CN104451615B - Chemical plating activator surface treatment method and chemical plating activator and application and polymer product and method for surface metallation - Google Patents
Chemical plating activator surface treatment method and chemical plating activator and application and polymer product and method for surface metallation Download PDFInfo
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- CN104451615B CN104451615B CN201310425960.8A CN201310425960A CN104451615B CN 104451615 B CN104451615 B CN 104451615B CN 201310425960 A CN201310425960 A CN 201310425960A CN 104451615 B CN104451615 B CN 104451615B
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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
Heating response is carried out in dispersant the invention provides a kind of surface treatment method of chemical plating activator, including by chemical plating activator and surface modifier, the surface modifier is selected from A (OH)n, A (OH) can be formed under hydrolysis and/or alcoholysis conditionsnMaterial and amorphous silica, wherein, A B, Al or Si.The surface treated chemical plating activator obtained present invention also offers the method by the present invention and its application.Invention further provides a kind of polymer product containing surface treated chemical plating activator and a kind of method for surface metallation.Chemical plating activator is handled using the method for the present invention, then the surface treated chemical plating activator is dispersed in polymeric matrix again, the probability that polymeric matrix is degraded can not only be substantially reduced, and the polymeric matrix for being dispersed with the surface treated chemical plating activator still has chemical plating activity.
Description
Technical field
The present invention relates to a kind of chemical plating activator surface treatment method and surface treatedization obtained by this method
Plating activator and its application are learned, the poly- of the surface treated chemical plating activator is wherein dispersed with the invention further relates to a kind of
Compound product, the invention further relates to a kind of surfaces of polymeric articles method for metallising.
Background technology
Surfaces of polymeric articles formed metal level, as electromagnetic signal conduction path, be widely used in automobile, industry,
The fields such as computer, communication.Surfaces of polymeric articles be formed selectively metal level be such polymer product manufacture one
Individual core link.
US2004/0241422A1 reports the inorganic compound powder that spinel structure is added in polymeric matrix, this
A little inorganic compounds contain the elements such as copper, nickel, cobalt, chromium, iron, then use Ultra-Violet Laser（Wavelength be 248nm, 308nm, 355nm,
532nm）And infrared laser（Wavelength is 1064nm and 10600nm）Activated.US2004/0241422A1, which should be particularly mentioned that, to be had
The oxide of spinel structure can restore metal simple-substance under laser action, using metal simple-substance as nucleus, induced chemical
Deposited metal, form metal level.The realization of this process needs strict technology controlling and process, it is necessary to irradiate higher laser energy
The oxide of spinel structure can be reduced to metal simple-substance, it is right so as to obtain the effect of expected induction-chemical deposition metal
The requirement of equipment and technique is all higher.
CN101747650B discloses a kind of frosting selective metal method, and this method includes：By a kind of plastics group
The well mixed simultaneously injection molding of each component in compound, obtains plastic sample；The plastic sample is entered by irradiation energy line
Row etching, so that partly plastic gasification is peeled off and exposes catalyst component particles；Plastic-like to exposing catalyst component particles
Product carry out electroless copper.Wherein, the plastics composite contains plastic basis material component and catalytic component, the catalytic component
For the ABO with delafossite structure2More than one or both of type composite oxides, A is selected from the periodic table of elements the 9th, 10
With one kind in 11 row metallic elements, B Ni, Mn, Cr, Al or Fe, and A is different from B.Urging used in CN101747650B
Agent component can directly facilitate electroless copper, it is not necessary to the metal component in catalytic component is reduced into list by induced with laser
This complicated and uppity process of matter.
The content of the invention
The present inventor has found in research process：Under equal conditions, with without catalytic component（That is, it is chemical
Plate activator）Plastic sample compare, the mechanical property of the plastic sample containing some catalytic components has declined.
The present inventor is studied for the problem, is found：Plastic sample containing some catalytic components
In plastic substrate degraded so that the mechanical properties decrease of the plastic sample containing the catalytic component.
On the basis of this, by further investigation revealed that；If before these catalytic components are scattered in into plastic substrate, with selected from
A(OH)n, A (OH) can be formed under hydrolysis and/or alcoholysis conditionsnMaterial and amorphous silica（Wherein, A B, Al
Or Si, n are the chemical valence identical integer with A）The catalytic component is heated, can substantially reduce plastics base
The degradation rate of body, it is often more important that, presetting the plastic substrate of the catalytic component will urge again without by induced with laser
Metal component in agent component is reduced to simple substance this complicated and uppity process, you can directly facilitates electroless copper.
It this completes the present invention.
According to the first aspect of the invention, should the invention provides a kind of surface treatment method of chemical plating activator
Method includes：Chemical plating activator and at least one surface modifier are subjected to heating response in dispersant, the surface changes
Property agent is selected from A (OH)n, A (OH) can be formed under hydrolysis and/or alcoholysis conditionsnMaterial and amorphous silica, wherein,
A is B, Al or Si, and n is the chemical valence identical integer with A.
According to the second aspect of the invention, the invention provides the surface treated that a kind of method by the present invention obtains
Chemical plating activator.
According to the third aspect of the present invention, the invention provides a kind of surface treated chemical plating activator to exist
Application in insulating properties base material surface selective metallization.
According to the fourth aspect of the present invention, the invention provides a kind of polymer product, the polymer product to include poly-
Compound matrix and scattered chemical plating activator in the polymer matrix, wherein, the chemical plating activator is this hair
The surface treated chemical plating activator of bright offer.
According to the fifth aspect of the present invention, the invention provides a kind of surfaces of polymeric articles method for metallising, the party
Method comprises the following steps：
（1）The surface metallized with the needs of energetic beam illumination polymer product, makes illuminated surface gasify；With
And
（2）Polymer product after irradiation is subjected to chemical plating,
Wherein, the polymer product is polymer product provided by the invention.
Chemical plating activator is handled using the method for the present invention, then the surface treated chemical plating lived again
Agent is dispersed in polymeric matrix, can not only substantially reduce the probability that polymeric matrix is degraded, and be dispersed with this
The polymeric matrix of surface treated chemical plating activator still has chemical plating activity.Its reason is probably：Chemical plating is lived
Agent also has certain facilitation to depolymerization, and processing energy is carried out to chemical plating activator using the method for the present invention
It is enough to form one layer of clad on chemical plating activator surface, polymeric matrix and chemical plating activator are separated, so as to effectively drop
The probability that low polymer matrix is degraded；Also, in follow-up energy line irradiation and/or plating process, described in formation
The material of clad can chemically plate activator sur-face peeling, expose chemical plating activator and come, assign polymeric matrix
With chemical plating activity.
Also, the face that will not make chemical plating activator is surface-treated to chemical plating activator using the method for the present invention
Color is deepened, it might even be possible to obtains lighter color.
In addition, the chemical plating activator surface treatment method of the present invention is easy to operate, it is easy to implement.
Embodiment
According to the first aspect of the invention, should the invention provides a kind of surface treatment method of chemical plating activator
Method includes：Chemical plating activator and at least one surface modifier are subjected to heating response in dispersant.
In the present invention, the chemical plating activator is the material for referring to induction-chemical deposition metal, can be conventional
The various materials that can realize above-mentioned function.Preferably, the chemical plating activator is selected from the metal compound shown in formula III
The one or more in the metallic compound shown in metallic compound, Formula V shown in thing, formula IV.
CuyM1 x(PO4)2(OH)z（Formula III）
In formula III, M1For one or both of the 2nd row selected from periodic table of elements above element, x+y=3,0≤x ＜
3, z be 0 or 1.
In formula III, M1Preferably more than one or both of Ca, Mg, Ba and Sr.
CuM2 2O4（Formula IV）
In formula IV, M2For selected from the periodic table of elements the 6th row, the 8th row and the 13rd row one or both of above element,
Preferably more than one or both of Al, B, Cr, Ga, Fe and In.
M3 mCunO （Formula V）
In Formula V, M3For one or both of the 2nd row selected from the periodic table of elements above element, preferably Ca, Mg, Ba
With it is more than one or both of Sr；m+n=1.
Specifically, the chemical plating activator can be selected from Cu2.7Mg0.3(PO4)2、Cu1.5Mg1.5(PO4)2、
Cu1.5Ba0.75Sr0.75(PO4)2、Cu0.15Mg2.85(PO4)2、Cu1.5Ca1.5(PO4)2、Cu0.15Ca2.85(PO4)2、Cu2Ba(PO4)2、
CuSr2(PO4)2、Cu0.4Sr2.6(PO4)2、CuCr2O4、CuB2O4、Mg0.78Cu0.22O、Ca0.5Cu0.5O、Sr0.6Cu0.4O、
Ba0.25Cu0.75O、、Cu3(PO4)2And Cu2(PO4) one or more in (OH).
The granular size of the chemical plating activator can be conventional selection.Usually, the body of the chemical plating activator
Product average grain diameter can be 0.1-5 μm, preferably 0.4-2 μm.
The color of metallic compound shown in formula III is generally light green color or light blue, therefore contains the metallic compound
The product of polymer can also show light color.
The chemical plating activator is commercially available, and known method can also be used to be prepared.Such as：It can lead to
The method of oversintering prepares the chemical plating activator, that is, by the component source containing the chemical plating activator
Mixture is sintered, so as to obtain the chemical plating activator.For purposes of brevity, herein with the chemical combination shown in formula III
Thing（Wherein, z 0, x are not 0）Exemplified by, the preparation method of chemical plating activator is described in detail.
Metallic compound shown in formula III（Wherein, z 0, x are not 0）Can be by the way that Cu sources, group iia metal will be contained
Source and phosphatic mixture are sintered and obtained.
The Cu sources can be CuO and/or CuO material can be formed under sintering condition, described under sintering condition
The material that CuO can be formed can be various mantoquitas, and such as the mantoquita of inorganic acid and/or the mantoquita of organic acid, its instantiation can
To include but is not limited to：Cupric oxalate and/or copper carbonate.
The group iia source metal can be the oxide of group iia metal and/or can form the under sintering condition
The compound of the oxide of Group IIA metal.The compound of the oxide that group iia metal can be formed under sintering condition
Can be the acylate and/or inorganic acid salt of group iia metal, such as the of the group iia metal salt of carbonic acid and/or oxalic acid
Group IIA metal salt.The instantiation of the group iia source metal can include but is not limited to：Magnesia, magnesium carbonate, magnesium oxalate,
One or more in calcium oxide, calcium carbonate, calcium oxalate, strontium oxide strontia, strontium carbonate, barium monoxide, barium carbonate and barium oxalate.
The phosphate can be the common metal salt of various phosphoric acid and/or the ammonium salt of phosphoric acid, and its instantiation can be with
Including but not limited to：Ammonium hydrogen phosphate and/or ammonium dihydrogen phosphate.
Relative scale between the Cu sources, group iia source metal and phosphate is to enable to the gold finally given
The content of various elements disclosure satisfy that previously described requirement is defined in category compound.
The sintering can use once sintered technique, can also use double sintering technique.Specifically, it is described once
Sintering process includes：Containing Cu sources, group iia source metal and phosphatic mixture 10- will be incubated at 900-1000 DEG C
20h, and grind obtained sinter；The double sintering technique includes：By Cu sources, group iia source metal and phosphatic
Mixture is incubated 2-10h at 600-900 DEG C, then grinds obtained solid matter, and then the material that grinding obtains exists again
900-1000 DEG C of insulation 10-20h.For being incubated 10-20h, either once sintered technique, or secondary burning at 900-1000 DEG C
Knot technique, when group iia metal and Cu mol ratio are less than 1, preferably it is incubated 10-20h at 900-950 DEG C.
It is described containing Cu sources, group iia source metal and phosphatic mixture can by by Cu sources, group iia gold
Category source and phosphate are ground and obtained.
In the present invention, the grinding can be dry grinding, or wet grinding, can also be semidry method,
Preferably wet grinding or semidry method, more preferably wet grinding.The dispersant of the wet grinding can be conventional
The various dispersants for being adapted as metal oxide.Specifically, the dispersant can be water and/or absolute ethyl alcohol.Dispersant
Dosage can be conventional selection, be not particularly limited.
The surface modifier is selected from A (OH)n, hydrolysis and/alcoholysis conditions under can form A (OH)nMaterial and without fixed
Shape silica, wherein, A B, Al or Si, n are the chemical valence identical integer with A.
For A (OH)n, its instantiation can include but is not limited to：Boric acid, Al (OH)3With Si (OH)4。
For A (OH) can be formed under hydrolysis and/or alcoholysis conditionsnMaterial, can be selected according to A difference
Select.
It is described that A (OH) can be formed under hydrolysis and/or alcoholysis conditions when A is AlnMaterial can be Formulas I shown in
Aluminum alkoxide,
In Formulas I, R1、R2And R3It is identical or different, respectively C1-C6Alkyl.
In the present invention, C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can be with
Including but not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 2- first
Base butyl, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, 2,3-
Dimethylbutyl, 2,2- dimethylbutyls, 3,3- dimethylbutyls and 2- ethyl-butyls.
It is described that A (OH) can be formed under hydrolysis and/or alcoholysis conditions when A is SinMaterial can be various organic
Siloxanes, the siloxanes as described in Formula II,
In Formula II, R4、R5、R6And R7It is identical or different, respectively C1-C6Alkyl orR8For C1-C6Alkane
Base.
It is B in A（That is, boron）When, it is described that A (OH) can be formed under hydrolysis and/or alcoholysis conditionsnMaterial can be each
Kind borate, the borate as shown in formula III,
In formula III, R8、R9And R10It is identical or different, respectively C1-C6Alkyl.
Can be the amorphous silicon di-oxide in various sources, the molecule of this kind of silica for amorphous silica
Contain-OH groups in structure, be reactive silicon dioxide.Such as：Aerosil and Ludox.The aerosil
Particle diameter can be conventional selection, general volume average particle size can be below 100nm, such as 20-60nm.
Specifically, the surface modifier is boric acid, aluminium isopropoxide, tert-butyl alcohol aluminium, tetramethoxy-silicane, tetraethoxy-silicane
Alkane, MTMS, ethyl trimethoxy silane, dimethyldimethoxysil,ne, diethyldimethoxysilane, first
One or more in ethyl triethoxy silicane alkane, dimethyldiethoxysilane and aerosil.
Relative scale between the surface modifier and the chemical plating activator can be according to chemical plating activator
Species carries out appropriate selection.Usually, the surface modifier is with A2OnMeter, is activated relative to chemical plating described in 100 parts by weight
Agent, the dosage of the surface modifier can be 1-20 parts by weight, preferably 1-15 parts by weight.
The dispersant can be it is various can make the chemical plating activator is scattered to form suspension, and can enough dissolve or
Disperse the material of the surface modifier.Preferably, the dispersant contains water and/or alcohol, on the one hand can so make described
Chemical plating activator is scattered to form suspension, and contain in the surface modifier can under hydrolysis and/or alcoholysis conditions
Form A (OH)nMaterial when, hydrolysis or alcoholysis for the material provide water source or alcohol source.It is highly preferred that the dispersant is water
And/or C1-C5Monohydric alcohol.C1-C5Monohydric alcohol can be methanol, ethanol, normal propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, 2-
Methyl isophthalic acid-propyl alcohol, 2- methyl-2-propanols, n-amyl alcohol, 2-methyl-1-butene alcohol, 3- methyl-1-butanols, 2- methyl -2- butanol, 3-
One or more in methyl -2- butanol and 2,2- dimethyl -1- propyl alcohol, preferably ethanol.
The dosage of the dispersant is defined by that can form uniform suspension.Usually, relative to described in 100 parts by weight
Chemical plating activator, the dosage of the dispersant can be 100-1000 parts by weight.
The condition of the heating response can occur hydrolysis-condensation reaction with the surface modifier or condensation occurs instead
It should be defined.Usually, the heating response is carried out under conditions of being 20-90 DEG C in temperature.Preferably, the heating response
Carried out under conditions of being 60-80 DEG C in temperature.
The time of the heating response can be selected according to the temperature of heating response.Usually, the heating response
Time can be 1-8 hours, preferably 1-3 hours.
It can also be included according to the surface treatment method of the present invention：Isolate the solid in the mixture that heating response obtains
Material, and solid matter drying will be obtained.The drying is carried out under conditions of being 80-150 DEG C in temperature.The drying
Time can be selected according to the temperature being dried, and typically can be 1-24 hours.The drying can be in oxygen-containing atmosphere
Middle progress（Carried out such as in air atmosphere）, can also be carried out in inert atmosphere.The inert atmosphere refer to by not with
The atmosphere of chemically interactive gas formation is occurred by dry material, such as can be by nitrogen atmosphere and/or zero group member
The atmosphere that plain gas is formed（The atmosphere such as formed by argon gas）.
According to the second aspect of the invention, the invention provides the surface treated that a kind of method by the present invention obtains
Chemical plating activator.The surface treated chemical plating activator obtained by the method for the present invention is dispersed in polymeric matrix
When middle, the degraded of polymeric matrix is small, thus the polymeric matrix for being wherein dispersed with the chemical plating activator of the present invention still can
It is enough that there is higher mechanical property；And the polymeric matrix of the chemical plating activator of the present invention is wherein dispersed with follow-up gold
During categoryization, still with chemical plating activity.
According to the third aspect of the present invention, the invention provides the surface treated chemical plating activator of the present invention to exist
By the application in insulating properties base material surface selective metallization.
The insulating properties base material can be the common various base materials without electric conductivity, such as：Polymeric substrate, ceramics
Base material and glass baseplate etc..
It can will be dispersed according to the chemical plating activator of the present invention in the insulating properties base material, and pass through irradiation energy line
The surface roughening that the needs of the insulating properties base material are metallized, then carrying out chemical plating can be by insulating properties base material
Surface selective metallization.Ink can also be made in the chemical plating activator of the present invention, and ink is coated in insulating properties base
The surface that the needs of material are metallized, and optionally by irradiation energy line make ink layer surface gasify after, carry out chemical plating, from
And by insulating properties base material surface selective metallization.
According to the fourth aspect of the present invention, the invention provides a kind of polymer product, the polymer product to include poly-
Compound matrix and scattered chemical plating activator in the polymer matrix, wherein, the chemical plating activator is this hair
The surface treated chemical plating activator of bright offer.
Detailed description has been carried out above for described surface treated chemical plating activator and preparation method thereof, this
Place repeats no more.
The content for the surface treated chemical plating activator being dispersed in the polymer product can be according to polymer
The specifically used requirement of product carries out appropriate selection.Usually, on the basis of the gross weight of the polymer product, describedization
The content for learning plating activator can be 1-40 weight %, more preferably preferably 10-40 weight %, 20-40 weight %.
The polymer product can use conventional forming polymer method to prepare.In one embodiment of the present invention
In, can be by the way that polymer matrix component be well mixed with the surface treated chemical plating activator, and will obtain
Mixture is molded, so as to obtain the polymer product.
The polymer matrix component refers to the component for forming polymeric matrix, including polymer and optional helps
Agent.
The polymer can carry out appropriate selection according to the concrete application occasion of the polymer product.Usually, institute
It can be the product formed by thermoplastic polymer to state polymer product, or the product formed by thermosetting polymer.
The polymer can be plastics, or rubber, can also be fiber.The instantiation of the polymer can include but
It is not limited to：Polyolefin（Such as polystyrene, polypropylene, polymethyl methacrylate and poly- (acrylonitrile-butadiene-styrene (ABS))）、
Makrolon, polyester（If polycyclohexylene is to diformazan alcohol ester, PDAIP, poly- terephthaldehyde
Diallyl phthalate, PBN, polyethylene terephthalate and polybutylene terephthalate (PBT)）, polyamide
（As polyhexamethylene adipamide, poly-hexamethylene azelamide, polybutadiene acyl hexamethylene diamine, nylon 612, poly- decanedioyl oneself
It is diamines, nylon 1010, nylon 11, poly-lauramide, poly-caprylamide, 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, PEI, makrolon/(acrylonitrile-butadiene-styrene (ABS)) alloy, polyphenylene oxide, polyphenylene sulfide, polyamides are sub-
Amine, polysulfones, polyether-ether-ketone, polybenzimidazoles, phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, alkyd
It is more than one or both of resin and polyurethane.
The auxiliary agent can be that can improve the performance of polymer product or assign polymer product with new performance
Material, such as filler, antioxidant and light stabilizer.The content of the auxiliary agent can be carried out according to its species and specifically used requirement
Appropriate selection, is not particularly limited.Usually, can be relative to polymer described in 100 parts by weight, the content of the filler
1-40 parts by weight, the content of the antioxidant can be 0.01-1 parts by weight, and the content of the light stabilizer can be 0.01-1
Parts by weight, the content of the lubricant can be 0.01-1 parts by weight.
The filler can not play any physics or the filler of chemical action to laser, for example, talcum powder and carbonic acid
Calcium.Although glass fibre is insensitive to laser, it is recessed to add plastic substrate after glass fibre can deepen laser activation significantly
Sunken depth, be advantageous to the adhesion of copper in electroless copper.The inorganic filler can also be the nothing to be played a role to laser
Machine filler, for example, tin oxide especially nano tin dioxide can increase energy utilization of the infrared laser when peeling off frosting
Rate；Functional filler also has carbon black, and it can also increase plastics to infrared absorption, increases the extent of exfoliation of plastics.It is described to fill out
Material can also be glass microballoon, calcium sulfate, barium sulfate, titanium dioxide, pearl essence, wollastonite, diatomite, kaolin, coal dust, pottery
One or more in soil, mica, kerosene shale ash, alumina silicate, aluminum oxide, carbon fiber, silica and zinc oxide.
The antioxidant can improve the antioxygenic property of the polymer product of the present invention, so as to improve the use longevity of product
Life.The antioxidant can be the various antioxidant commonly used in polymer arts, such as can contain primary antioxidant and aid in anti-
Oxygen agent.Relative usage between the primary antioxidant and the auxiliary antioxidant can carry out appropriate selection according to species.One
As, the weight ratio of the primary antioxidant and the auxiliary antioxidant can be 1：1-4.The primary antioxidant can be hindered phenol
Type antioxidant, its instantiation can include but is not limited to antioxidant 1098 and antioxidant 1010, wherein, the master of antioxidant 1098
It is N to want composition, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, antioxidant 1010 it is main into
It is divided into four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites.The auxiliary antioxidant can be phosphite ester
Type antioxidant, its instantiation can include but is not limited to irgasfos 168, and its main component is three (2,4- di-tert-butyl-phenyls)
Phosphite ester.
The light stabilizer can be known various light stabilizers, such as hindered amine type light stabilizer, its instantiation
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate can be included but is not limited to.
The auxiliary agent can also include the material of the various processing characteristicies that can improve polymeric matrix, such as lubricant.Institute
The material that lubricant can be the various mobility that can improve polymer melt is stated, such as can be selected from ethene/acetic acid second
The copolymerization wax of alkene（EVA waxes）, Tissuemat E（PE waxes）And more than one or both of stearate.
The method of the shaping can be the various forming methods that polymer forming art is commonly used, such as：Injection molding, squeeze
Go out shaping.
According to the fifth aspect of the present invention, the invention provides a kind of surfaces of polymeric articles method for metallising, the party
Method comprises the following steps：
（1）The surface metallized with the needs of energetic beam illumination polymer product, makes illuminated surface gasify；With
And
（2）Polymer product after irradiation is subjected to chemical plating,
Wherein, the polymer product is polymer product provided by the invention.
Described polymer product and preparation method thereof has been carried out describing above, is no longer described in detail herein.
According to the surfaces of polymeric articles method for metallising of the present invention, the cleaning after irradiation energy beam, irradiation energy beam
In process and plating process, the bag on the surface treated chemical plating activator surface being dispersed in the polymer product
Activator sur-face peeling can chemically be plated by covering material, make chemical plating activator expose come, so as to assign polymeric matrix with
Chemical plating activity.
The energy beam can be it is various can make polymer gasification peel off energy beams, such as laser, electron beam or from
Beamlet, preferably laser.The laser can be obtained by various known approach, preferably obtain laser by laser.
The condition of irradiation energy beam is can make the polymer gasification of surfaces of polymeric articles expose chemical plating activator
It is defined, can be selected according to the difference of the species of polymer and the type of energy beam.The method according to the invention, with energy
Measure beam elective irradiation surfaces of polymeric articles when, without too high energy using as the metallic compound of chemical plating activator also
Original need to only make polymer gasification expose metallic compound into metal simple-substance, you can directly carry out chemical plating, realize polymer
Product surface selective metallization, technique is simple, low to energy requirement.
Usually, when using laser as energy beam, the wavelength of the laser can be 157nm to 10.6 μm, scanning
Speed can be 500-8000mm/s, and step-length can be 3-9 μm, and 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 laser as irradiation, the polymer typically etched away
Thickness is several microns to more than ten microns, so that being dispersed in the metal compound as chemical plating activator in polymer product
Thing is exposed, and it is the coarse table with rugged space to be formed at least part surface of polymer product on microcosmic
Face structure；In follow-up chemical plating, metallic particles is just embedded into the hole of rough surface, so as to the shape between plastic sample
Into very strong adhesion.
Polymer product through energetic beam illumination is preferably cleaned, with clean surface before chemical plating is carried out.Can be with
The polymer product through energetic beam illumination is cleaned with the cleaning agent of such as water.
The method that chemical plating is carried out to the polymer product for exposing metallic compound has also been those skilled in the art institute
It is known.For example, when carrying out electroless copper, this method can include contacting the polymer product after etching with copper electrolyte, described
Copper electrolyte contains mantoquita and reducing agent, pH value 12-13, and copper ion in mantoquita can be reduced to copper simple substance by the reducing agent,
Such as the reducing agent can be the one or more in glyoxalic acid, hydrazine and sodium hypophosphite.
After chemical plating is carried out, it can also then be electroplated or carry out one or many chemical platings again, to enter one
The thickness of step increase coating forms other coats of metal on chemical deposit.For example, after electroless copper terminates, Ke Yizai
Chemical plating one layer of nickel prevents copper coating surface to be oxidized.
With reference to embodiments the present invention is described in detail with comparative example.
In following examples and comparative example, using inductively coupled plasma emission spectrography（ICP）To determine chemical plating
The composition of activator.
In following examples and comparative example, using the laser particle size commercially available from Jingxin Power Testing Apparatus Co., Ltd., Chengdu
Tester determines the average grain diameter of chemical plating activator, is volume average particle size.
In following examples and comparative example, the attachment of the metal level formed in substrate surface is determined using cross-cut tester method
Power.Specifically method of testing is：10 × 10 1mm × 1mm small grid, each line are drawn on testing sample surface with cross-cut tester
The bottom of depth and metal level, after the fragment of test zone is cleaned down with hairbrush, use adhesive tape（3M600 gummed papers）Cling tested
The small grid of examination, holds adhesive tape one end, and gummed paper is shut down rapidly in vertical direction, and 2 same tests are carried out in same position,
Adhesive force grade is determined according to following standard：
ISO grades 0：Scribing edge is smooth, at the edge of line and intersection without peeling paint；
ISO grades 1：There is the peeling paint of small pieces in the intersection of line, and the gross area that comes off is less than 5%；
ISO grades 2：Have the peeling paint of small pieces at the edge of line and intersection, and come off the gross area 5-15% it
Between；
ISO grades 3：There is sheet of peeling paint at the edge of line and intersection, and the gross area that comes off is in 15-35%
Between；
ISO class 4s：There is sheet of peeling paint at the edge of line and intersection, and the gross area that comes off is in 35-65%
Between；
ISO class 5s：There is sheet of peeling paint at the edge of line and intersection, and the gross area that comes off is more than 65%.
In following examples and comparative example, at a temperature of 300 DEG C, apply 11.76N load, determine raw material respectively and gather
The melt flow rate (MFR) of compound and polymer sheet containing chemical plating activator, polymer product is calculated using below equation
Degree of degradation,
Degree of degradation（%）=[| MI0- MI1︱/MI0] × 100%,
Wherein, MI0For the melt flow rate (MFR) of raw polymer, in terms of g/min,
MI1For the melt flow rate (MFR) of the polymer sheet containing chemical plating activator, in terms of g/min.
Embodiment 1-8 is used to illustrate the present invention.
Embodiment 1
（1）By CuO and Cr2O3It is well mixed, wherein, Cu2O and Cr2O3Mol ratio be 1：1.Obtained mixture is used
Grinder carries out wet grinding, wherein, dispersant is water, and relative to 100 parts by weight mixtures, the dosage of water is 150 parts by weight.
Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 100 DEG C, when
Between be 12 hours.
Dried powder is placed in Muffle furnace and is sintered, the temperature of sintering is 950 DEG C, and the time is 10 hours.Will
Sinter carries out dry grinding, obtains the ferrous metal compound that volume average particle size is 2 microns.After testing, the metal compound
The chemical formula of thing is CuCr2O4。
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 100 parts by weight）In, it is adjoint to be heated with stirring to 80 DEG C.Then, at 80 DEG C, 10 weight % boric acid aqueous solution is added dropwise to point
Dissipating has CuCr2O4Water（With B2O3Meter, relative to 100 part by weight of metal compounds, the dosage of boric acid is 15 parts by weight）In.Drop
After the completion of adding, continue after stirring 1 hour at such a temperature, be cooled to room temperature.Then obtained mixture is filtered, will
To solid matter be dried in air atmosphere, so as to obtain surface treated metallic compound（In black）, wherein,
Dry temperature is 100 DEG C, and the time is 12 hours.
（3）By makrolon, antioxidant 1098, lubricant PE waxes and step（2）The surface treated metallization prepared
Compound mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 40 parts by weight,
The dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, note is sent into
Injection molding in molding machine, obtain the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, plastic sample is cleaned with water, is subsequently placed in plating solution and carries out chemical plating, it is 2 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 10.01%.
Comparative example 1
Using with the step of embodiment 1（1）Identical method prepare metallic compound, using with the step of embodiment 1（3）It is identical
Method prepare polymer product, and using and the step of embodiment 1（4）Identical method is by the surface metal of polymer product
Change, unlike, without step（2）（It is, step（3）Use step（1）The metallic compound of preparation）.
After tested, plating rate is 7 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（3）The degree of degradation of obtained polymer sheet is 38.31%.
Embodiment 2
（1）By CuO, CaO and NH4H2PO4It is well mixed, wherein, CuO, CaO and NH4H2PO4Mol ratio be 1.5：1.5：
2.Obtained mixture is subjected to wet grinding with grinder, wherein, dispersant is absolute ethyl alcohol, is mixed relative to 100 parts by weight
Compound, the dosage of absolute ethyl alcohol is 150 parts by weight.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 80 DEG C, the time
For 12 hours.
Dried powder is placed in Muffle furnace and is sintered in air atmosphere, the temperature of sintering is 1000 DEG C, when
Between be 20 hours.Sinter is subjected to dry grinding；Obtain the metallic compound that volume average particle size is 2 microns.After testing, should
The chemical formula of metallic compound is Cu1.5Ca1.5(PO4)2.The metallic compound is in light green.
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 500 parts by weight）In, it is adjoint to be stirred and heated to 80 DEG C.Then, at 80 DEG C, by the aerosil containing 10 weight %
（Volume average particle size is 50nm）Aqueous dispersions be added dropwise to and be dispersed with Cu1.5Ca1.5(PO4)2Water（With SiO2Meter, relative to
100 parts by weight Cu1.5Ca1.5(PO4)2, the dosage of aerosil is 10 parts by weight）In, after being added dropwise to complete, continue in the temperature
After the lower stirring of degree 1 hour, room temperature is cooled to.Then obtained mixture is filtered, by obtained solid matter in air
It is dried in atmosphere, so as to obtain surface treated metallic compound（In light green color）, wherein, dry temperature is 100
DEG C, the time is 12 hours.
（3）By makrolon, antioxidant 1098, lubricant PE waxes and step（2）The surface treated metallization prepared
Compound mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 20 parts by weight,
The dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, note is sent into
Injection molding in molding machine, obtain the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, abatement processes are carried out to plastic sample, is subsequently placed in plating solution and carries out chemical plating, it is 12 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 9.51%.
Comparative example 2
Using with the step of embodiment 2（1）Identical method prepare metallic compound, using with the step of embodiment 2（3）It is identical
Method prepare polymer product, and using and the step of embodiment 2（4）Identical method is by the surface metal of polymer product
Change, unlike, without step（2）（It is, step（3）Using step（1）The metallic compound of preparation）.
After tested, plating rate is 6 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（3）The degree of degradation of obtained polymer sheet is 48.31%.
Embodiment 3
Surface-modified metallic compound, polymer product are prepared using method same as Example 2 and will be polymerize
Tetramune surface metalation, unlike, step（1）In, with the tetraethoxysilane of equivalent（With SiO2Meter）Instead of gas phase two
Silica.
After tested, plating rate is 7 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（3）The degree of degradation of obtained polymer sheet is 8.95%.
Embodiment 4
（1）By Cu2(PO4)(OH)（Commercially available from Shanghai Ao highland barleys Industrial Co., Ltd., for shallow white green）It is dispersed in ethanol（Contain
Measure as 95 weight %, relative to 100 parts by weight Cu2(PO4) (OH), the dosage of ethanol is 1000 parts by weight）In, with agitating and heating
To 60 DEG C.Then, at 60 DEG C, 2 weight % aluminium isopropoxide ethanol solution is added dropwise to and is dispersed with Cu2(PO4) (OH) ethanol（With
Al2O3Meter, relative to 100 parts by weight Cu2(PO4) (OH), the dosage of aluminium isopropoxide is 2 parts by weight）In, after being added dropwise to complete, at this
At a temperature of continue stirring 2 hours, be cooled to room temperature.Then it is small obtained mixture to be placed 12 in air atmosphere in 80 DEG C
When, so as to obtain surface treated metallic compound（In shallow white green）.
（2）By makrolon, antioxidant 1098, lubricant PE waxes and step（1）The surface treated chemical plating prepared
Activator mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 40 weight
Part, the dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, send
Enter injection molding in injection machine, obtain the polymer sheet that thickness is 2mm.
（3）By step（2）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, abatement processes are carried out to plastic sample, is subsequently placed in plating solution and carries out chemical plating, it is 12 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 10 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 15.51%.
Comparative example 3
Using with the step of embodiment 4（2）Identical method prepares polymer product and used and the step of embodiment 4（3）Phase
Same method metallizes surfaces of polymeric articles, unlike, directly using Cu2(PO4)(OH)（It is real commercially available from Shanghai Ao highland barleys
Industry Co., Ltd）.
After tested, plating rate is 10 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（3）The degree of degradation of obtained polymer sheet is 60.58%.
Embodiment 5
（1）By CuO, calcium oxalate and NH4H2PO4It is well mixed, wherein, CuO, calcium oxalate and NH4H2PO4Mol ratio be
0.15：2.85：2.Obtained mixture is subjected to wet grinding with grinder, wherein, dispersant is absolute ethyl alcohol, relative to
100 parts by weight mixtures, the dosage of absolute ethyl alcohol is 150 parts by weight.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 80 DEG C, the time
For 12 hours.
Dried powder is placed in Muffle furnace and is sintered in air atmosphere, the temperature of sintering is 900 DEG C, the time
For 10 hours.Sinter is subjected to dry grinding；The powder of gained is placed in Muffle furnace again and is sintered in air atmosphere,
The temperature of sintering is 1000 DEG C, and the time is 20 hours, and it is the metallic compound that 2 μm are nattierblue to obtain volume average particle size.Through
Detection, the chemical formula of the metallic compound is Cu0.15Ca2.85(PO4)2。
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 800 parts by weight）In, it is adjoint to be stirred and heated to 70 DEG C.Then, at 70 DEG C, tetramethoxy-silicane is added dropwise to and is dispersed with
Cu0.15Ca2.85(PO4)2Water（With SiO2Meter, relative to 100 parts by weight Cu0.15Ca2.85(PO4)2, the dosage of tetramethoxy-silicane
For 8 parts by weight）In, after being added dropwise to complete, continue after stirring 3 hours at such a temperature, be cooled to room temperature.Then the mixing that will be obtained
Thing is filtered, and obtained solid matter is dried in air atmosphere, so as to obtain surface treated metal compound
Thing（In nattierblue）, wherein, dry temperature is 80 DEG C, and the time is 12 hours.
（3）By polyhexamethylene adipamide, antioxidant 1098, lubricant PE waxes and step（2）What is prepared is surface treated
Chemical plating activator mixes, wherein, relative to 100 parts by weight polyhexamethylene adipamide, surface treated metallic compound
Dosage is 25 parts by weight, and the dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.The mixing that will be obtained
After thing is granulated, injection molding in injection machine is sent into, obtains the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, abatement processes are carried out to plastic sample, is subsequently placed in plating solution and carries out chemical plating, it is 12 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 9.5 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 10.51%.
Embodiment 6
（1）By CuO, BaCO3、SrCO3And NH4H2PO4It is well mixed, wherein, CuO, BaCO3、SrCO3And NH4H2PO4's
Mol ratio is 1.5：0.75：0.75：2.Obtained mixture is subjected to wet grinding with grinder, wherein, dispersant is anhydrous
Ethanol, relative to 100 parts by weight mixtures, the dosage of absolute ethyl alcohol is 150 parts by weight.Rotating speed during grinding is 500 revs/min,
Time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 80 DEG C, the time
For 12 hours.
Dried powder is placed in Muffle furnace and is sintered in air atmosphere, the temperature of sintering is 600 DEG C, the time
For 10 hours.Sinter is subjected to dry grinding；The powder of gained is placed in Muffle furnace again and is sintered in air atmosphere,
The temperature of sintering is 1000 DEG C, and the time is 15 hours, and it is absinthe-green metallic compound to obtain volume average particle size to be 2 μm.Through
Detection, the chemical formula of the metallic compound is Cu1.5Ba0.75Sr0.75(PO4)2。
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 200 parts by weight）In, it is adjoint to be heated with stirring to 65 DEG C.Then, at 65 DEG C, 10 weight % boric acid aqueous solution is added dropwise to point
Dissipating has Cu1.5Ba0.75Sr0.75(PO4)2Water（With B2O3Meter, relative to 100 part by weight of metal compounds, the dosage of boric acid is 5 weights
Measure part）In.After being added dropwise to complete, continue after stirring 1 hour at such a temperature, be cooled to room temperature.Then obtained mixture is entered
Row filtering, obtained solid matter is dried in air atmosphere, so as to obtain surface treated metallic compound（It is in
Light green）, wherein, dry temperature is 120 DEG C, and the time is 8 hours.
（3）By polyimides, antioxidant 1098, lubricant PE waxes and step（2）The surface treated metallization prepared
Compound mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 30 parts by weight,
The dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, note is sent into
Injection molding in molding machine, obtain the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, plastic sample is cleaned with water, is subsequently placed in plating solution and carries out chemical plating, it is 2 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 8.2 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 9.56%.
Embodiment 7
（1）By CuO and H3BO3It is well mixed, wherein, CuO and H3BO3Mol ratio be 1：2.Obtained mixture is used
Grinder carries out wet grinding, wherein, dispersant is water, and relative to 100 parts by weight mixtures, the dosage of water is 120 parts by weight.
Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 120 DEG C, when
Between be 8 hours.
Dried powder is placed in Muffle furnace and is sintered, the temperature of sintering is 980 DEG C, and the time is 10 hours.Will
Sinter carries out dry grinding, obtains the metallic compound for green that volume average particle size is 2 microns.After testing, the metal
The chemical formula of compound is CuB2O4。
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 500 parts by weight）In, it is adjoint to be stirred and heated to 80 DEG C.Then, at 80 DEG C, by the second of the tert-butyl alcohol aluminium containing 15 weight %
Alcohol dispersant liquid drop, which adds to, is dispersed with CuB2O4Water（With Al2O3Meter, relative to 100 parts by weight CuB2O4, the dosage of tert-butyl alcohol aluminium is
10 parts by weight）In, after being added dropwise to complete, continue after stirring 1 hour at such a temperature, be cooled to room temperature.Then the mixing that will be obtained
Thing is filtered, and obtained solid matter is dried in air atmosphere, so as to obtain surface treated metal compound
Thing（In green）, wherein, dry temperature is 100 DEG C, and the time is 12 hours.
（3）By makrolon, antioxidant 1098, lubricant PE waxes and step（2）The surface treated metallization prepared
Compound mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 20 parts by weight,
The dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, note is sent into
Injection molding in molding machine, obtain the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, abatement processes are carried out to plastic sample, is subsequently placed in plating solution and carries out chemical plating, it is 12 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 7 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 12.6%.
Embodiment 8
（1）CuO and MgO are well mixed, wherein, CuO and MgO mol ratio are 0.22：0.78.The mixture that will be obtained
Wet grinding is carried out with grinder, wherein, dispersant is water, and relative to 100 parts by weight mixtures, the dosage of water is 120 weight
Part.Rotating speed during grinding is 500 revs/min, and the time is 5 hours.
The powder that grinding obtains is placed in baking oven, is dried in air atmosphere, dry temperature is 120 DEG C, when
Between be 8 hours.
Dried powder is placed in Muffle furnace and is sintered, the temperature of sintering is 800 DEG C, and the time is 6 hours.It will burn
Tie thing and carry out dry grinding, it is jade-green metallic compound to obtain volume average particle size to be 2 microns.After testing, the metallization
The chemical formula of compound is Mg0.78Cu0.22O。
（2）By step（1）The metallic compound of preparation is dispersed in water（Relative to 100 part by weight of metal compounds, the use of water
Measure as 500 parts by weight）In, it is adjoint to be stirred and heated to 80 DEG C.Then, at 80 DEG C, by the second of the aluminium isopropoxide containing 15 weight %
Alcohol dispersant liquid drop, which adds to, is dispersed with Mg0.78Cu0.22O water（With Al2O3Meter, relative to 100 parts by weight Mg0.78Cu0.22O, isopropanol
The dosage of aluminium is 12 parts by weight）In, after being added dropwise to complete, continue after stirring 1 hour at such a temperature, be cooled to room temperature.Then will
Obtained mixture is filtered, and obtained solid matter is dried in air atmosphere, so as to obtain surface treated
Metallic compound（In light green color）, wherein, dry temperature is 100 DEG C, and the time is 12 hours.
（3）By makrolon, antioxidant 1098, lubricant PE waxes and step（2）The surface treated metallization prepared
Compound mixes, wherein, relative to 100 weight part polycarbonates, the dosage of surface treated metallic compound is 20 parts by weight,
The dosage of antioxidant is 0.05 parts by weight, and the dosage of lubricant is 0.04 parts by weight.After obtained mixture pelleting, note is sent into
Injection molding in molding machine, obtain the polymer sheet that thickness is 2mm.
（4）By step（3）Obtained polymer sheet is placed on laser sample stage, by Laser Focusing, computer program control
The movement of light beam or sample stage processed, laser used are big nation YLP-20 type lasers, and laser parameter is：Wavelength is 1064nm,
Sweep speed is 1000mm/s, and step-length is 6 μm, and it is 20 μm to be delayed as 50 μ s, frequency 30kHz, power 4kW, filling spacing.
After laser ablation, abatement processes are carried out to plastic sample, is subsequently placed in plating solution and carries out chemical plating, it is 12 microns to obtain thickness
Coating.Wherein, the composition of plating solution is：Cupric sulfate pentahydrate 5g/L, tartaric acid first sodium 25g/L, sodium hydroxide 7g/L, formaldehyde 10g/L,
Stabilizer 0.1g/L.
After tested, plating rate is 8.5 μm/h, and the adhesive force of coating is ISO grades 1.
After tested, step（4）The degree of degradation of obtained polymer sheet is 10.3%.
Embodiment 1-8 and comparative example 1-4's as a result, it was confirmed that carrying out table to chemical plating activator using the method for the present invention
Face is handled, and is then dispersed in polymeric matrix, can not only substantially be reduced the probability that polymeric matrix is degraded, and
Still it can make polymeric matrix that there is higher chemical plating activity.
Claims (17)
1. a kind of surface treatment method of chemical plating activator, this method include：By chemical plating activator and at least one surface
Modifying agent carries out heating response in dispersant, isolates the solid matter in the mixture that heating response obtains, and will obtain
Solid matter dry, the surface modifier is selected from A (OH)n, A (OH) can be formed under hydrolysis and/or alcoholysis conditionsn's
Material and amorphous silica, wherein, A B, Al or Si, n are the chemical valence identical integer with A；
The chemical plating activator is selected from the metallic compound shown in formula III, the metallic compound shown in Formula V and Cu2(PO4)
(OH) one or more in,
CuyM1 x(PO4)2(OH)z(formula III)
In formula III, M1More than one or both of Ca, Mg, Ba and Sr, x+y=3,0≤x ＜ 3, z are 0 or 1；
M3 mCunO (Formula V)
In Formula V, M3More than one or both of Ca, Mg, Ba and Sr, m+n=1.
2. according to the method for claim 1, wherein, the surface modifier is with A2OnMeter, relative to described in 100 parts by weight
Chemical plating activator, the dosage of the surface modifier is 1-15 parts by weight.
3. method according to claim 1 or 2, wherein, the surface modifier be boric acid, the aluminum alkoxide shown in Formulas I,
The one or more in siloxanes and aerosil shown in Formula II,
In Formulas I, R1、R2And R3It is identical or different, respectively C1-C6Alkyl；
In Formula II, R4、R5、R6And R7It is identical or different, respectively C1-C6Alkyl orR8For C1-C6Alkyl.
4. according to the method for claim 3, wherein, the surface modifier is aluminium isopropoxide, tert-butyl alcohol aluminium, tetramethoxy
One or more in silane and tetraethoxysilane.
5. method according to claim 1 or 2, wherein, the surfactant is MTMS, ethyl three
Methoxy silane, dimethyldimethoxysil,ne, diethyldimethoxysilane, MTES and dimethyl diethyl
One or more in TMOS.
6. according to the method for claim 1, wherein, the chemical plating accelerator is selected from Cu2.7Mg0.3(PO4)2、
Cu1.5Mg1.5(PO4)2、Cu1.5Ba0.75Sr0.75(PO4)2、Cu0.15Mg2.85(PO4)2、Cu1.5Ca1.5(PO4)2、Cu0.15Ca2.85
(PO4)2、Cu2Ba(PO4)2、CuSr2(PO4)2、Cu0.4Sr2.6(PO4)2、Mg0.78Cu0.22O、Ca0.5Cu0.5O、Sr0.6Cu0.4O、
Ba0.25Cu0.75O and Cu3(PO4)2In one or more.
7. according to the method for claim 1, wherein, the dispersant is water and/or C1-C5Monohydric alcohol.
8. according to the method for claim 7, wherein, the drying is carried out under conditions of being 80-150 DEG C in temperature.
9. according to the method for claim 1, wherein, the heating response is carried out under conditions of being 60-80 DEG C in temperature.
10. according to the method for claim 9, wherein, the time of the heating response is 1-3 hours.
11. the surface treated chemical plating activator that a kind of method in 1-10 as claim described in any one obtains.
12. the answering in insulating properties base material surface metalation of the surface treated chemical plating activator described in claim 11
With.
13. a kind of polymer product, the polymer product includes polymeric matrix and disperseed in the polymer matrix
Chemical plating activator, it is characterised in that the chemical plating activator is the surface treated chemical plating described in claim 11
Activator.
14. polymer product according to claim 13, wherein, it is described on the basis of the total amount of the polymer product
The content of chemical plating activator is 1-40 weight %.
15. a kind of surfaces of polymeric articles method for metallising, this method comprise the following steps：
(1) surface metallized with the needs of energetic beam illumination polymer product, makes illuminated surface gasify；And
(2) polymer product after irradiation is subjected to chemical plating,
Characterized in that, the polymer product is the polymer product described in claim 13 or 14.
16. according to the method for claim 15, wherein, the energy beam is laser.
17. according to the method for claim 16, wherein, the wavelength of the laser is 157nm to 10.6 μm, and sweep speed is
500-8000mm/s, step-length are 3-9 μm, and be delayed is for 30-100 μ s, frequency 30-40kHz, power 3-4kW, filling spacing
10-50μm。
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