CN104830247B - A kind of green economical conducting resinl of Halogen low silver content of sheet/dendritic silver-plated copper powder and alternative traditional high silver content - Google Patents
A kind of green economical conducting resinl of Halogen low silver content of sheet/dendritic silver-plated copper powder and alternative traditional high silver content Download PDFInfo
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Abstract
The present invention relates to sheet/dendritic silver-plated copper powder, the green economical epoxy conducting of Halogen low silver content of alternative traditional high silver content and preparation method thereof.Sheet/dendritic silver-plated copper powder, its pattern is sheet and/or dendritic, and the silver-colored area clad ratio of Copper Powder Surface is that the content of allumen in 90~95%, silver-plated copper powder is less than 15wt%.The green economical conducting resinl of Halogen low silver content of alternative traditional high silver content, it is made up of each raw material of following percentage by weight：Sheet/dendritic silver-plated copper powder 60~90%, micron order silver powder 0~30%, epoxy resin 6~12%, reactive diluent 1~8%, toughened resin 1~6%, curing agent 1~3%, curing accelerator 0~1%, coupling agent 0.5~2%.The sheet that the present invention is provided/dendritic silver-plated copper powder, Cu surfaces silver clad ratio is high, and electric conductivity is excellent, and then the conductive adhesive performance prepared by it is excellent, and price is low, intrinsic conductivity is good.
Description
Technical field
The present invention relates to a kind of conducting resinl and preparation method thereof, more particularly to a kind of epoxide resin conductive adhesive and its preparation side
Method.It can be widely used for electronics and microelectronics Packaging.
Background technology
In microelectronics Packaging field, the environmental pollution caused by tin-lead solder increasingly causes the concern of people, reduce or
Limit the use to lead turns into inexorable trend, starts within 2004 the use of lead in Japanese ban electronic product, in Europe
The use of legislation ban and limitation lead in this connection, and also there are the trend imitated in American States.
As the substitute of tin-lead solder, conducting resinl has that environment-friendly, processing conditions is gentle, technique is simple and line is differentiated
The advantages of rate is small, has caused the broad interest of people.Greatly develop conducting resinl substitution tin-lead solder, the development to electronic technology
And the protection of environment has extremely important meaning, more extensive with what is studied conductive adhesive performance, conducting resinl replaces tin
Kupper solder has become a kind of trend.But the problems such as conducting resinl generally existing electrical conductivity is relatively low and contact resistance is unstable poor.
Therefore, develop function admirable, the conducting resinl of traditional plumber's solder can be replaced to turn into the focus that people study.
Conducting resinl can be divided into structural type and the major class of filled-type two by matrix composition.Structural type refers to as conducting resinl matrix
High polymer material is conductive conducting resinl in itself；Filled-type refers to usual adhesive as matrix, and is led by addition
Conductive fillers make glue have the conducting resinl of electric action.Preparing for current conducting polymer composite is sufficiently complex, answered from actual
With also larger distance, therefore widely used is filled conductive glue.
Filled conductive glue is typically what is be made up of matrix resin and conductive filler two large divisions.Wherein, conductive filler master
If metal dust (Ag, Cu, Ni etc.), silver powder has good conductivity and the strong advantage of oxidation resistance concurrently, but expensive, and
Silver-colored transport phenomena easily occurs under hygrothermal environment, causes silver conductive adhesive resistance unstable；Copper powder price is relatively low, good conductivity,
But its oxidation resistance is poor, it is chronically exposed to surface in air and easily forms oxide-film to have a significant impact to its electrical property.And
Silver-plated copper powder remains the good electric conductivity of silver, and silver coating is effectively prevented the oxidation of copper, and its cost is relative to silver
Powder is greatly reduced.Therefore, it can be used as ideal conductive filler.But at present in industry the silver-plated copper powder for preparing there is also
Some problems：Copper Powder Surface by silverskin without being covered completely, and its electric conductivity, inoxidizability still are below fine silver powder；Silvering with
The adhesion of copper powder is not strong, causes the phenomenon that coating comes off during use.These problems limit silver-plated copper powder in electronic seal
The application in dress field.Patent of invention (patent No. CN101244459) is disclosed before the modifying function using rare earth, copper powder chemical plating
Ultrasonic assistant is used during activation, sensitization and chemical plating, institute's acquisition silver coating is evenly distributed, surface is smooth, there is higher
Conductance and inoxidizability.At present studies have reported that fusion method, which prepares silver alloy addition rare earth element, can improve inoxidizability
Can, but be in the case that a small amount of rare earth metal contained in above-mentioned patent in its silver coating forms stable metallographic without melting
The no inoxidizability that can improve waits discussion.Patent of invention (patent No. CN101709461) is the chemical silvering that a kind of copper powder is replaced
Method, it is necessary to the composition containing palladium salt catalytic liquid pretreatment, plant discrete palladium particle in advance in Copper Powder Surface.Patent of invention (patent
Number CN1369341) in prepared dendroid silver powder, the preparation method need to add appropriate height in the suspension of superfine cupper powder
The silver ion of molecule protection, makes silver ion occur displacement reaction with copper, finally obtains the fine silver powder of dendritic superfine.In this method
Copper is only displacement metal, eventually consumes complete, and which introduces macromolecule dispersant, and also the washing collection belt to silver powder comes numb
It is tired.
The content of the invention
There is provided a kind of sheet/dendritic silver-plated copper powder, alternative traditional Gao Yin for the problem of present invention exists for prior art
Green economical epoxy conducting of Halogen low silver content of content and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of sheet/dendritic silver-plated copper powder, pattern is sheet and/or dendritic, and the area clad ratio of Copper Powder Surface silver is 90
~95%, the content of allumen is less than 15wt% in silver-plated copper powder.
By such scheme, above-mentioned sheet/dendritic silver-plated copper powder is with diffused prealloy (pre-diffused alloy
Powder) copper powder (multi-element metal powder/alloyed powder) is substrate, is obtained after chemical silvering through post processing, the diffused is pre-
Alloy copper powder is mixed by 0~15wt% silver powder, 70~90wt% copper powders, 1~25wt% zinc aluminium alloy powders by weight percentage
What ball milling was obtained, wherein：Copper powder size ＞ silver powder particle diameter >=zinc aluminium alloy powder particle diameter.
By such scheme, 1~3wt% of allumen (allumen) the powder aluminum content.
By such scheme, the diffused prealloy copper powder is first under ultrasound condition, by acetone, diluted acid, deionization
Chemical silvering is carried out again after water cleaning.
By such scheme, the ball milling is high energy ball mill ball milling, and the high energy ball mill is oscillatory type ball mill, stirring
One kind in formula ball mill, planetary ball mill, ball grinder is steel matter, and abrading-ball uses steel ball or high-density zirconium ball, another to be equipped with
Jacket cooling system, to control system temperature during ball milling to be not higher than 200 DEG C；Ball-milling Time is 1~72 hour.
By such scheme, the particle diameter for the diffused prealloy copper powder that the ball milling is obtained is 0.1~15 micron.
By such scheme, the chemical plating liquid composition：
Soluble silver salt：10~50g/L,
Reducing agent：5~25g/L,
Complexing agent：10~60g/L,
Stabilizer：1~40mg/L,
Foaming agent：1~10 μ g/L.
By such scheme, it by the preconditioning of chemical plating liquid pH adjusting agent is after 10~14, to add that the chemical silvering, which is,
Diffused prealloy copper powder, carries out the silver-plated processing of sonochemistry.
By such scheme, described the sonochemistry silver-plated 20~80KHz of frequency used, 50~450W of power, temperature
25~70 DEG C, 5~30min of reaction time, using batch (-type) ultrasound.
By such scheme, described PH conditioning agents are ammoniacal liquor or acetic acid.
By such scheme, described silver salt is silver nitrate, and the reducing agent is formaldehyde, and complexing agent is EDTA, and stabilizer is
Bipyridyl, foaming agent is polyethylene glycol.
By such scheme, the post processing is is washed the system after chemical silvering, then at 150~300 after drying
DEG C reducing atmosphere calcines 30~120min and obtains silver-plated copper powder, is subsequently placed in nitrogen and protects storage
A kind of green economical conducting resinl of Halogen low silver content of alternative traditional high silver content, it is by following weight percent
Each raw material composition of ratio：Sheet/dendritic silver-plated copper powder 60~90%, micron order silver powder 0~30%, epoxy resin 6~12% is living
Property diluent 1~8%, toughened resin 1~6%, curing agent 1~3%, curing accelerator 0~1%, coupling agent 0.5~2%.
By such scheme, the mixing that described micron order silver powder is sheet, dendroid, spherical or various shapes are constituted
Thing, its particle size range is 0.1~15 micron.
By such scheme, described epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, acrylic acid modified
One or more in epoxy resin, modifying epoxy resin by organosilicon.
By such scheme, described reactive diluent is BDO glycidol ether, neopentyl glycol glycidol ether,
1,6- hexanediol diglycidyl ether, diethylene glycol glycidol ether, Isosorbide-5-Nitrae-cyclohexane diol glycidol ether, trihydroxy methyl third
One or more in alkane glycidol ether, polyethyleneglycol diglycidylether.
By such scheme, described toughened resin is amine terminated polyether imide resin, end carboxyl polyetherimide resin,
In nbr carboxyl terminal, hydroxy'terminated butadiene nitrile rubber, amino terminated butadiene acrylonitrile rubber, polysulfide rubber, phenolic hydroxy group polyimide resin
One or more of mixtures.
By such scheme, described curing agent selects many amines or its modifier, be dicyandiamide, MDA,
One or more in diaminodiphenyl ether, diaminodiphenylsulfone and its derivative.
By such scheme, described curing accelerator, from imidazoles or derivatives thereof, is 2- undecyl imidazoles, 2- 17
Alkyl imidazole, 2-ethyl-4-methylimidazole, 1- cyanoethyls -2-ethyl-4-methylimidazole, 2- phenyl -4,5- bishydroxymethyl miaows
Azoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles, 2,4- diaminourea -6- (2- undecyl imidazole -1- ethyls)-S- triazines,
The derivative or 2,4- diaminourea -6- (2- undecyls of 2,4- diaminourea -6- (2- undecyl imidazole -1- ethyls)-S- triazines
Imidazoles -1- ethyls) one or more in-S- triazine salt.
By such scheme, described coupling agent is 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, 3-
Methacryloxypropyl trimethoxy silane, N- (2- aminoethyls) -3- aminopropyl front three oxosilanes, N- aminoethyl -3- ammonia
One or more in hydroxypropyl methyl dimethoxysilane.
A kind of preparation method of the green economical conducting resinl of Halogen low silver content of alternative traditional high silver content, including with
Lower step：
1. by epoxy resin, 1~6% toughened resin and 1~8% reactive diluent that percentage by weight is 6~12%
First time mixing is carried out, A is obtained a homogeneous mixture；
2. percentage by weight is added for 1~3% curing agent, 0~1% curing accelerator, 0.5~2% coupling agent
Enter into mixture A made from step 1, carry out second and mix, obtain a homogeneous mixture；
3. by percentage by weight be 60~90% sheets/dendritic silver-plated copper powder, 0~30% micron order silver powder it is well mixed after
It is added in mixture made from step 2, carries out third time mixing, produce the green Halogen of alternative traditional high silver content
The economical conducting resinl of low silver content.
The electric conductivity of fillibility conducting resinl is provided by the metallic filled, phase mutual connection between colloid interior metal particle
Touch and form conductive path.Conductivity theory is thought to form contact resistance between colloid internal particle and particle, and all contact electricity
The summation of resistance and the intrinsic resistance of particle is the bulk resistor of conducting resinl.As shown by the equation：
Rc=ρi/d+ρi/a
R=M (Rc+Ri)/N
Wherein RcFor interparticle contact resistance, RiFor the intrinsic resistance of particle, d is particle size, ρiTunnel resistance, a
Contact area between son, R is system all-in resistance, and the number of the particle in mono- conductive path of M, N is the number of conductive path.
When the metallic of filling is spherical, contacted between particle and particle for point, contact area is small, electronics is difficult jump
Move, tunnel resistance is larger, poorly conductive.Therefore need to increase connecing between the contact area between particle, or raising particle
Probability is touched to form more conductive paths.When the pattern of particle filled composite is dendritic, interparticle contact area becomes big, and
In the case of the filling rate identical of spherical particle, with more contact points, that is, more conductive paths are formed, therefore it is led
Electrically it is substantially better than spherical particle.Although the contact point of sheet particle filled composite is less than dendroid in the case of identical filling rate,
But the contact area between flakelike powder is bigger, therefore with the electric conductivity more excellent than dendroid.Therefore, dendroid and flake gold
The electric conductivity for belonging to particle is better than spherical particle.Metal is the good conductor of heat, and the heat conduction of conducting resinl and conductive be mainly pass through solidification
The Multi-contact in colloid between conductive filler is realized to set up the path of good hot-fluid and electric current afterwards, so conducting resinl
High thermal conductivity and high conductivity can design realize by the proportion optimizing of conductive filler, the present invention be also based on this and
It is specifically designed synthesis and employs the silver-plated copper powder of sheet/dendritic morphology, and coordinates micron order silver powder, the ring of big particle size distribution range
The selection of each components such as oxygen tree fat and proportioning, to prepare the conducting resinl of electric-conductivity heat-conductivity high.The present invention has compared with prior art
Advantages below：
1. the sheet that the present invention is provided/dendritic silver-plated copper powder, copper surface silver clad ratio is high, electric conductivity is excellent.In addition, plating
The residual area on silver-colored coated copper surface is allumen in silver-bearing copper powder, and allumen can form conductive oxide in oxidation, by
This ensure that conducting resinl electric conductivity while preventing copper from being oxidized, so as to add the ageing-resistant performance of conducting resinl.Enter one
Step ground, the present invention has the laminated structure of dendritic Nano Silver by the superficial growth added silver powder in diffused prealloy powder and prepared
Silver-plated copper powder, can also the dendritic Nano Silver based on its table superficial growth occur to melt curtain coating in solidification, and realize silver-plated copper
The connection coated again between filler of powder, effectively increases the electric conductivity and stability of silver-plated copper powder/epoxide resin conductive adhesive.
Filled out 2. the present invention is prepared for a sheet that class price is low, intrinsic conductivity is good/dendritic silver-plated copper powder as conduction
Material, its main one side reason is that, which employs sheet/dendritic morphology silver-plated copper powder, the sheet/dendritic morphology silver-plated copper powder increases
Multi-contact between filler is added, so as to add conductive and heat conductivility, intrinsic conductivity is good；
3. the conductive adhesive performance that the present invention is provided is superior, is substituted using silver-plated copper powder or part substitutes fine silver powder, reduced
Cost, cheap, good heat conduction effect fully meets Electronic Packaging industry use requirement.
4. the conducting resinl that the present invention is provided can be improved by combination, coupling agent addition of the suitable Halogen resin of selection etc. and filled out
The interaction of particle and interlaminar resin is filled, interface bond strength is improved, the shear strength of silver conductive adhesive is improved, realizes nothing
Halogen.
Brief description of the drawings
Fig. 1 is the silver-plated copper powder shape appearance figure that the embodiment of the present invention 1 is obtained.
Fig. 2 is the flake silver-plated copper powder shape appearance figure that the embodiment of the present invention is obtained.
Embodiment
Preparation technology of the present invention is further described with reference to some examples.
The preparation of embodiment 1-5 silver-plated copper powders：
Embodiment 1：(1) 15g silver powder, 70g copper powders, 15g zinc aluminium alloy powders are placed in ball milling in high energy ball mill and forge 24h,
Obtain diffused prealloy copper powder 100g.Wherein：Copper powder size ＞ silver powder particle diameter >=Zn-Al alloy powder footpath, Zn-Al alloy powder
1~3wt%. of aluminum content
(2) take in step (1) under the conditions of 100g alloy copper powders, ultrasonic agitation respectively at washing 15min in acetone, 3%
2min is washed in dilute sulfuric acid, after deionized water is cleaned three times, is filtered out stand-by after water.
(3) chemical plating fluid is constituted：Main salt (silver nitrate 25g/L), reducing agent (formaldehyde 20g/L), complexing agent (EDTA30g/
L), stabilizer (bipyridyl 30mg/L), foaming agent (the μ g/L of PEG 5) adjusts pH value to 11 using ammoniacal liquor, adds step (2) place
Alloy copper powder after reason, (frequency 40KHz, power 200W, 25 DEG C of temperature, reaction time 10min, are used sonochemistry plating
Batch (-type) ultrasound 5s/min), it is separated by filtration, once, the silver-plated copper powder after washing is put for ethanol cleaning after multiple deionized water cleaning
In vacuum drying chamber, 60 DEG C of dryings 2 hours.
(4) silver-plated copper powder obtained in step (3) is placed in tube furnace, H2：N2=1:Under 9 atmosphere, in 150 DEG C of calcinings
30min, the silver-plated alloy copper powder nitrogen charging of finished product is preserved.
Gained silver-plated copper powder pattern is that how dendritic sheet is, and pattern is as shown in figure 1, measuring powder silver content through titration and being
32.5wt%, the area clad ratio of surface silver is 95%, and resistivity is 2.1 × 10-4Ω·cm.
Embodiment 2-5
The method of reference implementation example 1 prepares silver-plated copper powder.
Wherein in embodiment 2,
Step (3) is：Chemical plating fluid is constituted：Soluble silver salt silver nitrate：10g/L, reducing agent：Formaldehyde 5g/L, complexing agent：
EDTA10g/L, stabilizer：Bipyridyl 10mg/L, foaming agent：PEG 1μg/L.PH value is adjusted to 10 using ammoniacal liquor, adds step
(2) the alloy copper powder after handling, sonochemistry plating (frequency 20KHz, power 200W, temperature 70 C, reaction time 5min,
Using batch (-type) ultrasound, it is separated by filtration, once, the silver-plated copper powder after washing is placed in very for ethanol cleaning after multiple deionized water cleaning
Empty drying box, dries and obtains.
Step (4) is：The silver-plated copper powder obtained in step (3) is placed in tube furnace, H2：N2=1:Under 9 atmosphere, in 200 DEG C
60min is calcined, the silver-plated alloy copper powder nitrogen charging of finished product is preserved.
In embodiment 3, step (3) is：Chemical plating fluid is constituted：Soluble silver salt silver nitrate：50g/L, reducing agent：Formaldehyde
25g/L, complexing agent：EDTA60g/L, stabilizer：Bipyridyl 40mg/L, foaming agent：PEG10μg/L.PH value is adjusted using ammoniacal liquor
To 13, the alloy copper powder added after step (2) processing, sonochemistry plating, frequency 80KHz, power 200W, 25 DEG C of temperature,
Reaction time 10min, using batch (-type) ultrasound, is separated by filtration, and ethanol is cleaned once after multiple deionized water cleaning, after washing
Silver-plated copper powder is placed in vacuum drying chamber, dries and obtains.
Step (4) is：The silver-plated copper powder obtained in step (3) is placed in tube furnace, H2：N2=1:Under 9 atmosphere, in 300 DEG C
30min is calcined, the silver-plated alloy copper powder nitrogen charging of finished product is preserved.
Constituent content and each parameter setting and result in embodiment 1-5, which are characterized, see the table below 1.
Table 1
According to data in embodiment, silver-plated copper powder pattern is added with silver in prediffusion alloy copper powder preparation process in the present invention
Amount and ball-milling technology are relevant.When silver-colored addition is 0%, silver-plated copper powder pattern is based on sheet；With the increase of silver-colored addition, ball milling
Time lengthen, then silver-plated copper powder pattern gradually with sheet it is how dendritic based on.Gained silver-plated copper powder resistivity is relevant with pattern, sheet
Contact area is big, dendritic contact point is more, can reduce silver-plated copper powder powder resistance rate.
The silver-colored clad ratio in silver-plated copper powder powder silver content and surface and silver-colored addition in prediffusion alloy copper powder preparation process,
Zn-Al additions and Electroless Silver Plating are relevant.Allumen accelerates chemical silvering efficiency, removes silver caused by silver-colored addition
Content increases outer, increase chemical plating temperature, extension electroless plating time, can also improve silver-plated copper powder silver content.Except this, reduction is calcined
Post processing can further improve silver-colored clad ratio.
The preparation of embodiment 6-12 conducting resinls, unless otherwise specified, resin, solvent, additive use halogen in embodiment
Cellulose content is less than 50ppm raw material.
Embodiment 6
Weigh raw material according to each component weight proportion in embodiment 6 in table 2, by epoxy resin, reactive diluent Isosorbide-5-Nitrae-
Then butanediol glycidol ether, toughened resin amine terminated polyether imide resin mixing 10min add curing agent double to uniform
Cyanamide, curing accelerator 2- heptadecyl imidazoles and coupling agent 3- aminopropyl triethoxysilanes, 10min is mixed at room temperature to be turned into
Homogeneous mixture, after vacuum defoamation, adds silver-plated copper powder of the particle size range for 1~15 micron of embodiment 5, at room temperature low speed
30min is mixed, then is ground by three-roller until as fine and smooth homogeneous mixture, evacuation and centrifugal degassing 5 minutes, you can conduction is made
Glue.The preparation for preparing conducting resinl in reference implementation example 6 of embodiment 7-10 conducting resinl, simply using the silver-plated copper of embodiment 1
Powder.Comparative example 1 and 2 is provided simultaneously to compare.
Table 2
Conducting resinl made from above-described embodiment 6-10 places 1h in the baking oven that condition of cure is 175 DEG C.Sheared after solidification
Intensity is according to ASTM D1002 are tested, resistivity is tested according to ASTM D257, thermal conductivity factor is according to ASTM C518
Tested, content of halogen is according to EN 14582:2007 standards are tested, heat resisting temperature judges according to reliability test, always
Change experiment using double 85 agings (85 DEG C, 85%RH).Conducting resinl test result prepared by embodiment 6-10 and comparative example 1-2 is seen below
In table 3.
Table 3
As can be seen from the above table, the green Halogen low silver content economy for alternative traditional high silver content that the present invention is provided
Type conducting resinl obtains excellent heat conductivility while good conductance is maintained, and can meet wanting for Electronic Packaging
Ask.
As can be seen that the present invention is prepared using sheet/dendritic silver-plated copper powder from the contrast of embodiment 8 and comparative example 1,2
Conducting resinl, its weather resistance and silver powder (comparative example 1) approaches, and far wins common silver-plated copper powder (comparative example 2).This is adopted with the present invention
It is directly related with sheet/dendritic silver-plated copper powder, silver cladding Cu surfaces in sheet/dendritic silver-plated copper powder that the present invention is used
Residual area is allumen, forms conductive oxide after zinc-aluminium oxidation, ensure that conducting resinl is led while preventing Cu from being oxidized
Electrical property, so as to add the ageing-resistant performance of conducting resinl.Except this, the branch that Copper Powder Surface grows in the how dendritic silver-plated copper powder of sheet
Shape Nano Silver can occur to melt curtain coating in solidification, realize the connection coated again between filler of silver-plated copper powder, thus can enter one
Step effectively improves the electric conductivity and stability of silver-plated copper powder/epoxide resin conductive adhesive.
Claims (9)
1. a kind of sheet/dendritic silver-plated copper powder, pattern is sheet and/or dendritic, the area clad ratio of Copper Powder Surface silver for 90 ~
95%, the content of allumen is less than 15wt% in silver-plated copper powder；Described sheet/dendritic silver-plated copper powder is with diffused prealloy
Copper powder is substrate, is obtained after chemical silvering through post processing, the diffused prealloy copper powder by weight percentage by 0 ~
15wt% silver powder, 70 ~ 90wt% copper powders, 1 ~ 25wt% zinc aluminium alloy powder mixing and ball millings are obtained, wherein：Copper powder size ＞ silver powder grain
Footpath >=zinc aluminium alloy powder particle diameter.
2. sheet according to claim 1/dendritic silver-plated copper powder, it is characterised in that：The zinc aluminium alloy powder aluminum content 1 ~
3wt%。
3. sheet according to claim 1/dendritic silver-plated copper powder, it is characterised in that：The ball milling is high energy ball mill ball
Mill, the high energy ball mill is one kind in oscillatory type ball mill, stirring ball mill, planetary ball mill, and ball grinder is steel
Material, abrading-ball uses steel ball or high-density zirconium ball, jacket cooling system is separately equipped with, to control system temperature during ball milling to be not higher than
200℃；Ball-milling Time is 1 ~ 72 hour, and the particle diameter for the diffused prealloy copper powder that the ball milling is obtained is 0.1 ~ 15 micron.
4. sheet according to claim 1/dendritic silver-plated copper powder, it is characterised in that：
The chemical plating liquid composition：Soluble silver salt：10 ~ 50g/L, reducing agent：5 ~ 25g/L, complexing agent：10 ~ 60g/L, surely
Determine agent：1 ~ 40mg/L, foaming agent：1 ~ 10 μ g/L,
It by the preconditioning of chemical plating liquid pH adjusting agent is after 10 ~ 14, to add diffused prealloy copper powder that the chemical silvering, which is,
Carry out the silver-plated processing of sonochemistry, described the sonochemistry silver-plated 20 ~ 80kHz of frequency used, 50 ~ 450W of power, temperature
25 ~ 70 DEG C of degree, 5 ~ 30min of reaction time, using batch (-type) ultrasound.
5. sheet according to claim 4/dendritic silver-plated copper powder, it is characterised in that：Described pH adjusting agent be ammoniacal liquor or
Acetic acid, described silver salt is silver nitrate, and the reducing agent is formaldehyde, and complexing agent is EDTA, and stabilizer is bipyridyl, and foaming agent is
Polyethylene glycol.
6. sheet according to claim 1/dendritic silver-plated copper powder, it is characterised in that：The post processing is by chemical silvering
System afterwards is washed, and calcining 30 ~ 120min then at 150 ~ 300 DEG C of reducing atmospheres after drying obtains silver-plated copper powder, then puts
Storage is protected in nitrogen.
7. a kind of green economical conducting resinl of Halogen low silver content of alternative traditional high silver content, it is characterised in that：It by with
Each raw material composition of lower percentage by weight：Sheet/dendritic silver-plated copper powder 60 ~ 90% described in claim 1, micron order silver powder 0 ~
30%, epoxy resin 6 ~ 12%, reactive diluent 1 ~ 8%, toughened resin 1 ~ 6%, curing agent 1 ~ 3%, curing accelerator 0 ~ 1%, coupling
Agent 0.5 ~ 2%.
8. the green economical conducting resinl of Halogen low silver content of alternative traditional high silver content according to claim 7, its
It is characterised by：Described micron order silver powder is sheet, dendroid, the mixture of spherical or various shapes composition, its particle diameter model
Enclose for 0.1 ~ 15 micron；
Described epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, acrylic modified epoxy resin, organosilicon
One or more in modified epoxy；
Described reactive diluent is BDO glycidol ether, neopentyl glycol glycidol ether, 1,6- hexylene glycols two contract
Water glycerin ether, diethylene glycol glycidol ether, 1,4- cyclohexane diols glycidol ether, trimethylolpropane glycidol ether,
One or more in polyethyleneglycol diglycidylether；
Described toughened resin be amine terminated polyether imide resin, end carboxyl polyetherimide resin, nbr carboxyl terminal,
It is one or more of mixed in hydroxy'terminated butadiene nitrile rubber, amino terminated butadiene acrylonitrile rubber, polysulfide rubber, phenolic hydroxy group polyimide resin
Compound；
Described curing agent is in dicyandiamide, MDA, diaminodiphenyl ether, diaminodiphenylsulfone and its derivative
One or more；
Described curing accelerator is 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2-ethyl-4-methylimidazole, 1- cyanogen second
Base -2-ethyl-4-methylimidazole, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles,
2,4- diaminourea -6- (2- undecyl imidazole -1- ethyls)-S- triazines, 2,4- diaminourea -6- (2- undecyl imidazole -1- second
Base)-S- triazines derivative or 2,4- diaminourea -6- (2- undecyl imidazole -1- ethyls)-S- triazine salt in one kind or many
Kind；
Described coupling agent is 3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, 3- methacryloxies
Propyl trimethoxy silicane, N- (2- aminoethyls) -3- aminopropyl front three oxosilanes, N- aminoethyl -3- aminopropyltriethoxy dimethoxies
One or more in base silane.
9. the making side of the green economical conducting resinl of Halogen low silver content of alternative traditional high silver content described in claim 7
Method, comprises the following steps：
1）Percentage by weight is carried out for the first time for 6 ~ 12% epoxy resin, 1 ~ 6% toughened resin and 1 ~ 8% reactive diluent
Mixing, obtains a homogeneous mixture A；
2）Percentage by weight is added to step 1 and made for 1 ~ 3% curing agent, 0 ~ 1% curing accelerator, 0.5 ~ 2% coupling agent
In the mixture A obtained, carry out second and mix, obtain a homogeneous mixture；
3）By percentage by weight be 60 ~ 90% sheets/dendritic silver-plated copper powder, 0 ~ 30% micron order silver powder it is well mixed after be added to step
In mixture made from rapid 2, third time mixing is carried out, the green Halogen low silver content of alternative traditional high silver content is produced
Economical conducting resinl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105436499A (en) * | 2015-12-18 | 2016-03-30 | 贵州省冶金化工研究所 | Preparation method of silver-coated copper double-metal powder |
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| CN111205719A (en) * | 2020-03-03 | 2020-05-29 | 深圳市利红金科技有限公司 | Silver-copper conductive paint and preparation method thereof |
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| CN112280216B (en) * | 2020-11-02 | 2023-03-31 | 北京理工大学珠海学院 | Biomass PVC conductive plastic and preparation method thereof |
| CN113066600B (en) * | 2021-03-24 | 2023-03-14 | 北京梦之墨科技有限公司 | Conductive paste and electronic device |
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| CN101905321B (en) * | 2010-08-20 | 2011-11-16 | 中国兵器工业集团第五三研究所 | Preparation method of flake silver-plated copper powder |
| CN102426872B (en) * | 2011-12-28 | 2013-05-08 | 彩虹集团公司 | Low temperature solidified silver paste for keyboard lines and preparation method thereof |
| CN102766426A (en) * | 2012-07-03 | 2012-11-07 | 烟台德邦科技有限公司 | Conductive adhesive for encapsulating semiconductor chip and preparation method thereof |
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