CN109487249A - A kind of method of electroless copper activator and preparation method thereof and the full addition production route based on the activator - Google Patents
A kind of method of electroless copper activator and preparation method thereof and the full addition production route based on the activator Download PDFInfo
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- CN109487249A CN109487249A CN201910005820.2A CN201910005820A CN109487249A CN 109487249 A CN109487249 A CN 109487249A CN 201910005820 A CN201910005820 A CN 201910005820A CN 109487249 A CN109487249 A CN 109487249A
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- activator
- electroless copper
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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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- Engineering & Computer Science (AREA)
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- Manufacturing Of Printed Wiring (AREA)
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Abstract
The method of a kind of electroless copper activator and preparation method thereof and the full addition production route based on the activator, belongs to chemical plating and wire forming techniques field.The present invention by increase on the basis of conventional activation agent dissolve each other with adhesive and complexing agent containing unsaturated bond and with the matched curing agent of adhesive, in forming the solidification process after preinstalled circuit figure, adhesive is firmly combined by physical absorption and chemical action and substrate, the complexing agent of adsorption catalyst ion is chemically bonded with epoxy resin tackifier simultaneously, so that catalyst ion is uniformly distributed in the active layer of substrate surface, it is achieved that a step forms bridge layer and fixed catalyst in substrate surface, cooperation subsequent chemistry depositing process can form densification, it is bright, the strong coating of adhesive force, the problem of overcoming the metal nanoparticle reunion and additive influence route electric conductivity and substrate surface bridge layer universality difference that existing full addition line manufacturing process is faced and preparation complicated and time consumption.
Description
Technical field
The invention belongs to chemical plating and wire forming techniques fields, and in particular to a kind of electroless copper activator and its preparation
The method of method and the full addition production route based on the activator.
Background technique
The printed circuit board circuit manufacturing method of mainstream is following three kinds at present: subtractive process, semi-additive process and fully-additive process:
Subtractive process is to be formed with the base of specific thickness (this is with a thickness of the layers of copper line thicknesses finally needed) layers of copper on surface
The production method of the enterprising row line of plate, first layers of copper mask and develop form resist pattern, pass through selective etch later
Exposed layers of copper is removed, obtains line pattern after finally removing resist pattern.This method process flow is easy, by more
Production can be completed in mature etch process.However, the maximum defect of this method is, in etching process, exposed layers of copper is past
While lower etching also can lateral erosion, if copper layer thickness is thicker, fresh etching solution is difficult to enter, and pool effect is obvious, then due to
The limitation of etch process ability itself and the limitation of linewidth requirements and resist layer width, will complete the etching to layers of copper, reach rule
Route shape then certainly will need certain route spacing to meet the timely exchange of liquid medicine.With the raising of circuit board integrated level,
The line width of etched copper route is smaller and smaller, and under the action of lateral erosion, this method directly etched is difficult to meet dense copper
Sandwich circuit production requires, to largely limit application of the subtractive process in fine-line production.
Semi-additive process is to form relatively thin (thickness is less than the layers of copper line thicknesses finally needed) base copper-layer on surface
The enterprising row line of substrate production method, first on base copper-layer face, plating resist layer, followed by expose, develop, shape
At plating resist figure, later, plating copper facing is not carried out by plating resist layer covering part, removes plating resist layer, etching removal base copper-layer shape
At route.This method generally passes through deposition of chemical plating copper base copper-layer, since the layers of copper that electroless copper plating obtains is very thin, is easy to carve
Erosion, comparatively, reduces the lateral erosion of route, but chemical copper, being easy to appear are deposited on insulating substrate to a certain extent
Copper plate is insufficient with substrate adhesive force and there is a phenomenon where layerings to blister.
Either subtractive process or semi-additive process, production process is all sufficiently complex, and waste of material is serious, and institute
The heavy metal ion and etchant solution used will cause environmental pollution.Fully-additive process is as the printed wiring production risen in recent years
Technique complies with the development trend of printed wiring green high-efficient.Fully-additive process uses the insulating substrate containing light-sensitive catalyst, is pressing line
After the graph exposure of road, copper is sunk by selective chemical and obtains the technique of conductor fig.It is very suitable to production fine-line.Full addition
Legal system makees conducting wire and obtains tremendous development in recent years, but still also immature, it is difficult to realize heavy industrialization.At this stage
Full additive process is mainly realized by directly printing metallic conductive inks or selective chemical plating metal.
However, being easy to reunite there are electrically conductive ink based on the full additive process of type metal electrically conductive ink causes printing process
The metal nanoparticle of middle reunion is easy blocking spray head or mesh and is led due to the dispersing agent and stabilizer in electrically conductive ink
The problems such as causing the conductivity of conducting wire reduces.Such as Chinese patent " a kind of electrically conductive ink and preparation method thereof " (Shen Qing Publication
Number: it is disclosed in CN107446413A): nano-Ag particles, solvent, cellulose family viscosity modifier and tacky resin is mixed with
Then electrically conductive ink is prepared by silk-screen printing and obtains conducting wire on insulating substrate surface by electrically conductive ink.This method is selected
Tacky resin improves the binding force between nano-Ag particles route and substrate, may be present in nano-Ag particles as bridge material
Between tacky resin certainly will will affect the electric conductivity of route；In addition this method makes conductor wire using noble metal nano Argent grain
Road, higher cost big for noble metal dosage demand.
And the main problem that the full additive process based on selective chemical plating metal is faced is: generally selecting special base
Material realizes that surface is modified to substrate progress specially treated, then again in its surface grafting such as poly-dopamine, photoresist, silicon
The substances such as alkane coupling agent, polyacrylic acid, polyelectrolyte are as the further adsorption catalyst of bridge layer, to realize that surface modification is adopted
Specially treated is specifically such as first roughened substrate surface, and (being detailed in the article that Cai Jiqing is delivered, " fully-additive process lamination prints
Making sheet manufacturing process "), or use the high-energy radiation of ultraviolet light, plasma or laser to be modified substrate surface and (specifically ask
The paper " modified plastics surface laser induced selective chemical plating copper " delivered with reference to Peng Xiao, paper " the silver choosing that Chen Dongsheng is delivered
Selecting property activating chemical, which is plated on Kapton, makes fine-line " and the article delivered of Hu Xianqiao et al. " based on ultraviolet
The metallization of light/ozone chemistry modification-selective chemical plating polymethyl methacrylate surface region ").In addition, this method
Prepared bridge layer does not have universality usually, i.e., different substrates is generally required to choose different bridge layers, is grafted in addition
Process is complicated, elapsed time, and at high cost and production efficiency is relatively low, it is difficult to realize large-scale application.For example China is specially
It is disclosed in benefit " a kind of method and application thereof of polymeric substrate surface metallization " (application publication number: CN107012450A): first
First to polymeric substrate surface graft modification, polymer surfaces adsoption catalysis is then made by inkjet printing or silk-screen printing
Agent finally carries out chemical plating and obtains the polymeric substrates with metallic conductive pattern.But this method carries out polymeric substrate
Surface grafting technics comparing is complicated, and Surface graft process elapsed time is long, and production efficiency is relatively low.
Summary of the invention
Face that electrically conductive ink is easy to reunite for existing full addition line manufacturing process and additive influence route electric conductivity, with
And substrate surface bridge layer universality difference and the problems such as preparation complicated and time consumption, the present invention provides a kind of new electroless copper activator
And preparation method and the full addition circuit manufacturing method based on the activator.
To solve the above-mentioned problems, the present invention adopts the following technical scheme that:
A kind of electroless copper activator, which is characterized in that the activator includes that organic solvent and being dissolved in described has
Metal ion catalyst, complexing agent, adhesive and the curing agent of solvent；Make it solid containing unsaturated bond in the complexing agent
It is dissolved in solution system when change with chemical bond is formed between adhesive, the complexing agent adsorbs the metal ion catalyst
Middle metal ion, and complexing agent dissolves each other with adhesive so that the metal ion of complexing agent absorption is uniformly distributed in adhesive.
Further, the electroless copper activator is uniform, stable solution system.It is verified, chemical plating of the present invention
Copper activator is highly stable, at room temperature place 1 month it is still uniform, transparent.
Further, it is added when curing agent is activated again in the electroless copper activator after carrying out after mixing
Continuous operation.
Further, the metal ion catalyst is silver nitrate, silver acetate, silver oxalate, silver benzoate, palladium acetate and grass
Any one or more in sour palladium.
Further, the complexing agent is thiourea process, thiophene and derivatives, 3- mercaptopropyi triethoxy
The amyl- 2,4- dialkylene -1- thioketones (C of silane, 3-aminopropyltriethoxysilane, ring5H4) and 1- pyrroles's -1- mercaptan S
(C4H5NS any one or more in).Complexing agent of the invention is mainly used as the metal ion in adsorbing metal ions catalyst,
And then metal ion is prevented to be reduced to metal nanoparticle by the epoxy group in the epoxy resin tackifier of subsequent addition.
Further, the molar ratio of the complexing agent and metal ion catalyst is not less than 3: 1.
Further, the adhesive be bisphenol A epoxide resin, novolac epoxy resin, glycerin ether epoxy resin, shrink it is sweet
Any one or more object in oily ester type epoxy resin, aminoepoxy resins and cycloaliphatic epoxy resin.
Further requirement adhesive of the present invention dissolves each other with complexing agent, it is ensured that the metal ion of complexing agent absorption can be in gluing
It is uniformly distributed in agent, it is active since epoxy resin all has physical absorption for any substrate surface, and in epoxy resin
Epoxy group can be chemically bonded with the hydroxyl (- OH) of substrate surface, carbonyl (C=O) or group containing lone pair electrons,
And then guarantee to provide good binding force when forming activation modification layer using solution system for substrate and plating interlayer.
Curing agent of the present invention is selected according to different substrate materials and printed wiring application environment, the dosage of curing agent with used
Adhesive it is related.
Further, the organic solvent is propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, dipropyl
Any one or more in glycol methyl ether acetate and propandiol butyl ether.Due to having hydroxyl (- OH) and ether in these organic solvents
Base (R-O-R '), according to the similar principle that mixes, the complexing agent containing unsaturated bond and the adhesive containing ether are easy dissolution
Wherein.
Further, the curing agent is aliphatic polyol amine type curing agent, cycloaliphatic polyols amine type curing agent, aromatic amine type
Curing agent, anhydride curing agent, polyamide type curing agent, modified amine type curing agent and synthetic resin epoxy hardener
In any one or more.
Further, the molar concentration of complexing agent is preferably 0.03~0.6mol/L in the electroless copper activator, gold
The molar concentration for belonging to ionic catalyst is preferably 0.01~0.02mol/L, and the molar concentration of adhesive is preferably 1~5mol/L,
The molal weight of curing agent is preferably 0.2~1mol/L.
A kind of preparation method of electroless copper activator, which comprises the steps of:
Step 1: complexing agent, metal ion catalyst being dissolved in organic solvent, is uniformly mixed, obtains solution.
Step 2: adhesive and curing agent being dissolved in the solution that step 1 obtains, are uniformly mixed, obtain the chemical plating
Copper activator.
Further, the electroless copper activator needs to be used cooperatively with curing agent when in use, i.e., curing agent only has
It is added when needing using activator, is uniformly mixed and forms the progress subsequent chemistry copper facing operation of preinstalled circuit figure.
Further, the electroless copper activator is uniform, stable solution system.
Further, the metal ion catalyst is silver nitrate, silver acetate, silver oxalate, silver benzoate, palladium acetate and grass
Any one or more in sour palladium.
Further, the complexing agent is thiourea process, thiophene and derivatives, 3- mercaptopropyi triethoxy
The amyl- 2,4- dialkylene -1- thioketones (C of silane, 3-aminopropyltriethoxysilane, ring5H4) and 1- pyrroles's -1- mercaptan S
(C4H5NS any one or more in).Complexing agent of the invention is mainly used as the metal ion in adsorbing metal ions catalyst,
And then metal ion is prevented to be reduced to metal nanoparticle by the epoxy group in the epoxy resin tackifier of subsequent addition.
Further, the molar ratio of the complexing agent and metal ion catalyst is not less than 3: 1.
Further, the molar concentration of complexing agent is preferably 0.03~0.6mol/L in the electroless copper activator, gold
The molar concentration for belonging to ionic catalyst is preferably 0.01~0.02mol/L, and the molar concentration of adhesive is preferably 1~5mol/L,
The molal weight of curing agent is preferably 0.2~1mol/L.
Further, the adhesive be bisphenol A epoxide resin, novolac epoxy resin, glycerin ether epoxy resin, shrink it is sweet
Any one or more object in oily ester type epoxy resin, aminoepoxy resins and cycloaliphatic epoxy resin.
Further, the organic solvent is propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, dipropyl
Any one or more in glycol methyl ether acetate and propandiol butyl ether.Due to having hydroxyl (- OH) and ether in these organic solvents
Base (R-O-R '), according to the similar principle that mixes, the complexing agent containing unsaturated bond and the adhesive containing ether are easy dissolution
Wherein.
Further, the curing agent is aliphatic polyol amine type curing agent, cycloaliphatic polyols amine type curing agent, aromatic amine type
Curing agent, anhydride curing agent, polyamide type curing agent, modified amine type curing agent and synthetic resin epoxy hardener
In any one or more.
Further, after curing agent adds progress after mixing when being activated in the electroless copper activator
Continuous operation.
A kind of method of full addition production route, which comprises the steps of:
The preinstalled circuit figure with catalytic activity is formed in substrate surface using electroless copper activator；To described default
Electroless copper is carried out after circuitous pattern solidification, to form objective circuit in substrate surface.
Further, the method for the present invention full addition production route based on above-mentioned electroless copper activator, the present invention exists
This is repeated no more.
Further, the substrate is rigid insulation substrate or flexible insulating substrate, the rigid insulation substrate include:
FR-4 substrate, glass substrate, aluminium oxide ceramics or aluminum nitride ceramic substrate；The flexibility insulating substrate includes: paper base film, gathers
Ethylene glycol terephthalate film (PET, Polyethylene terephthalate), Kapton (PI,
) or polytetrafluoroethylene film (PTFE, Poly tetra fluoroethylene) Polyimide.
Further, the preinstalled circuit figure is prepared by the way of inkjet printing or silk-screen printing in substrate surface.
Further, it needs to clean substrate before ink jet printing or silk-screen printing activator, cleaning reagent used is to go
Ionized water and dehydrated alcohol, cleaning instrument are ultrasonic washing instrument；The concrete operations of substrate cleaning are as follows: in ultrasonic cleaning item
Under part, substrate is first put into 5~10min of cleaning in deionized water, is subsequently placed into dehydrated alcohol and cleans 5min, finally place into
5min is cleaned in deionized water；Ultrasonic washing instrument power is 110W, frequency 40KHz.
Further, to ensure that activator can make on substrate, inkjet printing or silk-screen printing activator it is viscous
Degree control is in 50~80mPaS, and surface tension is between 25~45mN/m.
According to embodiments of the present invention, the formula of copper plating bath used in the electroless copper is specific as follows: four hydration potassium tartrates
Sodium (32g/L), two ethylenediamine hydrate tetraacethyl disodiums (2.5g/L), Salzburg vitriol (12.5g/L), six hydration nickel sulfate
(3.5g/L), 2,2'- bipyridyl (10mg/L), three hydrations potassium ferrocyanide (23mg/L), sodium hydroxide (10g/L), formaldehyde are molten
Liquid (12ml/L).
It is preferred that blasting air to copper plating bath during electroless copper to improve the stability of plating solution, air
Flow is preferably 2.5~5cm3/min, and bath temperature controls between 36~45 DEG C, and electroless plating time is controlled in 30~60min.
The principle of the present invention is specific as follows:
(1), complexing agent is added in activator system of the present invention, on the one hand, (i.e. using complexing agent adsorption catalyst ion
Metal ion) and then can be stabilized in system, so that catalyst ion be avoided to be restored by the epoxy group in epoxy resin
For metal nanoparticle, there is metal nanoparticle catalyst reunion, cause catalyst distribution uneven, prevents activator from spraying
It is blocked in ink printing or screen printing process and the chemical layers of copper plated out is uneven.Ionic activator in the present invention can
Guarantee that catalyst ion is uniformly distributed, during electroless copper, catalyst metal ion in-situ reducing is by reducing agent first
Metallic atom, then metallic atom is reduced agent as catalysis core catalysis copper ion and is reduced to the table that metallic copper is deposited on catalysis core
Face forms uniform copper coating；On the other hand, complexing agent of the present invention contains unsatisfied chemical bond, in the curing process, complexing agent
In unsaturated bond and adhesive in epoxy group between can be chemically bonded.Compared to the complexing without containing saturation double bond
There is only physical absorptions between agent, with adhesive, and during electroless copper, the complexing agent of adsorption catalyst ion will be molten
It solves in chemical bronze plating liquid, plating solution is caused to scrap.Therefore the present invention can be avoided be adsorbed with the complexing agent of catalyst ion by
In can not solidify and subsequent bath system loss cause plating solution to scrap, guarantee substrate surface have enough catalytic sites come into
One step realizes subsequent chemistry copper facing.
(2), the present invention chooses various epoxy resin as the bridge layer between electroless copper and substrate, on the one hand, epoxy
Resin itself is used as a kind of adhesive, can adsorb various substrate surfaces, the epoxy group energy energy in another aspect epoxy resin
Enough hydroxyls with substrate surface, carbonyl and the group containing lone pair electrons are chemically bonded.Therefore, epoxy resin conduct is chosen
Bridge stratum bridge layer has universality.
(3), complexing agent and adhesive of the present invention dissolve each other, and catalyst ion can uniformly divide under complexing agent effect in this way
Cloth is evenly distributed in activator system in adhesive, can be completed by inkjet printing or silk-screen printing with a step
Insulating substrate Surface Creation bridge layer and uniform fixed catalyst ion enormously simplify production technology, last fiting chemical plating
Conductive pattern needed for copper obtains technique.
Compared with prior art, beneficial effects of the present invention are as follows:
The present invention by increase on the basis of conventional activation agent the complexing agent to dissolve each other and adhesive and with adhesive
The curing agent matched, by selecting the complexing agent containing unsaturated bond, so that being inhaled in forming the solidification process after preinstalled circuit figure
The complexing agent of attached catalyst can generate chemical reaction with adhesive and be stable in the presence of substrate surface；Due to adhesive itself with
Binding force is good between substrate, and equally distributed catalyst in the activator on substrate surface layer, therefore the present invention realizes a step
Bridge layer and catalyst are formed in substrate surface, cooperation subsequent chemistry depositing process can form fine and close, bright, adhesive force is strong plating
Layer.Compared to the method for existing full addition production route, for circuit manufacturing method of the present invention it is not necessary that bridge layer is prepared separately, substrate is suitable
It is strong with property, operating process is simplified, fabrication cycle is short, hence it is evident that improves production efficiency；Meanwhile with route production side of the present invention
Method, since when forming preinstalled circuit figure, sticky flux makes active layer and substrate surface binding force good, subsequent work
The activation site catalytic copper for changing layer surface deposits to form fine and close, uniform layers of copper, therefore dielectric resin material has been used to carry out glue
The viscous electric conductivity that route will not be influenced as conventional conductive ink.Electroless copper activator of the present invention is the molten of stable homogeneous
Liquid system, raw material is cheap and easy to get, wherein only it is applicable in a small amount of noble metal as metal ion catalyst, it is at low cost, and do not deposit
In nano-metal particle, thus the problem of conventional conductive ink is easy occluding device is also not present.
Detailed description of the invention
Fig. 1 is that a kind of electroless copper activator provided by the invention and full addition make printed wiring flow diagram.
Fig. 2 is Coating composition and crystallization situation analysis figure after electroless copper of the present invention: (a) being EDS energy spectrum analysis figure；(b)
For XRD diagram.
Fig. 3 is the SEM figure of conducting wire after electroless copper of the present invention.
Fig. 4 is the 3M adhesive tape test figure of conducting wire after electroless copper of the present invention.
Fig. 5 is the present invention in curved substrates surface production conducting wire figure.
Fig. 6 is that the present invention carries out radius r=2mm to flexible parent metal conducting wire and bending angle is 180 ° of antifatigue surveys
Examination.
Specific embodiment
Technical solution of the present invention is described in detail with Figure of description combined with specific embodiments below:
The present invention provides a kind of electroless copper activator, including organic solvent and is dissolved in the metal of the organic solvent
Ionic catalyst, complexing agent, adhesive and curing agent；Make its same adhesive in solidification containing unsaturated bond in the complexing agent
Between form chemical bond and be dissolved in solution system, the complexing agent adsorbs metal ion in the metal ion catalyst,
And complexing agent dissolves each other with adhesive so that the metal ion of complexing agent absorption is uniformly distributed in adhesive.
The present invention also provides a kind of full additions to make circuit technique thereof, and process flow is as shown in Figure 1, specifically include following step
It is rapid:
(a) under room temperature condition and magnetic agitation, complexing agent is dissolved in organic solvent；
(b) catalyst is added, keeps magnetic agitation until being completely dissolved；
(c) adhesive is added, continues magnetic agitation until being completely dissolved；
(d) curing agent, magnetic agitation 1h is added；Substrate is cleaned simultaneously, be first placed into deionized water ultrasound 5~
10min is subsequently placed into ultrasound 5min in dehydrated alcohol, is then rinsed again with deionized water, is finally putting into baking oven drying；
(e) activator is printed on by ink jet printing device or silk-screen printing the surface of clean insulating substrate, forms tool
There is the preinstalled circuit figure of catalytic activity；
(f) after room temperature curing, fiting chemical copper facing obtains required conductive pattern.
Embodiment 1:
Thiocarbamide is chosen as complexing agent, is dissolved in propylene glycol monomethyl ether, obtains under the conditions of room temperature and magnetic agitation 200r/min
Thiourea concentration is the solution of 0.03mol/L；Catalyst AgNO is added3, it is completely dissolved under magnetic agitation, obtaining concentration of silver ions is
The solution of 0.01mol/L；It is subsequently added into the bisphenol A epoxide resin of 1.5mol/L, is completely dissolved under magnetic agitation；Then it is added suitable
593 magnetic agitation of curing agent of amount is uniform, and until viscosity is 50~80mPaS, surface tension is between 25~45mN/m；It borrows
It helps ink jet printing device activator to be printed on the surface of epoxy glass substrate, forms the preinstalled circuit figure with catalytic activity；
Fiting chemical copper facing after room temperature curing obtains required conductive pattern.
Fig. 2 a is the EDS energy spectrum analysis figure of layers of copper after electroless copper, as we know from the figure the only energy spectral peak of copper, illustrates conduction
The metal deposited in route only has copper, Fig. 2 b is the XRD diffraction analysis figure of layers of copper after electroless copper, as we can see from the figure copper
Crystal face peak crystallization is sharp, illustrates the well-crystallized of copper in plating process.
Fig. 3 is the SEM figure of conducting wire after electroless copper, and the crystal grain distribution that can see coating in figure is uniform, and particle is big
Small is 300~400nm and compact crystallization.Resistivity by copper conductive traces known to test is about 2.8 × 10-6Ω cm, tool
There is good electric conductivity.
Embodiment 2:
The operation of the present embodiment is substantially same as Example 1, the difference is that the composition of electroless copper activator is specific
Are as follows: organic solvent is propylene glycol methyl ether acetate, and the concentration of 3- Mercaptopropyltriethoxysilane is 0.1mol/L, AgNO3's
Concentration is 0.015mol/L, and the concentration of novolac epoxy resin is 2mol/L, and it is uniform to be added suitable 593 magnetic agitation of curing agent,
Until viscosity is 50~80mPaS, surface tension is between 25~45mN/m.
The amyl- 2,4- dialkylene -1- thioketones (C of ring5H4) and 1- pyrroles's -1- mercaptan (C S4H5NS)
Embodiment 3:
The operation of the present embodiment is substantially same as Example 1, the difference is that the composition of electroless copper activator is specific
Are as follows: organic solvent is dipropylene glycol methyl ether, and the concentration of 3-aminopropyltriethoxysilane is 0.5mol/L, AgNO3Concentration
For 0.02mol/L, the concentration of glycerin ether epoxy resin is 3mol/L, and it is uniform to be added suitable 593 magnetic agitation of curing agent, until
Viscosity is 50~80mPaS, and surface tension is between 25~45mN/m.
Embodiment 4:
The operation of the present embodiment is substantially same as Example 1, the difference is that the composition of electroless copper activator is specific
Are as follows: organic solvent is dipropylene glycol methyl ether acetate, and the concentration of amyl- 2, the 4- dialkylene -1- thioketones of ring is 0.4mol/L, AgNO3
Concentration be 0.01mol/L, the concentration of cycloaliphatic epoxy resin is 5mol/L, and it is equal that suitable 593 magnetic agitation of curing agent is added
Even, until viscosity is 50~80mPaS, surface tension is between 25~45mN/m.
Embodiment 5:
The operation of the present embodiment is substantially same as Example 1, the difference is that the composition of electroless copper activator is specific
Are as follows: organic solvent is propylene glycol monomethyl ether, and the concentration of thiosemicarbazides is 0.5mol/L, AgNO3Concentration be 0.02mol/L, bisphenol-A
The concentration of epoxy resin is 3mol/L, and it is uniform to be added suitable 593 magnetic agitation of curing agent, until viscosity is 50~80mPa
S, surface tension is between 25~45mN/m.
Embodiment 6:
The operation of the present embodiment is substantially same as Example 1, the difference is that the composition of electroless copper activator is specific
Are as follows: organic solvent is propandiol butyl ether, and α-chloromethyl thiophene concentration is 0.05mol/L, AgNO3Concentration be 0.01mol/L,
The concentration of glycerin ether epoxy resin is 6mol/L, and it is uniform to be added suitable 593 magnetic agitation of curing agent, until viscosity is 50~
80mPaS, surface tension is between 25~45mN/m.
Embodiment 7:
Compared with Example 1, difference is the present embodiment: it is thin that embodiment 2 chooses the polyimides that base material thickness is 125 μm
Film (PI), remaining operating procedure are same as Example 1.
From Fig. 4 a can be seen that electroless copper after conducting wire be uniformly distributed on the surface PI, it can be seen that warp from Fig. 4 b
There is no copper scale to be sticked on 3M adhesive tape after crossing 3M adhesive tape test, illustrates to have between copper conductive traces and substrate prepared by the present invention good
Good caking property.
Embodiment 8:
Compared with Example 1, difference is the present embodiment, and embodiment 3 chooses the poly- terephthaldehyde that base material thickness is 125 μm
Sour glycol ester film (PET), activator are printed on the surface of substrate by inkjet printing, remaining operating procedure and embodiment 1
It is identical.
It is seen from figure 5 that conducting wire can be prepared in curved pet sheet face, illustrate that the present invention can not only be in plane base
Material surface prepares conducting wire, equally can prepare conducting wire on three-dimensional substrates surface.
Crooked test further is carried out to the copper wire for being produced on PET concave surface, test results are shown in figure 6.Fig. 6 a is
To copper conductive traces carry out radius be 2mm and bending angle be 180 ° of pulling force and pressure crooked test test；Fig. 6 b is right respectively
Copper wire carries out the ratio (R of 1000 180 ° of pulling force and pressure resistance after bending and initial resistance0Represent initial resistance, R generation
Table carries out the resistance value after certain number of bends), from Fig. 6 b it can be seen that carry out 1000 180 ° of pressure bend tests after,
R/R0=1.006, carry out R/R after 1000 180 ° of pulling force bend tests0=1.034, illustrate regardless of carrying out 1000 180 ° of pressure
Bend test or pulling force bend test, the variation of resistance are all very small.Therefore, have with our the flexible copper circuits of method production
Certain application value.
Embodiment 9:
Compared with Example 1, difference is the present embodiment, embodiment 4 choose substrate be glass baseplate, remaining operation with
Embodiment 1 is identical.Illustrated by EDS, XRD, SEM and 3M adhesive tape test identical with embodiment 1 and embodiment 2: in glass base
The metal of the conductive pattern deposition obtained on material equally also only has metallic copper, and copper grain crystalline even compact, electric conductivity is good,
Copper conductive traces and substrate have good binding force.
Embodiment 10:
The present embodiment studies the influence of the proportion of complexing agent and metal ion catalyst:
In the present embodiment under the conditions of room temperature and magnetic agitation 200r/min, in 10ml propylene glycol monomethyl ether solubility range
It is interior, when n (thiocarbamide): when n (silver nitrate) < 3:1, white precipitate generation is had in solution, it is preliminary to infer that white precipitate is silver ion
The product generated is combined with propylene glycol monomethyl ether, confirms that white precipitate is ((1- methoxyl group by XRD test and thermogravimetric analysis (TGA)
Propyl- 2- yl) oxygroup) silver；Under similarity condition, in 10ml propylene glycol monomethyl ether solubility range, when n (thiocarbamide): n (silver nitrate) >=
When 3:1, colourless transparent solution can be obtained.When n (thiocarbamide): when n (silver nitrate) >=3:1, all silver ions of solution all with thiocarbamide
Complexing, the silver ion not dissociated exist, and avoid silver ion and solvent propylene glycol methyl ether generates white precipitate.Therefore, in order to
Guarantee stability requirement n (thiocarbamide): n (silver nitrate) >=3:1 of activator of the present invention.
Embodiment 11:
The present embodiment studies action principle of the different complexing agents in system:
Thiocarbamide or thiophene containing double bonds are matched as complexing agent according to present invention process process in the present embodiment selecting structure
Activator processed, is similarly obtained clear solution, and printing activator carries out infrared spectroscopy survey after to be activated dose of solidification at preinstalled circuit
Examination.Test result shows that double bond in complexing agent and adhesive epoxide epoxy group group disappear, illustrate in adhesive solidification process with
Complexing agent is chemically bonded, and cooperation subsequent chemistry copper facing in this way can obtain the good layers of copper of binding force.
Comparative example 1:
The 3-aminopropyltriethoxysilane that selection molecular structure only contains singly-bound in the present embodiment is pressed as complexing agent
Activator is prepared according to present invention process process, clear solution is obtained, preinstalled circuit figure is prepared by inkjet printing or silk screen, to
Electroless copper is carried out after activator solidification.
Comparative example 2:
Molecular structure is chosen in the present embodiment only contains the carboxyl benzenethiol of singly-bound as complexing agent, according to present invention process
Process prepares activator, obtains clear solution, preinstalled circuit figure is prepared by inkjet printing or silk screen, after to be activated dose of solidification
Carry out electroless copper.
By being carried out to above-mentioned two comparative example the study found that carrying out full addition using the complexing agent only containing singly-bound
Route production, institute is scrapped quickly using chemical plating fluid, and there is no layers of copper depositions for activation layer surface；Pass through examination of infrared spectrum
It was found that illustrating that there is only physical absorptions between adhesive and complexing agent, in electroless copper with the presence of complexing agent in chemical bronze plating liquid
When complexing agent can be dissolved in chemical bronze plating liquid.
In conclusion the present invention provides a kind of electroless copper activators and full addition to make printed wiring method, we
Method has universality to different substrates, easy to operate, economic and environment-friendly, and the copper wire surface of production is bright fine and close, electric conductivity
Excellent, route and substrate binding force are good, and can make conducting wire on three-dimensional substrates surface, and there is certain scale to push away
Wide value.
The embodiment of the present invention is elaborated in conjunction with attached drawing above, but the invention is not limited to above-mentioned
Specific embodiment, above-mentioned specific embodiment is only schematical, rather than restrictive, the ordinary skill people of this field
Member under the inspiration of the present invention, can also make many in the case where not departing from present inventive concept and claimed range
Deformation, these belong to protection of the invention.
Claims (10)
1. a kind of electroless copper activator, which is characterized in that the activator includes organic solvent and is dissolved in described organic
Metal ion catalyst, complexing agent, adhesive and the curing agent of solvent；Solidifying it containing unsaturated bond in the complexing agent
When with chemical bond is formed between adhesive, the complexing agent adsorbs the metal ion catalyst, and complexing agent and adhesive
It dissolves each other so that the metal ion of complexing agent absorption is uniformly distributed in adhesive.
2. electroless copper activator as described in claim 1, which is characterized in that the metal ion catalyst be silver nitrate,
Any one or more in silver acetate, silver oxalate, silver benzoate, palladium acetate and oxalic acid palladium.
3. electroless copper activator as described in claim 1, which is characterized in that the complexing agent be thiourea process,
The amyl- 2,4- dialkylene-of thiophene and derivatives, 3- Mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, ring
Any one or more in 1- thioketones and 1- pyrroles's -1- mercaptan.
4. electroless copper activator as described in claim 1, which is characterized in that the complexing agent and metal ion catalyst
Molar ratio is not less than 3: 1.
5. electroless copper activator as described in claim 1, which is characterized in that the adhesive is epoxy resin gluing
Agent, including bisphenol A epoxide resin, novolac epoxy resin, glycerin ether epoxy resin, glycidyl ester type epoxy resin, amido ring
Any one or more object in oxygen resin and cycloaliphatic epoxy resin.
6. electroless copper activator as described in claim 1, which is characterized in that the organic solvent is propylene glycol monomethyl ether, third
Any one or more in glycol methyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate and propandiol butyl ether.
7. electroless copper activator as described in claim 1, which is characterized in that the curing agent is the solidification of aliphatic polyol amine type
Agent, cycloaliphatic polyols amine type curing agent, aromatic amine type curing agent, anhydride curing agent, polyamide type curing agent, modified amine
Any one or more in type curing agent and synthetic resin epoxy hardener.
8. electroless copper activator as described in claim 1, which is characterized in that complexing agent in the electroless copper activator
Molar concentration is 0.03~0.6mol/L, and the molar concentration of catalyst is 0.01~0.02mol/L, and the molar concentration of adhesive is
1~5mol/L, the molal weight of curing agent are 0.2~1mol/L.
9. the preparation method of electroless copper activator as described in any one of claim 1 to 8, which is characterized in that including walking as follows
It is rapid:
Step 1: complexing agent, metal ion catalyst being dissolved in organic solvent, is uniformly mixed, obtains solution；
Step 2: adhesive and curing agent being dissolved in the solution that step 1 obtains, are uniformly mixed, obtain the chemical plating work in copper
Agent.
10. the method for the full addition production route based on any one of claim 1 to the 8 electroless copper activator, feature
It is, includes the following steps: to form the preinstalled circuit figure with catalytic activity in substrate surface using electroless copper activator；
Electroless copper is carried out after preinstalled circuit figure solidification, to form objective circuit in substrate surface.
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| CN201910005820.2A CN109487249B (en) | 2019-01-03 | 2019-01-03 | Chemical copper plating activator, preparation method thereof and method for manufacturing circuit by full addition based on activator |
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| CN115537788A (en) * | 2022-08-29 | 2022-12-30 | 深圳大学 | Chemical plating activator and preparation method and application thereof |
| CN115976501A (en) * | 2022-12-27 | 2023-04-18 | 电子科技大学 | Metal pattern on surface of insulating base material and additive manufacturing method |
| CN116782516A (en) * | 2023-07-13 | 2023-09-19 | 南华大学 | Universal process for preparing copper printed circuit based on homogeneous ion type catalytic ink |
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