CN1010266B - Conductive paste which is directly solderable and flexible and can be directly bonded to a substrate - Google Patents
Conductive paste which is directly solderable and flexible and can be directly bonded to a substrateInfo
- Publication number
- CN1010266B CN1010266B CN 86100151 CN86100151A CN1010266B CN 1010266 B CN1010266 B CN 1010266B CN 86100151 CN86100151 CN 86100151 CN 86100151 A CN86100151 A CN 86100151A CN 1010266 B CN1010266 B CN 1010266B
- Authority
- CN
- China
- Prior art keywords
- substrate
- sizing material
- vinyl chloride
- silver
- acetic acid
- 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.)
- Expired
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 111
- 238000004513 sizing Methods 0.000 claims description 79
- 229910052709 silver Inorganic materials 0.000 claims description 45
- 239000004332 silver Substances 0.000 claims description 45
- 239000003292 glue Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 229940117958 vinyl acetate Drugs 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000005476 soldering Methods 0.000 abstract description 3
- 239000011797 cavity material Substances 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 238000003466 welding Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The present invention provides conductive pastes that are solderable and flexible and capable of being directly bonded to a substrate. These pastes are composed solely of silver powder in flake form in combination with a resin system comprising a vinyl chloride/vinyl acetate copolymer, an epoxy resin and an epoxy hardener, and a method of making such pastes, and another embodiment of the invention is a method of applying an electrically conductive paste directly to a substrate by directly bonding the electrically conductive paste to the substrate. Upon curing, the conductive cavity material exhibits good direct adhesion to the substrate in addition to excellent conductivity, soldering properties and flexibility.
Description
The present invention relates to the pliable and tough electroconductive glue materials that can weld and its production method.More particularly, the present invention relates to have good flexility and welding characteristic, and can be directly bonded to on-chip sizing material.
Be added to that electroconductive glue materials on bearing or the substrate structure must have enough good conductivity so that transmission current, and must be glued fast on bearing or the substrate.Also requiring this electroconductive glue materials is directly can weld with pliable and tough.
United States Patent (USP) 3,030,237 disclose a kind of improved coating, mainly comprise: organic resin carrier and a kind of suitable metallic pigments.This invention has been to invent a kind of coating that contains the metallic pigments composition, this composition is made up of according to certain mixed sphere with special size and sheet type particle, this metallic pigments and organic resin carrier are combined, have good adhesiveness and conductivity.Disclosed herein also have, and can go general lead silver soldering on cured coating with very common silver soldering technology.
United States Patent (USP) 2,959,498 disclose a kind of method that forms silver-colored conducting channel, morals are added to not completely crued thermoset resin layer dielectric surface of resin, on described layer, apply one deck and the silver layer that comprises the thermoplastic resin fusion of above-mentioned two kinds of resin solvents then, this layer is that conducting channel figure according to demand has divided subtly, and added two layers of resin then is heating and curing.Importantly earlier thermosetting resin is coated onto on the resin plate, and applies before this electroconductive glue materials, this resin is partly solidified.Preferably circuit diagram as requested pushes a kind of silver paste, makes to form conducting channel on this bottom.The silver-colored particle that this silver paste is opened by fine division in a kind of thermoplastic resin is formed, and silver is 4: 1 to 10: 1 with the ratio of resin.Resulting silver-colored circuit diagram adheres on this resin substrate securely, and is easy to silver-colored line is welded.
United States Patent (USP) 4,371, but 459 a kind of conducting resinl sizing material of pliable and tough silk screen printing is disclosed, comprise conductive phase (a).Copolymer (b) and volatile non-hydrocarbon solvent (c).This conductive phase (a) comprises silver and the alkali metal powder that is dispersed in copolymer (b) solution, and copolymer (b) is to prepare by the co-polymerization that is dissolved in vinylacetate, vinyl chloride, ethylene linkage unsaturation dicarboxylic acids and the aromatic mylar of straight chain in the volatile non-hydrocarbon solvent (c).It is very useful that these compositions touch switch for film.
September 30 nineteen eighty-three, sequence number a kind of welding electroconductive glue materials that has been 537,740 U.S. Patent Application Publication comprised the metallic silver particles that is embedded in the matrix that is formed by propylene, carboxylation acetate and epoxy.By being dissolved into, propylene powder and ethene powder form first solution in the solvent separately and second solution generates this sizing material.Then these solution are mixed with metallic silver particles and epoxy and form the seal China ink.This seal China ink is added to film of formation on the substrate.The heating of this film, with evaporating solvent and produce polymerization, thereby obtain a welding conductive film.In addition, EPO143530 also is the invention relevant with the application, is disclosed on June 5th, 1985.
The feature of the electroconductive glue materials that being used for of being studied so far is connected with bearing or substrate structure or other electric equipment is: the satisfied high resistivity of people in addition not, or to the low adhesion of bearing or substrate material.And many sizing materials of the prior art have the shortcoming that can not directly weld; In other words, must use not only time-consuming but also expensive chemical plating or similar method on this electroconductive glue materials in order to be welded to.Another shortcoming is that the electroconductive glue materials of in fact many prior aries is not pliable and tough, therefore can not be applied to it on the pliable and tough substrate.In addition, the sizing material in many existing technology can not directly adhere on the substrate that they will add.
Although the sizing material of some prior aries has solved in the above-mentioned defective some really, their weak point is to adopt the complexity prescription that comprises some added compound, and must implement some additional treatment steps.And sizing material of the prior art does not have enough conductivity, pliability and reliability, all can not directly adhere on the substrate again.
A kind of have good conductivity, adhesiveness and pliability are provided, and do not need just can be to its electroconductive glue materials that directly welds by means of the process of complexity or prescription, this is the target of always seeking for a long time, people wish to obtain a kind of have enough conductivity and flexible electroconductive glue materials always, make it can replace mechanical terminal adapter on the pliable and tough polymer thick film circuit.
Therefore, one of purpose of the present invention provide can directly be bonded in on the substrate and be pliable and tough and electroconductive glue materials that can directly weld.
Two of purpose of the present invention provides the sizing material with satisfactory electrical conductivity.
Three of purpose of the present invention provides and need not to use the electroconductive glue materials that just can weld such as the such complex process of chemical plating.
Four of purpose of the present invention provides has enough conductances and pliability, enables to replace the electroconductive glue materials of the mechanical terminal adapter on flexible polymeric thing thick film circuit.
Five of purpose of the present invention provides the method that a kind of preparation has the electroconductive glue materials of above-mentioned characteristic.
It will be apparent that below, by the purpose of obtained these and other of the present invention.The present invention includes a kind of single flake silver powder end and the electroconductive glue materials of resin system on the one hand, it is directly weldable and pliable and tough.Said resin system comprises vinyl chloride/vinyl acetic acid salt copolymer, epoxy resin and epoxy curing agent; On the other hand, the present invention is a method of making electroconductive glue materials, comprise: vinyl chloride/vinyl acetic acid salt copolymer is dissolved in first solution that forms in the ketone solvent, epoxy resin and epoxy curing agent are dissolved in second solution that forms in the ester solvent, then first solution and second solution are mixed forming mixture with silver strip shape powder, make silver strip moist basically and scatter.Another aspect of the present invention is that electroconductive glue materials is added to on-chip method, and this is directly bonded to electroconductive glue materials on the substrate and forms.
Sizing material of the present invention comprises silver strip sprills and a resin system, and said resin system comprises: vinyl chloride/vinyl acetic acid salt copolymer, epoxy resin and epoxy curing agent.In fact, these silver strip sprills are distributed in the whole resin system.
This resin system has not only been fixed suspension silver strip powder but also is provided the silver strip powder to the substrate adhesion, the silver strip powder is kept together, to form conductive path and pliability is provided.In addition, resin is deviate to substrate from silver strip when cured, just stays the silver layer of high concentration like this at the top.
When liquid state sizing material of the present invention being added on the substrate, promptly is that sizing material is mixed mutually with the solvent that plays instrumentality.In case after being coated on the substrate, just sizing material is solidified, has stayed sizing material drying, that solidify that only contains trace solvent after solvent evaporation is fallen.In the following discussion, we will be open the ratio of employed some one-tenth branch.Its important point is that these ratios for this sizing material are its drying and solid state, rather than refers to the sizing material of the liquid state in the production process, that is to say to have only just to comprise solvent when pointing out in addition.
The more important that should note is, must be 100% silver strip sprills for the used silver of the present invention's purpose.Adopt the silver of other shape, for example, mixing spherical or ball and sheet all can not be produced the sizing material of all advantages with sizing material of the present invention.When across the size of particle face during than its big at least five times of thickness, we think that it is a sheet-like particle, preferably big ten times.Only having another advantage that the silver strip sprills are had is that it is as the silver-colored mobile problem of being seen in the sizing material that can reduce or eliminate in the prior art.The average-size of silver strip sprills can be from about 0.5 micron to about 50 microns, preferably greatly about from 2 to 4 micrometer ranges.Certainly the size of silver strip powder particle can have less than 0.5 micron or greater than 50 microns, as long as the mean value of the size of silver strip powder particle just can be prepared sizing material of the present invention between 0.5 to 50 micron.The average-size of supposing the silver strip powder particle will be difficult to obtain containing the sizing material of such quantity silver less than 0.5 micron.If silver powder is too thin, the denseness of sizing material will be the spitting image of claylike.If the average-size of silver strip powder is greater than 50 microns, so this sizing material will be difficult to use.Such as, sizing material will clog mesh in the process of screening and so on.The ratio of the silver strip powder that the curing sizing material contains is between 88% and 93% (by weight) greatly.
Can be used on vinyl chloride/vinyl acetic acid salt copolymer in the sizing material of the present invention and have average molecular weight range greatly between 14,000 to 35,000, best, the mean molecule quantity of this copolymer is about 20,000.Compare with low-molecular-weight vinyl chloride/vinyl acetic acid salt copolymer, the vinyl chloride of higher molecular weight/vinyl acetic acid salt copolymer has good durability and pliability.Vinyl chloride/vinyl acetic acid the salt copolymer that we have found that other types can not play as the vinyl chloride/vinyl acetic acid salt copolymer role among the present invention.E.I.Dupou de Nemours sells a kind of vinyl chloride/vinyl acetic acid salt copolymer-VMCC that changes carboxyl.The weight ratio of vinyl chloride, vinylacetate and maleic acid is 83: 16: 1 in this product.In case weld, the sizing material quality made from this product just degenerates.Obviously, the existence of dicarboxylic acids is harmful to final application disclosed in this invention.The also tested mistake of polyvinylidene alcohol, this is a kind of improved polyvinyl alcohol, the sizing material made from this resin also degenerates through welding its quality.Sizing material of the present invention needs a kind of high-performance vinyl chloride/vinyl acetic acid salt copolymer; The vinyl chloride of low molecular vinyl chloride/vinyl acetic acid salt copolymer or change/vinyl acetic acid salt copolymer does not become.The weight ratio of vinyl chloride and vinylacetate can be from about 80: 20 to about 90: 10.Best weight ratio is about 86: 16 to 88: 12.Mean molecule quantity is that 35,000 vinyl chloride/its vinyl chloride of vinyl acetic acid salt copolymer and the weight ratio of vinylacetate are approximately 90: 10; Mean molecule quantity is that 14,000 vinyl chloride/its vinyl chloride of vinyl acetic acid salt copolymer and the weight ratio of vinylacetate are approximately 86: 14.
Although the embodiment in this specification realizes by the vinyl chloride that is called VYHH/vinyl acetic acid salt copolymer that Llnion Carbide provides, still can adopt other kind vinyl chloride/vinyl acetic acid salt copolymer as long as meet specification mentioned above.
Epoxy resin as the part of this resin system can be the epoxy resin that meets the commercially available any kind of of following specification.The epoxy resin that is called epoxylite 6010 that we have used ciba Geigy to sell.This is a kind of moderately viscous liquid (with respect to bisphenol-A and chloropropylene oxide) of unmodified.Used epoxy curing agent is called HY940, is provided by Ciba Geigy.The purpose that adds epoxy curing agent is and cross linking of epoxy resin, so that form solid-state under condition of cure; Used epoxy resin and epoxy curing agent at room temperature must can not be crosslinked among the present invention.Therefore, it must be the heat cured system of an one step, and compatible with other compositions (such as solvent).Last condition is that this epoxy resin can not be water-based epoxy resin.
Used silver strip sprills are very important to the weight ratio of resin system.If at the proportion of regulation, the sizing material of being produced will not possess all features mentioned above to these composition consumptions so.From in broad terms, the silver strip sprills should be about 88: 12 to 95: 5 the weight ratio of resin system, preferably are about 89: 11 to 91: 9.
In this resin system, vinyl chloride/vinyl acetic acid salt copolymer approximately is from 100: 1 to 2: 1 to the weight ratio of epoxy resin and curing agent, preferably approximately is from 2: 1 to 4: 1.Epoxy resin is about 30: 70 to 40: 60 to the weight ratio of epoxy curing agent, preferably is about 34: 66 to 38: 62.Vinyl chloride/vinyl acetic acid salt copolymer approximately is from 100: 1 to 2: 1 to the weight ratio of epoxy resin and epoxy curing agent in addition.
Sizing material of the present invention contain silver strip sprills amount should be whole sizing material about 88% to 95%(by weight), the amount of contained resin system should be whole sizing material about 7% to 12%(by weight).In addition, contained vinyl chloride/vinyl acetic acid salt copolymer should be about 4% of whole sizing material and arrives 7%(by weight), contained epoxy curing agent should be about 0.5% of whole sizing material and arrives 3%(by weight), contained epoxy resin should be about 0.25% of whole sizing material and arrives 2%(by weight).
As previously mentioned, sizing material of the present invention is compared with the sizing material of existing technology and is shown many advantages.For example: sizing material of the present invention is pliable and tough, makes it it is added on the pliable and tough substrate (such as the Thin-film key plate).When we say this sizing material is pliable and tough, this means that being added to on-chip sizing material can stand deformation power, can not separate, break or fracture from substrate.This sizing material is the same good during with non-deformed state in the function of deformed state.The most serious deformation will form folding line in sizing material, even the function of this sizing material is still in this case.If the result of deformation is broken sizing material or is fractureed then just can not think that this sizing material is pliable and tough; Conductivity that breaking in sizing material will make it and other electric and mechanical performance produce rapid decline.
Another advantage of sizing material of the present invention is directly to weld.This means them directly to accept to weld and do not need the time-consuming expensive operation of engineers and technicians by means of chemical plating and so on.As long as welding temperature is no more than 205 ℃, can weld by in the several different methods any this sizing material, for example: dipping or reflow solder technique.Certainly, can not get rid of the needs that use solder flux (medicine) with sizing material of the present invention.Solder flux is a kind of resin-based materials that sizing material soaks ability that increases.Solder flux is nonconducting.It is widely used and generally is liquid.Can use solder flux by several different methods.Can adopt the precoating solder flux, at first the sizing material that will weld on the ground that uses the precoating solder flux be soaked liquid flux, then, when sizing material is still moist, weld.Solder flux also can be a composition in a kind of solder alloy mixture on the other hand.In this case, medium is solder flux, and does not need prefluxing.In addition, solder flux can be that activated or non-activated.Solder flux with activation cleans the surface of being welded.
Can be added to sizing material of the present invention on rigidity or the pliable and tough various substrates, and these substrates can be made of multiple material.Specifically, these substrates in nature can be pottery or resin.A kind of typical substrate is exactly a printed substrate.Unique restriction to substrate is can stand the condition of welding and not therefore distortion or damage, earlier this sizing material is added on the substrate with liquid state, is cured then.
Sizing material of the present invention is made like this: vinyl chloride/vinyl acetic acid salt copolymer is dissolved into forms first solution in the ketone solvent; Epoxy resin and epoxy curing agent are dissolved into formation second solution in the ester solvent; Then first and second solution and silver strip powder are formed mixture, the silver strip powder is disperseed fully with wetting.The weight ratio of silver strip powder, vinyl chloride/vinyl acetic acid salt copolymer and epoxy resin approximately is from 68: 4: 4 to 75: 6: 2.Epoxy resin approximately is from 40: 60 to 36: 63 to the weight ratio of epoxy curing agent.Vinyl chloride/vinyl acetic acid salt copolymer approximately is from 15: 85 to 25: 75 to the weight ratio of ketone solvent, and epoxy resin and epoxy curing agent approximately are from 100: 1 to 75: 25 to the weight ratio of ester solvent.First solution approximately is that the vinyl chloride first solution/vinyl acetic acid salt copolymer amount approximately is from 15% to 25%(by weight from 100: 1 to 88: 12 to the weight ratio of second solution).Epoxy resin in second solution and hardenable epoxy dosage approximately are from 70% to 99%(by weight), the amount of contained silver strip sprills is approximately 68% of whole mixture and arrives 75(by weight).
Except being dissolved in vinyl chloride/vinyl acetic acid salt copolymer ketone solvent and, in implementing method of the present invention, not having what special technique epoxy resin and hardenable epoxy solvolysis are in ester solvent.Can add the silver strip sprills by any common technology.Ketone solvent wherein can be any ketone solvent, for example gamma butyrolactone, acetone or cyclohexane, or analog.Ester solvent can be any ester solvent, for example, and acetate of butyl carbitol or the like; Acetate of butyl carbitol is a kind of ester solvent that is provided by Union Carbide.Before substrate is applied this sizing material, must check the grind size of this sizing material, it must be 25 microns or littler.Can use and take any standard technique of abrasive particle gauge to check grind size.If grind size is not 25 microns or littler.Then allow this sizing material by one 3 roll grinding machine, up to obtaining suitable grind size.The utilization feeler gauge is provided with the gap of cylinder as follows: the gap between the front and the middle cylinder is 0.002 ", and the gap between the cylinder middle and back is 0.015 ".This sizing material can not be more than 3 times by 3 roll grinding machines.In addition, when the Brookfield viscometer of utilization standard was measured, the range of viscosities of this sizing material approximately should be from 30 under 25 ℃ situation, 000CPS to 100,000CPS.Preferably this viscosity is about 30, and 000CPS to 70 is between the 000CPS.
Can such as silk screen print method, metallikon or brushing method, the mixture that forms like this be added on the substrate by in many technology any.This substrate may be pliable and tough or rigidity, and it can be made of multiple material, such as resin and the pottery.Typical substrate is printed circuit board (PCB) and Thin-film key plate.The thickness of this mixture can be 1 mil or more.After being added on the substrate, in temperature approximately from 100 ℃ to 170 ℃ the oven dry of this mixture with solidified about 15 to 60 minutes.Can realize oven dry and curing by any (such as in baking oven) in the common multiple technologies.
Can directly be adhered to sizing material of the present invention on the substrate.This method only is that electroconductive glue materials is added on the substrate, this realizes by electroconductive glue materials directly is adhered on the substrate, this electroconductive glue materials comprises single flake silver powder and resin system, and this resin system mainly is made up of vinyl chloride/vinyl acetic acid salt copolymer, epoxy resin and epoxy curing agent.This substrate is not needed preliminary treatment, or with any special sizing material precoating, or by any process.This sizing material one drying and curing just show good adhesiveness to substrate.Remove the required mean force of this sizing material greater than the 500P.S.i(PSI from the substrate of a rigidity).The example of the flexible substrate that sizing material can be enough of the present invention applies has: by E.I.Dupontde Nemour make with trade mark Kapten
The polyimide base film of selling, and by I.E.Dupot de Nemour make with trade mark MYlar
The polyester substrate of selling.
During measuring the process remove (or damage) the needed power of this sizing material from a rigid substrate, a pad of sizing material material is coated onto on 1/10 square inch the substrate.Then on this welding with backing.Again the tinning copper cash of A22 specification and this substrate vertically are welded on the liner.Measure with common device this liner is torn required power from substrate.Failure all is to occur on the adhesive power of liner to substrate, rather than is to bond to the lead of liner.Any mobile or damage of sizing material all is considered to failure.On to flexible substrate, in the adhering measurement of sizing material, used the cross figure adhesiveness method of testing of standard, in a circuit diagram printing; On this circuit diagram, cut a cross pattern with a blade, be attached to adhesive tape on this pattern and exert pressure.Whether then adhesive tape is peelled off, observing has any sizing material to go (transmission of sizing material or damage) from the substrate disengaging.
In order to enable those skilled in the art to implement goodly, provided more following examples by specifying, but they are not limitation of the present invention.
The embodiment I
Make the method for electroconductive glue materials
By being average mark 2 amount that vinyl chloride/vinyl acetic acid salt copolymer of 20,000 is dissolved in and prepares first solution in the gamma butyrolactone.
By being dissolved into butyl length, epoxy resin (epoxy resin that Ciba Geigy sells with trade mark Araldite6010) and epoxy curing agent (by Ciba Geigy with trade mark HY940 sale) must prepare second solution in the alcohol acetic ester.
Then these two solution are mixed, and to add average particle size be 2 microns silver strip sprills, so total component is made of following:
69.52% silver strip sprills
22.0% gamma butyrolactone
5.44% vinyl chloride/vinyl acetic acid salt copolymer
0.66% acetate of butyl carbitol
（butyl Carbitol
acetate）
0.87% Araldite
6010
1.49% epoxy curing agent-HY940
The mixture that is in harmonious proportion is disperseed fully and is soaked until the silver strip powder.
Allow this sizing material by one 3 roll grinding machine then, the front roll of this grinder and the gap of intermediate calender rolls are decided to be 0.002 ", the gap between the back roll of intermediate calender rolls is decided to be 0.015 ".This sizing material is by this 3 roll grinding machine, reaches 23 microns until the fineness of particle.
The viscosity of this sizing material is 60,000CPS.
The embodiment II
The sizing material of example 1 being made with silk screen print method directly is coated onto on the substrate of rigidity.Then 125 ℃ of baking and curing 30 minutes.
Adhesion is 500P.S.i.
Resistivity is 25milliohm/sq/mil(milliohm/square/mil).
When 200 ℃ of welding, its welding characteristic is that well scolder is grouped into by following one-tenth: 62% tin; 36% lead; 2% silver medal.
The embodiment III
The sizing material of embodiment 1 directly is coated onto on the pliable and tough substrate, dries and solidified 30 minutes at 125 ℃ then.
Of the adhesion test of this sizing material by cross figure.
Resistivity is 25-27milliohm/sq/mil(milliohm/square/mil).
When 200 ℃ of welding, its weldability is good, and scolder is grouped into by following one-tenth: 62% tin; 36% lead; 2% silver medal.
Claims (16)
1, a kind of directly can the weldering and pliable and tough electroconductive glue materials comprises the silver and the resin system of about 88%-95% weight, and said system comprises:
A) vinyl chloride/vinyl acetic acid salt copolymer of about 4-7% weight;
B) epoxy resin of about 0.25-2%;
C) epoxy curing agent of about 0.5%-3%.
Described silver-colored 100% all is the form with silver powder, and the particle of its silver powder is the 0.5-50 micron; The mean molecule quantity of described vinyl chloride/vinyl acetic acid salt copolymer is 14000-35000, and does not comprise the carboxylic acid group; Described epoxy curing agent be non-water quality and be heat cured.
2, according to the sizing material of claim 1, wherein vinyl chloride is about 80: 20 to 90: 10 to the weight ratio of vinylacetate.
3, a kind of manufacture method of the pliable and tough sizing material that can directly weld comprises: vinyl chloride/vinyl acetic acid salt copolymer is dissolved into forms first solution in the ketone solvent; Epoxy resin and epoxy curing agent are dissolved into formation second solution in the ester solvent; Then first and second solution are formed a kind of mixture with the silver strip powder.
4, according to the method for claim 3, wherein the silver strip powder is about 68: 4: 4 to 75: 6: 2 to vinyl chloride/vinyl acetic acid salt copolymer with to the weight ratio of epoxy resin.
5, according to the method for claim 3, wherein epoxy resin is about 40: 60 to 36: 63 to the weight ratio of epoxy curing agent.
6, according to the method for claim 3, wherein vinyl chloride/vinyl acetic acid salt copolymer is about 15: 85 to 25: 75 to the weight ratio of ketone solvent.
7, according to the method for claim 3, wherein epoxy resin and epoxy curing agent are about 100: 1 to 75: 25 to the weight ratio of ester solvent.
8, according to the method for claim 3, wherein first solution is about 100: 1 to 88: 12 to the weight ratio of second solution.
9, according to the method for claim 3, wherein the content of vinyl chloride/vinyl acetic acid salt copolymer is approximately 15% of first solution and arrives 25%(by weight), epoxy resin and not the content of oxygen curing agent be approximately second solution 70% to 99%(by weight), the content of silver strip sprills be approximately whole mixture 68% to 75%(by weight).
10, according to the method for claim 3, also comprise this mixture is coated onto on the substrate, dry, solidify this mixture then.
11, according to the method for claim 10, mixture is wherein coated with silk screen printing.
12, according to the method for claim 10, substrate wherein is pliable and tough.
13,, wherein be about 100 ℃ to 170 ℃ this mixture oven dry and curing be approximately 15 to 60 minutes in temperature according to the method for claim 10.
14, electroconductive glue materials is coated onto on-chip a kind of method, comprises the electroconductive glue materials of claim 1 is directly adhered on the substrate.
15, according to the method for claim 14, wherein remove the required power of this electroconductive glue materials greater than 500P.S.i from a rigid substrate.
16, according to the method for claim 14, substrate wherein is pliable and tough.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86100151 CN1010266B (en) | 1984-07-18 | 1986-01-11 | Conductive paste which is directly solderable and flexible and can be directly bonded to a substrate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/631,973 US4595604A (en) | 1984-07-18 | 1984-07-18 | Conductive compositions that are directly solderable and flexible and that can be bonded directly to substrates |
| CN 86100151 CN1010266B (en) | 1984-07-18 | 1986-01-11 | Conductive paste which is directly solderable and flexible and can be directly bonded to a substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86100151A CN86100151A (en) | 1987-07-22 |
| CN1010266B true CN1010266B (en) | 1990-10-31 |
Family
ID=25742163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86100151 Expired CN1010266B (en) | 1984-07-18 | 1986-01-11 | Conductive paste which is directly solderable and flexible and can be directly bonded to a substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010266B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101855543B1 (en) * | 2010-10-05 | 2018-05-08 | 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 | Single component, low temperature curable polymeric composition and related method |
| CN103400637B (en) * | 2013-08-05 | 2016-07-13 | 清华大学深圳研究生院 | A kind of electrocondution slurry and preparation method thereof and printed wire material |
| CN105646968A (en) * | 2016-03-02 | 2016-06-08 | 安徽汇精模具研发科技有限公司 | Denoising electroconductive rubber gasket |
-
1986
- 1986-01-11 CN CN 86100151 patent/CN1010266B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86100151A (en) | 1987-07-22 |
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