CN104830247A - Sheet/branch silver-coated copper powder and green halogen-free low-silver-content economical electrically conductive adhesive capable of replacing traditional electrically conductive adhesives with high silver contents - Google Patents
Sheet/branch silver-coated copper powder and green halogen-free low-silver-content economical electrically conductive adhesive capable of replacing traditional electrically conductive adhesives with high silver contents Download PDFInfo
- Publication number
- CN104830247A CN104830247A CN201510129222.8A CN201510129222A CN104830247A CN 104830247 A CN104830247 A CN 104830247A CN 201510129222 A CN201510129222 A CN 201510129222A CN 104830247 A CN104830247 A CN 104830247A
- Authority
- CN
- China
- Prior art keywords
- silver
- copper powder
- sheet
- powder
- plated copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to sheet/branch silver-coated copper powder, a green halogen-free low-silver-content economical electrically conductive adhesive capable of replacing traditional electrically conductive adhesives with high silver contents, and a preparing method of the electrically conductive adhesive. The morphology of the sheet/branch silver-coated copper powder is in a sheet shape and/or a branch shape. The silver coating area rate on the surface of copper powder is 90-95%. The content of a zinc-aluminum alloy in the silver-coated copper powder is lower than 15 wt%. The electrically conductive adhesive comprises following raw materials by weight: 60-90% of the sheet/branch silver-coated copper powder, 0-30% of micron order silver power, 6-12% of epoxy resin, 1-8% of an active diluting agent, 1-6% of toughening resin, 1-3% of a curing agent, 0-1% of a curing promoter and 0.5-2% of a coupling agent. The sheet/branch silver-coated copper powder is high in silver coating rate on the surface of Cu and excellent in electrically conductive performance, so that the electrically conductive adhesive prepared from the sheet/branch silver-coated copper powder is excellent in performance, low in cost and good in intrinsic conductivity.
Description
Technical field
The present invention relates to a kind of conductive resin and preparation method thereof, particularly a kind of epoxide resin conductive adhesive and preparation method thereof.Electronics and microelectronics Packaging can be widely used in.
Background technology
In microelectronics Packaging field, environmental pollution caused by wiping solder more and more causes the concern of people, reduce or limit and inexorable trend is become to the use of lead, within 2004, start use plumbous in Japanese ban electronic product, ban of having made laws in Europe use in this connection plumbous with restriction, and also there are the trend imitated in American States.
As the substitute of wiping solder, the advantages such as conductive resin has environmental friendliness, processing conditions is gentle, technique is simple and linear resolution is little, have caused the broad interest of people.Greatly develop conductive resin and replace wiping solder, have extremely important meaning to the development of electronic technology and the protection of environment, more extensive along with to conductive adhesive performance research, conductive resin replacement wiping solder has become a kind of trend.But the problems such as conductive resin ubiquity specific conductivity lower and contact resistance instability difference.Therefore, develop excellent property, the focus that the conductive resin of traditional plumber's solder becomes people's research can be replaced.
Conductive resin can be divided into structure-type and the large class of filled-type two by matrix composition.Structure-type refers to that namely the macromolecular material itself as conductive resin matrix has the conductive resin of electroconductibility; Filled-type refers to that usual tackiness agent is as matrix, and relies on interpolation electroconductive stuffing to make glue have the conductive resin of electric action.The preparation of current conducting polymer composite is very complicated, also have larger distance from practical application, is therefore widely usedly filled conductive glue.
Filled conductive glue is normally made up of matrix resin and conductive filler material two parts.Wherein, conductive filler material is metal-powder (Ag, Cu, Ni etc.) mainly, and silver powder has good conductivity and the strong advantage of resistance of oxidation concurrently, but expensive, and easily silver-colored transport phenomena occurs under hygrothermal environment, causes silver conductive adhesive resistance unstable; Copper powder price is lower, good conductivity, but its resistance of oxidation is poor, and long-term exposure in atmosphere surface easily forms oxide film thus has a significant impact its electrical property.And silver-plated copper powder remains the good electroconductibility of silver, and silver coating effectively prevents the oxidation of copper, and its cost reduces widely relative to silver powder.Therefore, it can be used as ideal conductive filler material.But also there are some problems in the silver-plated copper powder prepared in industry at present: Copper Powder Surface is not covered by silverskin completely, and its electroconductibility, oxidation-resistance are still lower than fine silver powder; The bonding force of silvering and copper powder is not strong, causes the phenomenon that coating in use procedure comes off.These problems limit the application of silver-plated copper powder in Electronic Packaging field.Patent of invention (patent No. CN101244459) discloses the modifying function utilizing rare earth, ultrasonic assistant is adopted in the process of copper powder electroless plating front activating, sensitization and electroless plating, institute's acquisition silvered film is evenly distributed, smooth surface, has higher electric conductivity and oxidation-resistance.Studies have reported that at present scorification is prepared silver alloys and added rare earth element and can improve antioxidant property, but whether can improve oxidation-resistance a small amount of rare earth metal contained in its silvered film in above-mentioned patent forms stable metallographic without melting and wait to inquire into.The method of the chemical silvering that patent of invention (patent No. CN101709461) is replaced for a kind of copper powder, needs the catalytic liquid pre-treatment containing palladium salt component, plants discrete palladium particle in advance at Copper Powder Surface.Dendroid silver powder has been prepared in patent of invention (patent No. CN1369341); this preparation method need add the silver ions of appropriate polymer protection in the suspension liquid of superfine cupper powder; make silver ions and copper generation replacement(metathesis)reaction, finally obtain the fine silver powder of dendritic superfine.In the method, copper is only displacement metal, finally can consume completely, and which introduce macromolecule dispersant, collects also to the washing of silver powder and makes troubles.
Summary of the invention
The present invention is directed to prior art Problems existing, economical epoxy conducting of green Halogen low silver content that a kind of sheet/dendritic silver-plated copper powder, alternative traditional high silver content are provided and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in 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%, and in silver-plated copper powder, the content of aluminium zinc is less than 15wt%.
By such scheme, above-mentioned sheet/dendritic silver-plated copper powder is for substrate with dispersion pattern prealloy (pre-diffused alloy powder) copper powder (multi-element metal powder/alloy powder), obtain through aftertreatment after chemical silvering, described dispersion pattern prealloy copper powder is obtained by 0 ~ 15wt% silver powder, 70 ~ 90wt% copper powder, 1 ~ 25wt% zinc aluminium alloy powder mixing and ball milling by weight percentage, wherein: copper powder size > silver powder particle diameter >=zinc aluminium alloy powder particle diameter.
By such scheme, described aluminium zinc (aluminium zinc) powder aluminum content 1 ~ 3wt%.
By such scheme, described dispersion pattern prealloy copper powder is that through acetone, diluted acid, carries out chemical silvering after washed with de-ionized water more first under ultrasound condition.
By such scheme, described ball milling is high energy ball mill ball milling, described high energy ball mill is the one in oscillatory type ball mill, stirring ball mill, planetary ball mill, ball grinder is steel matter, abrading-ball adopts steel ball or high-density zirconium ball, another outfit jacket cooling system, during to control ball milling, system temperature is not higher than 200 DEG C; Ball-milling Time is 1 ~ 72 hour.
By such scheme, the particle diameter of the dispersion pattern prealloy copper powder that described ball milling obtains is 0.1 ~ 15 micron.
By such scheme, described chemical plating liquid composition:
Soluble silver salt: 10 ~ 50g/L,
Reductive agent: 5 ~ 25g/L,
Complexing agent: 10 ~ 60g/L,
Stablizer: 1 ~ 40mg/L,
Pore forming material: 1 ~ 10 μ g/L.
By such scheme, described chemical silvering, for being after 10 ~ 14 by the preconditioning of chemical plating liquid pH adjusting agent, adding dispersion pattern prealloy copper powder, carries out the silver-plated process of sonochemistry.
By such scheme, the frequency 20 ~ 80KHz of the silver-plated use of described sonochemistry, power 50 ~ 450W, temperature 25 ~ 70 DEG C, reaction times 5 ~ 30min, adopts intermittent type ultrasonic.
By such scheme, described PH conditioning agent is ammoniacal liquor or acetic acid.
By such scheme, described silver salt is Silver Nitrate, and described reductive agent is formaldehyde, and complexing agent is EDTA, and stablizer is dipyridyl, and pore forming material is polyoxyethylene glycol.
By such scheme, described aftertreatment is the system after chemical silvering washed, and obtains silver-plated copper powder again, be then placed in nitrogen protection and store after drying in 150 ~ 300 DEG C of reducing atmosphere calcining 30 ~ 120min
A kind of economical conductive resin of green Halogen low silver content of alternative traditional high silver content, it is made up of each raw material of following weight percent: sheet/dendritic silver-plated copper powder 60 ~ 90%, micron order silver powder 0 ~ 30%, epoxy resin 6 ~ 12%, reactive thinner 1 ~ 8%, toughened resin 1 ~ 6%, solidifying agent 1 ~ 3%, curing catalyst 0 ~ 1%, coupling agent 0.5 ~ 2%.
By such scheme, described micron order silver powder is the mixture of sheet, dendroid, spherical or various shape composition, and its particle size range is 0.1 ~ 15 micron.
By such scheme, described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, acrylic modified epoxy resin, modifying epoxy resin by organosilicon.
By such scheme, described reactive thinner is 1,4-butyleneglycol glycidyl ether, neopentyl glycol glycidyl ether, 1, one or more in 6-hexanediol diglycidyl ether, Diethylene Glycol glycidyl ether, Isosorbide-5-Nitrae-cyclohexane diol glycidyl ether, TriMethylolPropane(TMP) glycidyl ether, polyethyleneglycol diglycidylether.
By such scheme, described toughened resin is the mixture of one or more in Amino Terminated polyether(ATPE) imide resin, end carboxyl polyetherimide resin, nbr carboxyl terminal, hydroxy'terminated butadiene nitrile rubber, amino terminated butadiene acrylonitrile rubber, thiorubber, phenolic hydroxy group polyimide resin.
By such scheme, described solidifying agent selects polyamines class or its modifier, is one or more in Dyhard RU 100, diaminodiphenylmethane, diaminodiphenyl oxide, diaminodiphenylsulfone(DDS) and derivative thereof.
By such scheme, described curing catalyst selects imidazoles or derivatives thereof, for 2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine, 2, the derivative or 2 of 4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine, one or more in 4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine salt.
By such scheme, described coupling agent is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-methacryloxypropyl trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, one or more in N-aminoethyl-3-aminopropyltriethoxy dimethoxysilane.
A making method for the economical conductive resin of green Halogen low silver content of alternative traditional high silver content, comprises the following steps:
1. be the epoxy resin of 6 ~ 12% by weight percent, the toughened resin of 1 ~ 6% and 1 ~ 8% reactive thinner carry out first time mixing, obtain a homogeneous mixture A;
2. be the solidifying agent of 1 ~ 3% by weight percent, the curing catalyst of 0 ~ 1%, the coupling agent of 0.5 ~ 2% join in the obtained mixture A of step 1, carry out second time and mix, obtain a homogeneous mixture;
3. be that 60 ~ 90% sheets/dendritic silver-plated copper powder, 0 ~ 30% micron order silver powder join in the obtained mixture of step 2 after mixing by weight percent, carry out third time mixing, obtain the economical conductive resin of green Halogen low silver content of described alternative traditional high silver content.
The electroconductibility of fillibility conductive resin is that the metallics by filling provides, and contact with each other between colloid interior metal particle formation conductive path.Conductivity theory is thought and is formed contact resistance between colloid inner particles and particle, and the summation of the intrinsic resistance of all contact resistances and particle is the body resistance of conductive resin.As shown by the equation:
R
c＝ρ
i/d+ρ
i/a
R＝M(R
c+R
i)/N
Wherein R
cfor interparticle contact resistance, R
ifor the intrinsic resistance of particle, d is size, ρ
ithen wear resistance, a particle contact area, R is system total electrical resistance, and the number of the particle in M conductive path, N is the number of conductive path.
When the metallics of filling is spherical, be point cantact between particle and particle, contact area is little, and electronics is transition not easily, then wears resistance comparatively large, poorly conductive.Therefore need to increase the contact area between particle, or the contact probability improved between particle is to form more conductive path.When the pattern of particle filled composite is dendritic, interparticle contact area becomes large, and when identical with the filling ratio of spherical particle, has more point of contact, and namely form more conductive path, therefore its electroconductibility is obviously better than spherical particle.Although the point of contact of sheet particle filled composite is less than dendroid when identical filling ratio, the contact area between plate is larger, therefore has the electroconductibility more excellent than dendroid.Therefore, the electroconductibility of dendroid and platelet-like metal particle is better than spherical particle.Metal is the good conductor of heat, the path that the heat conduction of conductive resin and conduction mainly set up good hot-fluid and electric current by the Multi-contact in cured glue body between conductive filler material realizes, so the high thermal conductivity of conductive resin and high conductivity can be realized by the proportion optimizing design of conductive filler material, also based on this, special design and synthesis have employed the silver-plated copper powder of sheet/branched structure just in the present invention, and coordinate selection and the proportioning of each component such as micron order silver powder, epoxy resin of Large stone distribution range, prepare the conductive resin of electric-conductivity heat-conductivity high.The present invention compared with prior art has the following advantages:
1. sheet provided by the invention/dendritic silver-plated copper powder, the silver-colored clad ratio in copper surface is high, and conductivity is excellent.In addition, in silver-plated copper powder, the residual area on silver-colored coated copper surface is aluminium zinc, and aluminium zinc can form conductive oxide when being oxidized, and ensure that conductive resin conductivity thus, thus add the ageing-resistant performance of conductive resin while prevention copper is oxidized.Further, the surface growth that the present invention is prepared by adding silver powder at dispersion pattern prealloy powder has the silver-plated copper powder of the sheet structure of dendritic nanometer silver, also can show epontic dendritic nanometer silver based on it to occur when solidifying to melt curtain coating, and the connection realized between the coated again of silver-plated copper powder and filler, effectively improve conductivity and the stability of silver-plated copper powder/epoxide resin conductive adhesive.
2. the present invention has prepared a sheet that class price is low, intrinsic conductivity is good/dendritic silver-plated copper powder as conductive filler material, its main reason on the one hand which employs sheet/branched structure silver-plated copper powder, this sheet/branched structure silver-plated copper powder adds Multi-contact between filler, thus adding conduction and heat conductivility, intrinsic conductivity is good;
3. conductive adhesive performance provided by the invention is superior, uses silver-plated copper powder to substitute or Some substitute fine silver powder, reduces cost, low price, good heat conduction effect, fully meet the service requirements of Electronic Packaging industry.
4. conductive resin provided by the invention improves the interaction of particle filled composite and interlaminar resin by select the combination of applicable Halogen resin, coupling agent adds etc., improves interface bond strength, improves the shearing resistance of silver conductive adhesive, realize Halogen.
Accompanying drawing explanation
Fig. 1 is the silver-plated copper powder shape appearance figure that the embodiment of the present invention 1 obtains.
Fig. 2 is the flake silver-plated copper powder shape appearance figure that the embodiment of the present invention obtains.
Embodiment
Below in conjunction with some examples, preparation technology of the present invention is further described.
The preparation of embodiment 1-5 silver-plated copper powder:
Embodiment 1:(1) 15g silver powder, 70g copper powder, 15g zinc aluminium alloy powder be placed in high energy ball mill ball milling forging 24h, obtains dispersion pattern prealloy copper powder 100g.Wherein: copper powder size > silver powder particle diameter >=Zn-Al alloy powder footpath, Zn-Al alloy powder aluminum content 1 ~ 3wt%.
(2) get 100g alloy copper powder in step (1), wash 15min respectively in acetone under ultrasonic agitation condition, in the dilute sulphuric acid of 3%, wash 2min, after washed with de-ionized water three times, stand-by after filtering water.
(3) chemical plating fluid composition: main salt (Silver Nitrate 25g/L), reductive agent (formaldehyde 20g/L), complexing agent (EDTA30g/L), stablizer (dipyridyl 30mg/L), pore forming material (PEG 5 μ g/L), utilize ammoniacal liquor adjust ph to 11, add the alloy copper powder after step (2) process, sonochemistry plating (frequency 40KHz, power 200W, temperature 25 DEG C, reaction times 10min, adopt the ultrasonic 5s/min of intermittent type), filtering separation, repeatedly after washed with de-ionized water, ethanol purge is once, silver-plated copper powder after washing is placed in vacuum drying oven, 60 DEG C of dryings 2 hours.
(4) silver-plated copper powder obtained in step (3) is placed in tube furnace, H
2: N
2under=1:9 atmosphere, in 150 DEG C of calcining 30min, the silver-plated alloy copper powder of finished product fills nitrogen and preserves.
Gained silver-plated copper powder pattern is sheet racemosus shape, and as shown in Figure 1, record powder silver content through volumetry is 32.5wt% to pattern, and the area clad ratio of surface silver is 95%, and resistivity is 2.1 × 10
-4Ω cm.
Embodiment 2-5
The method of reference example 1 prepares silver-plated copper powder.
Wherein in embodiment 2,
Step (3) is: chemical plating fluid forms: soluble silver salt Silver Nitrate: 10g/L, reductive agent: formaldehyde 5g/L, complexing agent: EDTA10g/L, stablizer: dipyridyl 10mg/L, pore forming material: PEG 1 μ g/L.Utilize ammoniacal liquor adjust ph to 10, add the alloy copper powder after step (2) process, sonochemistry plating (frequency 20KHz, power 200W, temperature 70 C, reaction times 5min, employing intermittent type is ultrasonic, filtering separation, and repeatedly after washed with de-ionized water, ethanol purge is once, silver-plated copper powder after washing is placed in vacuum drying oven, dry and obtain.
Step (4) is: the silver-plated copper powder obtained in step (3) is placed in tube furnace, H
2: N
2under=1:9 atmosphere, in 200 DEG C of calcining 60min, the silver-plated alloy copper powder of finished product fills nitrogen and preserves.
In embodiment 3, step (3) is: chemical plating fluid forms: soluble silver salt Silver Nitrate: 50g/L, reductive agent: formaldehyde 25g/L, complexing agent: EDTA60g/L, stablizer: dipyridyl 40mg/L, pore forming material: PEG10 μ g/L.Utilize ammoniacal liquor adjust ph to 13, add the alloy copper powder after step (2) process, sonochemistry plating, frequency 80KHz, power 200W, temperature 25 DEG C, reaction times 10min, adopts intermittent type ultrasonic, filtering separation, repeatedly after washed with de-ionized water ethanol purge once, the silver-plated copper powder after washing is placed in vacuum drying oven, dry and obtain.
Step (4) is: the silver-plated copper powder obtained in step (3) is placed in tube furnace, H
2: N
2under=1:9 atmosphere, in 300 DEG C of calcining 30min, the silver-plated alloy copper powder of finished product fills nitrogen and preserves.
Component concentration in embodiment 1-5 and each optimum configurations and result characterize and see the following form 1.
Table 1
According to data in embodiment, in the present invention, silver-plated copper powder pattern is relevant with silver-colored addition in prediffusion alloy copper powder preparation process and ball-milling technology.When silver-colored addition is 0%, silver-plated copper powder pattern is based on sheet; Increase with silver-colored addition, Ball-milling Time lengthens, then silver-plated copper powder pattern is gradually based on sheet racemosus shape.Gained silver-plated copper powder resistivity is relevant with pattern, and sheet contact area is large, dendritic contact point is many, all can reduce silver-plated copper powder powder resistance rate.
Silver-plated copper powder powder silver content and surperficial silver-colored clad ratio relevant with silver-colored addition, Zn-Al addition and Electroless Silver Plating in prediffusion alloy copper powder preparation process.Aluminium zinc accelerates chemical silvering efficiency, removes outside silver content that silver-colored addition causes increases, increases electroless plating temperature, extends electroless plating time, also can improve silver-plated copper powder silver content.Except this, reduction calcining aftertreatment can improve silver-colored clad ratio further.
The preparation of embodiment 6-12 conductive resin, if no special instructions, in embodiment, resin, solvent, additive all adopt content of halogen lower than the raw material of 50ppm.
Embodiment 6
Raw material is taken according to each composition weight proportioning in embodiment in table 26, by epoxy resin, reactive thinner 1, 4-butyleneglycol glycidyl ether, toughened resin Amino Terminated polyether(ATPE) imide resin mixing 10min is to even, then curing agent dicyandiamide is added, curing catalyst 2-heptadecyl imidazole and coupling agent 3-aminopropyl triethoxysilane, mix 10min under room temperature and become uniform mixture, after vacuum defoamation, add the silver-plated copper powder that particle size range is the embodiment 5 of 1 ~ 15 micron, low speed mixing 30min under room temperature, grind until become fine and smooth uniform mixture through three-roller again, evacuation and centrifugal degassing 5 minutes, conductive resin can be obtained.The preparation of conductive resin in the preparation reference example 6 of the conductive resin of embodiment 7-10, just uses the silver-plated copper powder of embodiment 1.There is provided comparative example 1 and 2 to contrast simultaneously.
Table 2
The conductive resin that above-described embodiment 6-10 obtains is place 1h in the baking oven of 175 DEG C at condition of cure.After solidification, shearing resistance carries out testing according to ASTM D1002, resistivity carries out testing according to ASTM D257, thermal conductivity carries out testing according to ASTM C518, content of halogen carries out testing according to EN 14582:2007 standard, heat resisting temperature judges according to reliability test, and weathering test adopts two 85 aging (85 DEG C, 85%RH).Conductive resin test result prepared by embodiment 6-10 and comparative example 1-2 sees the following form in 3.
Table 3
As can be seen from the above table, the economical conductive resin of green Halogen low silver content of alternative traditional high silver content provided by the invention obtains excellent heat conductivility while maintaining good electric conductivity, can meet the requirement of Electronic Packaging.
As can be seen from embodiment 8 with the contrast of comparative example 1,2, the conductive resin that the present invention adopts sheet/dendritic silver-plated copper powder to prepare, its weather resistance is close with silver powder (comparative example 1), far wins common silver-plated copper powder (comparative example 2).This is directly related with present invention employs sheet/dendritic silver-plated copper powder, in sheet/dendritic silver-plated copper powder that the present invention adopts, silver-colored coated Cu surface residual area is aluminium zinc, conductive oxide is formed after zinc-aluminium oxidation, ensure that conductive resin conductivity while stoping Cu oxidized, thus add the ageing-resistant performance of conductive resin.Except this, in sheet racemosus shape silver-plated copper powder, the dendritic nanometer silver of Copper Powder Surface growth can occur when solidifying to melt curtain coating, realize the connection between the coated again of silver-plated copper powder and filler, effectively can improve conductivity and the stability of silver-plated copper powder/epoxide resin conductive adhesive thus further.
Claims (10)
1. 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%, and in silver-plated copper powder, the content of aluminium zinc is less than 15wt%.
2. sheet according to claim 1/dendritic silver-plated copper powder, it is characterized in that: described sheet/dendritic silver-plated copper powder is for substrate with dispersion pattern prealloy copper powder, obtain through aftertreatment after chemical silvering, described dispersion pattern prealloy copper powder is obtained by 0 ~ 15wt% silver powder, 70 ~ 90wt% copper powder, 1 ~ 25wt% zinc aluminium alloy powder mixing and ball milling by weight percentage, wherein: copper powder size > silver powder particle diameter >=zinc aluminium alloy powder particle diameter.
3. sheet according to claim 1/dendritic silver-plated copper powder, is characterized in that: described zinc aluminium alloy powder aluminum content 1 ~ 3wt%.
4. sheet according to claim 1/dendritic silver-plated copper powder, it is characterized in that: described ball milling is high energy ball mill ball milling, described high energy ball mill is the one in oscillatory type ball mill, stirring ball mill, planetary ball mill, ball grinder is steel matter, abrading-ball adopts steel ball or high-density zirconium ball, another outfit jacket cooling system, during to control ball milling, system temperature is not higher than 200 DEG C; Ball-milling Time is 1 ~ 72 hour, and the particle diameter of the dispersion pattern prealloy copper powder that described ball milling obtains is 0.1 ~ 15 micron.
5. sheet according to claim 1/dendritic silver-plated copper powder, is characterized in that:
Described chemical plating liquid composition: soluble silver salt: 10 ~ 50g/L, reductive agent: 5 ~ 25g/L, complexing agent: 10 ~ 60g/L, stablizer: 1 ~ 40mg/L, pore forming material: 1 ~ 10 μ g/L,
Described chemical silvering is for being after 10 ~ 14 by the preconditioning of chemical plating liquid pH adjusting agent, add dispersion pattern prealloy copper powder, carry out the silver-plated process of sonochemistry, frequency 20 ~ the 80KHz of the silver-plated use of described sonochemistry, power 50 ~ 450W, temperature 25 ~ 70 DEG C, reaction times 5 ~ 30min, adopts intermittent type ultrasonic.
6. sheet according to claim 1/dendritic silver-plated copper powder, is characterized in that: described PH conditioning agent is ammoniacal liquor or acetic acid, and described silver salt is Silver Nitrate, described reductive agent is formaldehyde, complexing agent is EDTA, and stablizer is dipyridyl, and pore forming material is polyoxyethylene glycol.
7. sheet according to claim 1/dendritic silver-plated copper powder; it is characterized in that: described aftertreatment is the system after chemical silvering washed; obtain silver-plated copper powder in 150 ~ 300 DEG C of reducing atmosphere calcining 30 ~ 120min again after drying, be then placed in nitrogen protection and store.
8. the economical conductive resin of green Halogen low silver content of an alternative traditional high silver content, it is characterized in that: it is made up of each raw material of following weight percent: sheet/dendritic silver-plated copper powder 60 ~ 90%, micron order silver powder 0 ~ 30%, epoxy resin 6 ~ 12%, reactive thinner 1 ~ 8%, toughened resin 1 ~ 6%, solidifying agent 1 ~ 3%, curing catalyst 0 ~ 1%, coupling agent 0.5 ~ 2%.
9. the economical conductive resin of green Halogen low silver content of alternative traditional high silver content according to claim 8, it is characterized in that: described micron order silver powder is the mixture of sheet, dendroid, spherical or various shape composition, and its particle size range is 0.1 ~ 15 micron;
Described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, acrylic modified epoxy resin, modifying epoxy resin by organosilicon;
Described reactive thinner is 1,4-butyleneglycol glycidyl ether, neopentyl glycol glycidyl ether, 1, one or more in 6-hexanediol diglycidyl ether, Diethylene Glycol glycidyl ether, Isosorbide-5-Nitrae-cyclohexane diol glycidyl ether, TriMethylolPropane(TMP) glycidyl ether, polyethyleneglycol diglycidylether;
Described toughened resin is the mixture of one or more in Amino Terminated polyether(ATPE) imide resin, end carboxyl polyetherimide resin, nbr carboxyl terminal, hydroxy'terminated butadiene nitrile rubber, amino terminated butadiene acrylonitrile rubber, thiorubber, phenolic hydroxy group polyimide resin;
Described solidifying agent selects polyamines class or its modifier, is one or more in Dyhard RU 100, diaminodiphenylmethane, diaminodiphenyl oxide, diaminodiphenylsulfone(DDS) and derivative thereof;
Described curing catalyst selects imidazoles or derivatives thereof, for 2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine, 2, one or more in the derivative of 4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine or 2,4-diamino-6-(2-undecyl imidazole-1-ethyl)-S-triazine salt;
Described coupling agent is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-methacryloxypropyl trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl trimethoxy silane, one or more in N-aminoethyl-3-aminopropyltriethoxy dimethoxysilane.
10. the making method of the economical conductive resin of green Halogen low silver content of alternative traditional high silver content according to claim 8, comprises the following steps:
1. be the epoxy resin of 6 ~ 12% by weight percent, the toughened resin of 1 ~ 6% and 1 ~ 8% reactive thinner carry out first time mixing, obtain a homogeneous mixture A;
2. be the solidifying agent of 1 ~ 3% by weight percent, the curing catalyst of 0 ~ 1%, the coupling agent of 0.5 ~ 2% join in the obtained mixture A of step 1, carry out second time and mix, obtain a homogeneous mixture;
3. be that 60 ~ 90% sheets/dendritic silver-plated copper powder, 0 ~ 30% micron order silver powder join in the obtained mixture of step 2 after mixing by weight percent, carry out third time mixing, obtain the economical conductive resin of green Halogen low silver content of described alternative traditional high silver content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129222.8A CN104830247B (en) | 2015-03-24 | 2015-03-24 | 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129222.8A CN104830247B (en) | 2015-03-24 | 2015-03-24 | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104830247A true CN104830247A (en) | 2015-08-12 |
| CN104830247B CN104830247B (en) | 2017-08-08 |
Family
ID=53808454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510129222.8A Active CN104830247B (en) | 2015-03-24 | 2015-03-24 | 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104830247B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106753027A (en) * | 2017-01-06 | 2017-05-31 | 金陵科技学院 | A kind of quick low-temperature cured conductive glue of double-component |
| CN106916558A (en) * | 2015-11-27 | 2017-07-04 | 日东电工株式会社 | The manufacture method of adhesive sheet, dicing tape integrated adhesive sheet and semiconductor device |
| CN107236485A (en) * | 2017-07-25 | 2017-10-10 | 深圳科诺桥科技股份有限公司 | A kind of dendritic heat curing-type pastes conducting resinl and preparation method thereof |
| WO2018006503A1 (en) * | 2016-07-07 | 2018-01-11 | 深圳先进技术研究院 | Silver salt-doped conductive silver adhesive, and preparation method and use thereof |
| CN108231281A (en) * | 2017-12-20 | 2018-06-29 | 西安工程大学 | A kind of preparation method of titanium aluminium carbon/copper electric slurry |
| CN108300360A (en) * | 2016-10-10 | 2018-07-20 | 昆山雅森电子材料科技有限公司 | Profiled metal particle conductive glued membrane and preparation method thereof |
| CN108300345A (en) * | 2017-10-11 | 2018-07-20 | 广东正业科技股份有限公司 | A kind of epoxide resin conductive adhesive film and preparation method |
| CN108410388A (en) * | 2018-03-09 | 2018-08-17 | 太原氦舶新材料有限责任公司 | A kind of room temperature curing conducting resinl |
| CN108913057A (en) * | 2017-03-27 | 2018-11-30 | 昆山雅森电子材料科技有限公司 | A kind of incorgruous type conductive fabric glue of multilayer and preparation method thereof |
| 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 |
| CN111394007A (en) * | 2020-04-30 | 2020-07-10 | 张家港保税区汇英聚福材料科技合伙企业(有限合伙) | High-conductivity adhesive tape |
| CN112280216A (en) * | 2020-11-02 | 2021-01-29 | 珠海京工检测技术有限公司 | Biomass PVC conductive plastic and preparation method thereof |
| US10994334B2 (en) * | 2016-12-29 | 2021-05-04 | Foundation For Research And Business, Seoul National University Of Science And Technology | Method for preparing rice ear-shaped copper particles, rice ear-shaped copper particles prepared thereby, and conductive paste using same |
| CN113066600A (en) * | 2021-03-24 | 2021-07-02 | 北京梦之墨科技有限公司 | Conductive paste and electronic device |
| CN116618647A (en) * | 2023-07-21 | 2023-08-22 | 安徽诺星航空科技有限公司 | Molybdenum-copper alloy composite material and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905321A (en) * | 2010-08-20 | 2010-12-08 | 中国兵器工业集团第五三研究所 | Preparation method of flake silver-plated copper powder |
| CN102426872A (en) * | 2011-12-28 | 2012-04-25 | 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 |
-
2015
- 2015-03-24 CN CN201510129222.8A patent/CN104830247B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905321A (en) * | 2010-08-20 | 2010-12-08 | 中国兵器工业集团第五三研究所 | Preparation method of flake silver-plated copper powder |
| CN102426872A (en) * | 2011-12-28 | 2012-04-25 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 单连伟等: "《无机材料生产设备》", 31 March 2013 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916558A (en) * | 2015-11-27 | 2017-07-04 | 日东电工株式会社 | The manufacture method of adhesive sheet, dicing tape integrated adhesive sheet and semiconductor device |
| 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 |
| WO2018006503A1 (en) * | 2016-07-07 | 2018-01-11 | 深圳先进技术研究院 | Silver salt-doped conductive silver adhesive, and preparation method and use thereof |
| CN108300360A (en) * | 2016-10-10 | 2018-07-20 | 昆山雅森电子材料科技有限公司 | Profiled metal particle conductive glued membrane and preparation method thereof |
| US10994334B2 (en) * | 2016-12-29 | 2021-05-04 | Foundation For Research And Business, Seoul National University Of Science And Technology | Method for preparing rice ear-shaped copper particles, rice ear-shaped copper particles prepared thereby, and conductive paste using same |
| CN106753027B (en) * | 2017-01-06 | 2018-12-14 | 金陵科技学院 | A kind of quick low-temperature cured conductive glue of two-component |
| CN106753027A (en) * | 2017-01-06 | 2017-05-31 | 金陵科技学院 | A kind of quick low-temperature cured conductive glue of double-component |
| CN108913057B (en) * | 2017-03-27 | 2023-11-10 | 昆山雅森电子材料科技有限公司 | Multilayer anisotropic conductive cloth adhesive and manufacturing method thereof |
| CN108913057A (en) * | 2017-03-27 | 2018-11-30 | 昆山雅森电子材料科技有限公司 | A kind of incorgruous type conductive fabric glue of multilayer and preparation method thereof |
| CN107236485A (en) * | 2017-07-25 | 2017-10-10 | 深圳科诺桥科技股份有限公司 | A kind of dendritic heat curing-type pastes conducting resinl and preparation method thereof |
| CN107236485B (en) * | 2017-07-25 | 2019-02-15 | 深圳科诺桥科技股份有限公司 | A kind of dendritic heat curing type pastes conducting resinl and preparation method thereof |
| CN108300345A (en) * | 2017-10-11 | 2018-07-20 | 广东正业科技股份有限公司 | A kind of epoxide resin conductive adhesive film and preparation method |
| CN108231281A (en) * | 2017-12-20 | 2018-06-29 | 西安工程大学 | A kind of preparation method of titanium aluminium carbon/copper electric slurry |
| CN108410388A (en) * | 2018-03-09 | 2018-08-17 | 太原氦舶新材料有限责任公司 | A kind of room temperature curing conducting resinl |
| 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 |
| CN111394007A (en) * | 2020-04-30 | 2020-07-10 | 张家港保税区汇英聚福材料科技合伙企业(有限合伙) | High-conductivity adhesive tape |
| CN112280216A (en) * | 2020-11-02 | 2021-01-29 | 珠海京工检测技术有限公司 | Biomass PVC conductive plastic and preparation method thereof |
| 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 |
| CN113066600A (en) * | 2021-03-24 | 2021-07-02 | 北京梦之墨科技有限公司 | Conductive paste and electronic device |
| CN116618647A (en) * | 2023-07-21 | 2023-08-22 | 安徽诺星航空科技有限公司 | Molybdenum-copper alloy composite material and preparation process thereof |
| CN116618647B (en) * | 2023-07-21 | 2023-10-13 | 安徽诺星航空科技有限公司 | Molybdenum-copper alloy composite material and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104830247B (en) | 2017-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104830247A (en) | Sheet/branch silver-coated copper powder and green halogen-free low-silver-content economical electrically conductive adhesive capable of replacing traditional electrically conductive adhesives with high silver contents | |
| CN103194165B (en) | Method for preparing high-heat-conductivity conductive adhesive containing graphene | |
| CN101928540B (en) | Epoxy conductive adhesive and preparation method thereof | |
| CN108133768A (en) | A kind of high conductivity low temperature curing type electrocondution slurry and preparation method thereof | |
| JP5402350B2 (en) | Method for producing conductive paste and conductive paste | |
| KR101856802B1 (en) | Conductive paste and base with conductive film | |
| JP5440645B2 (en) | Conductive particles, insulating coated conductive particles and manufacturing method thereof, anisotropic conductive adhesive | |
| CN102585743A (en) | Conductive adhesive and preparation method thereof | |
| CN102675960A (en) | Nano copper-tin alloy conductive ink and preparation method and usage of nano copper-tin alloy conductive ink | |
| WO2018006503A1 (en) | Silver salt-doped conductive silver adhesive, and preparation method and use thereof | |
| CN101781541A (en) | Situ preparation method of nano silver/epoxy conductive adhesive | |
| CN111261320A (en) | Epoxy resin-based low-temperature conductive silver paste and preparation method thereof | |
| CN101214547A (en) | Micrometer silver-copper granule containing nano level surface structure and preparation and application thereof | |
| CN112175562A (en) | Preparation method of epoxy silver conductive adhesive containing graphene/silver heat conduction network | |
| CN102399523A (en) | Nano-grade-silver-filled room-temperature-cured conductive adhesive | |
| CN104464887A (en) | Nanometer silver wire conductive silver paste and preparing method thereof | |
| KR102109944B1 (en) | Paste for electromagnetic interference shielding and preparation method for thereof | |
| CN109161358A (en) | A kind of preparation method of conducting resinl | |
| CN105778841A (en) | Conductive silver adhesive for notebook keyboard and preparation method thereof | |
| CN104629643B (en) | Conducting resinl, its preparation method and wiring board | |
| CN104530873A (en) | Copper-based electromagnetic shielding coating and preparation method thereof | |
| CN104673128A (en) | High-performance modified bismaleimide conductive adhesive as well as preparation method and curing method thereof | |
| CN114603133B (en) | Conductive silver paste containing nano filler with multilevel structure and preparation method thereof | |
| CN115762848A (en) | Heterojunction low-temperature silver paste and preparation method thereof | |
| JP5034577B2 (en) | Conductive paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170324 Address after: 402160 Yongchuan District, Phoenix Lake Industrial Park, Chongqing electronics district, two Applicant after: Chongqing New Material Co., Ltd. Address before: 100081 Beijing, Zhongguancun, South Street, No. 89, unit 133, No. 5, No. Applicant before: Wang Chuanguang Applicant before: Xu Jie |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |