.After testing, the chemical formula of this metallic compound is Cu
1.5ca
1.5(PO
4)
2.This metallic compound is light green.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 500 weight parts), with stirring and being heated to 80 DEG C.Then, at 80 DEG C, the aqueous dispersions of the aerosil (volume average particle size is 50nm) containing 10 % by weight is dropped to and is dispersed with Cu
1.5ca
1.5(PO
4)
2water (with SiO
2meter, relative to 100 weight part Cu
1.5ca
1.5(PO
4)
2, the consumption of aerosil is 10 weight parts) in, after being added dropwise to complete, continuing to stir after 1 hour at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in light green), wherein, dry temperature is 100 DEG C, and the time is 12 hours.
(3) the surface treated metallic compound mixing prepared by polycarbonate, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 20 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, abatement processes is carried out to plastic sample, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 12 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 9.51%.
Comparative example 2
The method identical with embodiment 2 step (1) is adopted to prepare metallic compound, adopt the method identical with embodiment 2 step (3) to prepare polymer product, and adopt the method identical with embodiment 2 step (4) by the surface metalation of polymer product, unlike, do not carry out step (2) (namely, step (3) adopts metallic compound prepared by step (1)).
After tested, plating rate is 6 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (3) obtains is 48.31%.
Embodiment 3
The method identical with embodiment 2 is adopted to prepare through the metallic compound of surface modification, polymer product being metallized by surfaces of polymeric articles, unlike, in step (1), with the tetraethoxysilane of equivalent (with SiO
2meter) replace aerosil.
After tested, plating rate is 7 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (3) obtains is 8.95%.
Embodiment 4
(1) by Cu
2(PO
4) (content is 95 % by weight to (OH) (being purchased from Shanghai Ao highland barley Industrial Co., Ltd., is shallow white green), relative to 100 weight part Cu to be dispersed in ethanol
2(PO
4) (OH), the consumption of ethanol is 1000 weight parts) in, with being heated with stirring to 60 DEG C.Then, at 60 DEG C, the aluminum isopropylate ethanolic soln of 2 % by weight is dropped to and is dispersed with Cu
2(PO
4) ethanol of (OH) is (with Al
2o
3meter, relative to 100 weight part Cu
2(PO
4) (OH), the consumption of aluminum isopropylate is 2 weight parts) in, after being added dropwise to complete, continuing stirring 2 hours at such a temperature, be cooled to room temperature.Then the mixture obtained is placed 12 hours in 80 DEG C in air atmosphere, thus obtain surface treated metallic compound (in shallow white green).
(2) by surface treated electroless plating activator mix prepared by polycarbonate, oxidation inhibitor 1098, lubricant PE wax and step (1), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 40 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(3) polymer sheet that step (2) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, abatement processes is carried out to plastic sample, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 12 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 10 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 15.51%.
Comparative example 3
The method identical with embodiment 4 step (2) is adopted to prepare polymer product and adopt the method identical with embodiment 4 step (3) to be metallized by surfaces of polymeric articles, unlike, directly use Cu
2(PO
4) (OH) (being purchased from Shanghai Ao highland barley Industrial Co., Ltd.).
After tested, plating rate is 10 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (3) obtains is 60.58%.
Embodiment 5
(1) by CuO, caoxalate and NH
4h
2pO
4mix, wherein, CuO, caoxalate and NH
4h
2pO
4mol ratio be 0.15:2.85:2.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is dehydrated alcohol, and relative to 100 weight part mixtures, the consumption of dehydrated alcohol is 150 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 80 DEG C, and the time is 12 hours.
Dried powder is placed in retort furnace sinter in air atmosphere, the temperature of sintering is 900 DEG C, and the time is 10 hours.Sinter is carried out dry grinding; Again the powder of gained is placed in retort furnace to sinter in air atmosphere, the temperature of sintering is 1000 DEG C, and the time is 20 hours, and obtaining volume average particle size is 2 μm of metallic compounds for nattierblue.After testing, the chemical formula of this metallic compound is Cu
0.15ca
2.85(PO
4)
2.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 800 weight parts), with stirring and being heated to 70 DEG C.Then, at 70 DEG C, tetramethoxy-silicane is dropped to and is dispersed with Cu
0.15ca
2.85(PO
4)
2water (with SiO
2meter, relative to 100 weight part Cu
0.15ca
2.85(PO
4)
2, the consumption of tetramethoxy-silicane is 8 weight parts) in, after being added dropwise to complete, continuing to stir after 3 hours at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in nattierblue), wherein, dry temperature is 80 DEG C, and the time is 12 hours.
(3) by surface treated electroless plating activator mix prepared by polyhexamethylene adipamide, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polyhexamethylene adipamide, the consumption of surface treated metallic compound is 25 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, abatement processes is carried out to plastic sample, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 12 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 9.5 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 10.51%.
Embodiment 6
(1) by CuO, BaCO
3, SrCO
3and NH
4h
2pO
4mix, wherein, CuO, BaCO
3, SrCO
3and NH
4h
2pO
4mol ratio be 1.5:0.75:0.75:2.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is dehydrated alcohol, and relative to 100 weight part mixtures, the consumption of dehydrated alcohol is 150 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 80 DEG C, and the time is 12 hours.
Dried powder is placed in retort furnace sinter in air atmosphere, the temperature of sintering is 600 DEG C, and the time is 10 hours.Sinter is carried out dry grinding; Again the powder of gained is placed in retort furnace to sinter in air atmosphere, the temperature of sintering is 1000 DEG C, and the time is 15 hours, obtain volume average particle size be 2 μm for absinthe-green metallic compound.After testing, the chemical formula of this metallic compound is Cu
1.5ba
0.75sr
0.75(PO
4)
2.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 200 weight parts), with being heated with stirring to 65 DEG C.Then, at 65 DEG C, the boric acid aqueous solution of 10 % by weight is dropped to and is dispersed with Cu
1.5ba
0.75sr
0.75(PO
4)
2water (with B
2o
3meter, relative to 100 part by weight of metal compounds, the consumption of boric acid is 5 weight parts) in.After being added dropwise to complete, continuing to stir after 1 hour at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in light green), wherein, dry temperature is 120 DEG C, and the time is 8 hours.
(3) the surface treated metallic compound mixing prepared by polyimide, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 30 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, with water, plastic sample is cleaned, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 2 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 8.2 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 9.56%.
Embodiment 7
(1) by CuO and H
3bO
3mix, wherein, CuO and H
3bO
3mol ratio be 1:2.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is water, and relative to 100 weight part mixtures, the consumption of water is 120 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 120 DEG C, and the time is 8 hours.
Dried powder is placed in retort furnace sinter, the temperature of sintering is 980 DEG C, and the time is 10 hours.Sinter is carried out dry grinding, obtains the metallic compound for green that volume average particle size is 2 microns.After testing, the chemical formula of this metallic compound is CuB
2o
4.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 500 weight parts), with stirring and being heated to 80 DEG C.Then, at 80 DEG C, the alcohol dispersion liquid of the trimethyl carbinol aluminium containing 15 % by weight is dropped to and is dispersed with CuB
2o
4water (with Al
2o
3meter, relative to 100 weight part CuB
2o
4, the consumption of trimethyl carbinol aluminium is 10 weight parts) in, after being added dropwise to complete, continuing to stir after 1 hour at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in green), wherein, dry temperature is 100 DEG C, and the time is 12 hours.
(3) the surface treated metallic compound mixing prepared by polycarbonate, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 20 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, abatement processes is carried out to plastic sample, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 12 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 12.6%.
Embodiment 8
(1) mixed by CuO and MgO, wherein, the mol ratio of CuO and MgO is 0.22:0.78.The mixture shredder obtained is carried out wet grinding, and wherein, dispersion agent is water, and relative to 100 weight part mixtures, the consumption of water is 120 weight parts.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
Be placed in baking oven by grinding the powder obtained, in air atmosphere, carry out drying, dry temperature is 120 DEG C, and the time is 8 hours.
Dried powder is placed in retort furnace sinter, the temperature of sintering is 800 DEG C, and the time is 6 hours.Sinter is carried out dry grinding, obtain volume average particle size be 2 microns for jade-green metallic compound.After testing, the chemical formula of this metallic compound is Mg
0.78cu
0.22o.
(2) metallic compound prepared by step (1) is dispersed in water (relative to 100 part by weight of metal compounds, the consumption of water is 500 weight parts), with stirring and being heated to 80 DEG C.Then, at 80 DEG C, the alcohol dispersion liquid of the aluminum isopropylate containing 15 % by weight is dropped to and is dispersed with Mg
0.78cu
0.22the water of O is (with Al
2o
3meter, relative to 100 weight part Mg
0.78cu
0.22o, the consumption of aluminum isopropylate is 12 weight parts) in, after being added dropwise to complete, continuing to stir after 1 hour at such a temperature, be cooled to room temperature.Then filtered by the mixture obtained, the solid matter obtained is carried out drying in air atmosphere, thus obtain surface treated metallic compound (in light green), wherein, dry temperature is 100 DEG C, and the time is 12 hours.
(3) the surface treated metallic compound mixing prepared by polycarbonate, oxidation inhibitor 1098, lubricant PE wax and step (2), wherein, relative to 100 weight part polycarbonates, the consumption of surface treated metallic compound is 20 weight parts, the consumption of oxidation inhibitor is 0.05 weight part, and the consumption of lubricant is 0.04 weight part.By after the mixture pelleting that obtains, send into injection moulding in injection moulding machine, obtain the polymer sheet that thickness is 2mm.
(4) polymer sheet that step (3) obtains is placed in laser apparatus sample table, by laser focusing, computer program controls the movement of light beam or sample table, and laser apparatus used is big nation YLP-20 type laser apparatus, and laser parameter is: wavelength is 1064nm, sweep velocity is 1000mm/s, step-length is 6 μm, and time delay is 50 μ s, and frequency is 30kHz, power is 4kW, and filling spacing is 20 μm.After laser ablation, abatement processes is carried out to plastic sample, be then placed in plating solution and carry out electroless plating, obtain the coating that thickness is 12 microns.Wherein, consisting of of plating solution: cupric sulfate pentahydrate 5g/L, tartrate first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L, stablizer 0.1g/L.
After tested, plating rate is 8.5 μm/h, and the sticking power of coating is ISO grade 1.
After tested, the degree of degradation of polymer sheet that step (4) obtains is 10.3%.
The result of embodiment 1-8 and comparative example 1-4 confirms, method of the present invention is adopted to carry out surface treatment to electroless plating activator, then be dispersed in polymeric matrix, obviously can not only reduce the probability that degraded occurs polymeric matrix, and it is active that polymeric matrix still can be made to have higher electroless plating.
Claims (21)
1. a surface treatment method for electroless plating activator, the method comprises: electroless plating activator and at least one surface-modifying agent are carried out reacting by heating in dispersion agent, and described surface-modifying agent is selected from A (OH)
n, hydrolysis and/or alcoholysis conditions under can form A (OH)
nmaterial and soft silica, wherein, A is B, Al or Si, and n is the integer identical with the valency of A.
2. method according to claim 1, wherein, described surface-modifying agent is with A
2o
nmeter, relative to electroless plating activator described in 100 weight parts, the consumption of described surface-modifying agent is 1-15 weight part.
3. method according to claim 1 and 2, wherein, described surface-modifying agent is boric acid, one or more in the siloxanes shown in the aluminum alkoxide shown in formula I, formula II and aerosil,
In formula I, R
1, R
2and R
3identical or different, be C separately
1-C
6alkyl;
In formula II, R
4, R
5, R
6and R
7identical or different, be C separately
1-C
6alkyl or
r
8for C
1-C
6alkyl.
4. method according to claim 3, wherein, described surface-modifying agent is one or more in boric acid, aluminum isopropylate, trimethyl carbinol aluminium, tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyldimethoxysilane, Union carbide A-162, dimethyldiethoxysilane and aerosil.
5. method according to claim 1 and 2, wherein, one or more for being selected from the metallic compound shown in the metallic compound shown in the metallic compound shown in formula III, formula IV and formula V of described electroless plating activator,
Cu
ym
1 x(PO
4)
2(OH)
z(formula III)
In formula III, M
1for being selected from one or more elements in the 2nd row of the periodic table of elements, x+y=3,0≤x < 3, z is 0 or 1;
CuM
2 2o
4(formula IV)
In formula IV, M
2for be selected from the periodic table of elements the 6th row, the 8th row and the 13rd row in one or more elements;
M
3 mcu
no (formula V)
In formula V, M
3for being selected from one or more elements in the 2nd row of the periodic table of elements, m+n=1.
6. method according to claim 5, wherein, in formula III, M
1for one or more in Ca, Mg, Ba and Sr.
7. method according to claim 5, wherein, in formula IV, M
2for one or more in Al, B, Cr, Ga, Fe and In.
8. method according to claim 5, wherein, in formula V, M
3for one or more in Ca, Mg, Ba and Sr.
9. method according to claim 1, wherein, described electroless plating promotor is for being selected from Cu
2.7mg
0.3(PO
4)
2, Cu
1.5mg
1.5(PO
4)
2, Cu
1.5ba
0.75sr
0.75(PO
4)
2, Cu
0.15mg
2.85(PO
4)
2, Cu
1.5ca
1.5(PO
4)
2, Cu
0.15ca
2.85(PO
4)
2, Cu
2ba (PO
4)
2, CuSr
2(PO
4)
2, Cu
0.4sr
2.6(PO
4)
2, CuCr
2o
4, CuB
2o
4, Mg
0.78cu
0.22o, Ca
0.5cu
0.5o, Sr
0.6cu
0.4o, Ba
0.25cu
0.75o, Cu
3(PO
4)
2and Cu
2(PO
4) one or more in (OH).
10. method according to claim 1, wherein, described dispersion agent is water and/or C
1-C
5monohydroxy-alcohol.
11. methods according to claim 1, wherein, the method also comprises: isolate the solid matter in the mixture that reacting by heating obtains, and the solid matter that will obtain is dry.
12. methods according to claim 11, wherein, described drying is carried out under temperature is the condition of 80-150 DEG C.
13. methods according to claim 1 or 11, wherein, described reacting by heating is carried out under temperature is the condition of 60-80 DEG C.
14. methods according to claim 13, wherein, the time of described reacting by heating is 1-3 hour.
15. 1 kinds of surface treated electroless plating activators obtained by the method in claim 1-14 described in any one.
The application of 16. surface treated electroless plating activators according to claim 15 in the metallization of insulativity substrate surface.
17. 1 kinds of polymer products, this polymer product comprises polymeric matrix and dispersion electroless plating activator in the polymer matrix, and it is characterized in that, described electroless plating activator is surface treated electroless plating activator according to claim 15.
18. polymer products according to claim 17, wherein, with the total amount of described polymer product for benchmark, the content of described electroless plating activator is 1-40 % by weight.
19. 1 kinds of surfaces of polymeric articles method for metallising, the method comprises the following steps:
(1) with energetic beam illumination polymer product need carry out metallized surface, make irradiated surface gasification; And
(2) postradiation polymer product is carried out electroless plating,
It is characterized in that, described polymer product is the polymer product described in claim 17 or 18.
20. methods according to claim 19, wherein, described energy-beam is laser.
21. methods according to claim 20, wherein, the wavelength of described laser is 157nm to 10.6 μm, sweep velocity is 500-8000mm/s, and step-length is 3-9 μm, and time delay is 30-100 μ s, frequency is 30-40kHz, and power is 3-4kW, and filling spacing is 10-50 μm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543813A (en) * | 2016-03-01 | 2016-05-04 | 上海安费诺永亿通讯电子有限公司 | Method for producing precise metal circuit on plastic surface |
| CN106929836A (en) * | 2015-12-31 | 2017-07-07 | 比亚迪股份有限公司 | The surface treatment method and chemical plating activator and polymer product and surfaces of polymeric articles selective metallization method of inorganic particle |
| CN106929834A (en) * | 2015-12-31 | 2017-07-07 | 比亚迪股份有限公司 | The surface selective metallization method of inorganic powder surface processing method and chemical plating activator and polymer product and polymer product |
| CN113278955A (en) * | 2021-06-08 | 2021-08-20 | 惠州市四维化工有限公司 | Surface metallization treatment method for chemical plating activator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000129448A (en) * | 1998-10-23 | 2000-05-09 | Inoac Corp | Vessel having plating layer on inside face and its production |
| CN101747650A (en) * | 2009-12-17 | 2010-06-23 | 比亚迪股份有限公司 | Plastic compound, application thereof and method of selective metallization of plastic surface |
| CN102206817A (en) * | 2011-03-17 | 2011-10-05 | 比亚迪股份有限公司 | Preparation method of plastic product |
-
2013
- 2013-09-17 CN CN201310425960.8A patent/CN104451615B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000129448A (en) * | 1998-10-23 | 2000-05-09 | Inoac Corp | Vessel having plating layer on inside face and its production |
| CN101747650A (en) * | 2009-12-17 | 2010-06-23 | 比亚迪股份有限公司 | Plastic compound, application thereof and method of selective metallization of plastic surface |
| CN102206817A (en) * | 2011-03-17 | 2011-10-05 | 比亚迪股份有限公司 | Preparation method of plastic product |
Non-Patent Citations (1)
| Title |
|---|
| 孙企达: "《冷冻干燥超细粉体技术及应用》", 28 February 2006, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106929836A (en) * | 2015-12-31 | 2017-07-07 | 比亚迪股份有限公司 | The surface treatment method and chemical plating activator and polymer product and surfaces of polymeric articles selective metallization method of inorganic particle |
| CN106929834A (en) * | 2015-12-31 | 2017-07-07 | 比亚迪股份有限公司 | The surface selective metallization method of inorganic powder surface processing method and chemical plating activator and polymer product and polymer product |
| CN105543813A (en) * | 2016-03-01 | 2016-05-04 | 上海安费诺永亿通讯电子有限公司 | Method for producing precise metal circuit on plastic surface |
| CN113278955A (en) * | 2021-06-08 | 2021-08-20 | 惠州市四维化工有限公司 | Surface metallization treatment method for chemical plating activator |
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