CN101921505B - Conductive printing ink composite for printing of wireless radio frequency identification devices (RFID) - Google Patents
Conductive printing ink composite for printing of wireless radio frequency identification devices (RFID) Download PDFInfo
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- CN101921505B CN101921505B CN 201010133151 CN201010133151A CN101921505B CN 101921505 B CN101921505 B CN 101921505B CN 201010133151 CN201010133151 CN 201010133151 CN 201010133151 A CN201010133151 A CN 201010133151A CN 101921505 B CN101921505 B CN 101921505B
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- 238000007639 printing Methods 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 239000011231 conductive filler Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 51
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- -1 alkyl phosphate Chemical compound 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000012745 toughening agent Substances 0.000 claims description 3
- ITEXGQMQVGHHHS-UHFFFAOYSA-N (amino-methoxy-methylsilyl)oxymethylcyclohexane Chemical compound C1(CCCCC1)CO[Si](OC)(C)N ITEXGQMQVGHHHS-UHFFFAOYSA-N 0.000 claims description 2
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 2
- HIMXAERGQMNODV-UHFFFAOYSA-N 2-N,4-N,1,2,3,4-hexamethoxy-2-N-methyl-1,3,5-triazine-2,4,6-triamine Chemical group CONC1(N(C(N(C(=N1)N)OC)(N(C)OC)OC)OC)OC HIMXAERGQMNODV-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920013649 Paracril Polymers 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- PWBLFPFEBXCQBP-UHFFFAOYSA-N 3-nonylnaphthalene-1,2-disulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(CCCCCCCCC)=CC2=C1 PWBLFPFEBXCQBP-UHFFFAOYSA-N 0.000 claims 1
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 2
- 239000002318 adhesion promoter Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 49
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
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- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 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 1
- 229920003319 Araldite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a conductive printing ink composite for printing of wireless radio frequency identification devices (RFID), which comprises the following components in percentage by weight: 2%-10% of at least one type of epoxy resin, 5%-10% of epoxy resin toughness modifier, 30%-50% of reactive diluent, 2%-4% of curing agent, 1%-1.5% of curing accelerator, 30%-50% of conductive filler, 10%-30% of organic solvent, and 0-1.5% of flowing additive, adhesion promoter, rheological control agent and filler surface modifier. The conductive printing ink for the printing of the RFID has the advantages of high conductivity, high adhesion strength, stable electrical property and the like, and has good printing property on high-energy surfaces of metal, ceramics, glass and polymers.
Description
Technical field
The present invention relates to electrically conductive ink, refer in particular to a kind of radio frequency identification system printing and use conductive ink composition.
Background technology
Along with the rise of Internet of Things industry, intelligent label progresses into people's the visual field.Intelligent label is also claimed electronic tag; It is radio frequency identification system (RFID); Be a kind ofly to reach the new high-tech product that non-contacting RFID is the label field through radiowave; Nowadays the packing of product and false proof in play an important role, have progressively the traditional Product labelling and the trend of barcode of substituting.The RFID label is the radio circuit that is made up of multilayers such as chip, antennas.Utilize the characteristic of differing materials, bringing into play different effects, accomplish the function of electronic tag on the product RF identification.Wherein antenna stack is the major function layer of electronic tag, and it is the electronic circuit that designs according to the desired function of RF identification, with conductive silver paste or conductive carbon paste wire mark on PVC, PC or PET, again with synthetic such as surface layer, resist and bottoms.Therefore, the seal carving of intelligent label antenna are most important.In the intelligent label printing, electrically conductive ink is mainly used in the antenna of printing intelligent label, substitutes the metal antenna that traditional blocking method or etch are made.It has two main advantages: the metal antenna that blocking method that (1) is traditional or etch are made; Complex process, finished product Production Time is long, is to utilize the high speed printing process and use the electrically conductive ink printed antenna; Efficient fast, be in printed antenna and the circuit first-selected not only soon but also cheap method.Nowadays; Electrically conductive ink has begun to replace the etching antenna of each frequency band; Like hyper band (860MHz～950MHz) and microwave frequency band (2450MHz); Antenna with the electrically conductive ink printing can be compared with the etched copper antenna of tradition mutually, and in addition, electrically conductive ink also is used for printing transmitter and the circuit printing of RFID; (2) metal antenna made of traditional blocking method or etch is wanted the high metallic substance of consumption costs, and cost is higher, and the material cost of electrically conductive ink will be lower than traditional metal antenna, and this cost of manufacture for the reduction intelligent label has very big meaning.
The requirement of the electrically conductive ink characteristic of at present the RFID field being used mainly contains: (1) resistance to bend(ing).Printed circuit cable road on diaphragm if printing ink is flexible poor, just possibly fracture in the place of bending, even perhaps do not fracture but resistance value also can increase and can not use; (2) tackiness; (3) resistivity.Require the resistivity of printing ink itself low more good more, when using silk screen (forming same thickness) with a kind of order number to print, the printing ink that resistivity is low is more favourable; (4) size-grade distribution.Refer to the distribution of electroconductive particle, the distribution of fine more then tackiness agent of the granularity of conducting particles and particle is good more, and because the printing ink good-extensibility on the forme, so the lining area is also just big; (5) condition of cure.Be necessary time of drying of anti-electrically conductive ink completely solidified and drying temperature, the printing ink of cryodrying type can be reduced work hours, and boosts productivity; (6) printability.
The main drawback of electrically conductive ink existence has on the market at present: 1) specific conductivity is on the low side, and for flowability and the cohesive strength that guarantees printing ink, often the addition of conductive filler material silver is not very big, so it is low to cause the electricity of printing ink to be led.2) adhesive property is bad, owing to will guarantee the flowability of printing ink, often in ink formulations, has added a large amount of solvents and thinner, and these additives produce negative influence to the adhesive property of printing ink.3) resistance is unstable, in common electrically conductive ink all be with sheet or granulous silver powder as conductive filler material because the restriction of the pattern of filler, these electrically conductive inks the resistivity wild effect often occurs in long-time use.
Therefore develop a kind of high-performance conductive printing ink that can overcome these shortcomings of existing electrically conductive ink is badly in need of very much; Nano silver wire is owing to have filamentary structure; This structure can guarantee that filler can form very stable conductive network in resin matrix; Filler content required when reaching the requirement specific conductivity simultaneously can be low; So just can guarantee the adhesive property of electrically conductive ink, these excellent performances have obtained embodying (Chinese patent: publication number CN1948414) in contriver's another one patent.Adopt contriver's oneself patented process (Chinese patent: publication number 101310899) prepare nano silver wire and nanoparticle in this patent as conductive filler material; Prepared the electrically conductive ink of planting the novel RFID printing of high-performance usefulness; Has specific conductivity height, high, advantages such as stable electrical properties with the base material cohesive strength.
Summary of the invention
The electric conductivity that the objective of the invention is in order to overcome existing electrically conductive ink is low; Shortcomings such as cohesive strength is low; Provide a kind of mechanical strength height, stable electrical properties, cohesive strength high, the high-performance conductive ink composite that electric conductivity is high, and the preparation method of conductive ink composition is provided.
Conductive ink composition components based on weight percentage of the present invention is calculated, and forms as follows:
2%～10% at least a epoxy resin;
5～10% epoxy resin toughness properties-correcting agent;
30%～50% reactive diluent;
2%～4% solidifying agent;
The curing catalyst of 1%～1.5% weight;
The conductive filler material of 30～50% weight;
10%～30% organic solvent;
The flowing additive of 0～1.5% weight, adhesion promotor, rheological control agent and stuffing surface modification agent.
The better epoxy resin that uses among the present invention is chloropharin deutero-solid or liquid epoxies.Each molecule of this epoxy resin on average has 1～11 hydroxyl to add terminal epoxy groups, for example EPON 1007 (HEXION company).A kind of better solidifying agent is for example Cymel303 (Cytec company) of hexamethoxy methyl cyanuramide.
Can adopt various acid curing catalysts in this electrically conductive ink, comprise the mixture of mineral acid, tosic acid, dinonyl certain herbaceous plants with big flowers disulfonic acid, Witco 1298 Soft Acid, oxalic acid, toxilic acid, hexamic acid, phosphoric acid, alkyl phosphate, phthalic acid, vinylformic acid or above-mentioned substance.Consider the factor such as room temperature staging life and curing speed of glue, the better acid of result of use is that the mixture of dinonyl certain herbaceous plants with big flowers disulfonic acid or dinonyl certain herbaceous plants with big flowers disulfonic acid and above-mentioned other materials is (like Cycat500 (Cytec company).
The conductive filler material that uses in this electrically conductive ink is the mixture of nano silver wire and Nano silver grain, and wherein the weight ratio of nano silver wire and Nano silver grain is between 8: 2～9: 1.This since with the mixture of nano silver wire and Nano silver grain as conductive filler material, contacting between the contact gear ratio particle between line and the line and the particle forms conductive network more easily.
Concrete preparation method is: be that 1: 2 AgN03 mixes with PVP with the ratio of amount of substance 1,, in the ultrasonic water bath of 100～300W, slowly add it is dissolved fully.2, in mixing solutions, adding volume is the terepthaloyl moietie of 3 times of mixing solutionss, thorough mixing.3, this solution is transferred in the 1.5GHz household microwave oven heats, microwave power is adjusted into 100w, microwave treatment 3～4min.4, after question response finishes; The mixture that obtains is cooled to room temperature; The acetone that in mixture, adds volume and be 3～4 times of volume of mixture is in order to flush away terepthaloyl moietie and excessive PVP, and supersound process 2min then is with mixture spinning 2min under 10000 rev/mins of speed.Solid after the separation adds deionized water wash again, supersound process, spinning, and the pressed powder that repeats to obtain for 5 times places the mixture that obtains nano silver wire and Nano silver grain behind the dry 6h of vacuum drying oven.
The effect of epoxy resin toughness properties-correcting agent be used for more crisp epoxy-resin systems is carried out toughness reinforcing, to improve the shock-resistant and collision performance of conductive ink composition.The epoxy resin toughness properties-correcting agent that can adopt comprises: the mixture of nucleocapsid structure rubber, paracril, thiorubber, urethane, poly ether imide or above-mentioned substance, the nucleocapsid structure rubber toughening agent that effect is best.Epoxy adhesive second-order transition temperature after adopting nucleocapsid structure rubber toughened does not significantly descend, and the resistance toheat of electrically conductive ink is had no damage.More typical product is MX130 (Japanese KANEKA chemical company).
When being to reduce system viscosity, the effect of reactive thinner will not spend the cohesive strength of printing ink.The reactive diluent that can adopt comprises the glycidyl ether resin that contains bis-epoxy functional group, three epoxy-functionals or Fourth Ring oxygen functional group.Contain a plurality of epoxide groups in the above-mentioned thinner, in solidification process, can react, can increase the intensity and the adhesive property of printing ink itself with amine.More typical product has Araldite DY-T (three functional group epoxide diluents, Huntsman company).
The organic solvent agent is used for dissolving the viscosity of this resin system and this tackiness agent of adjustment in fact, to make the electrically conductive ink that is suitable on base material, carrying out silk screen printing most.The solvent that can adopt comprises dipropylene glycol methyl ether, ETHYLE ACETATE, ethyl carbitol, diglyme, dibasic ester flux, Trivalin SF, Ethyl carbitol acetate ester, diethylene glycol monobutyl ether, acetate of butyl carbitol, acetone, methylethylketone, pimelinketone, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, trihydroxymethylpropanyltri diglycidyl ether; The mixture of neopentylglycol diglycidyl ether, 1,4 butanediol diglycidyl ether or above-mentioned substance.The best organic solvent of effect is a dipropylene glycol methyl ether.
Randomly, can add suitable flowing additive, adhesion promotor, conductive filler material surface-modifying agent and rheology control agent as required.Optional flowing additive comprises silicon polymer, vinylformic acid/ethyl acrylate multipolymer, the hydroxyalkyl ammonium salt of the phosphate ester acid of ketoxime or the mixture of above-mentioned substance.Adhesion promotor mainly is the organosilicon alkanes; The mixture that comprises 3-chloropropylmethyldimethoxysilane, 3-cyclohexyl-amino methyl dimethoxy silane, 3-mercapto propyl group diethoxy silane, 3-mercapto propyl group methyl dimethoxysilane or above-mentioned substance, best is 3-mercapto propyl group diethoxy silane (chemistry ltd of moral nation).What rheology control agent was best is to adopt aerosil.The stuffing surface modification agent comprises the mixture of SULPHOSUCCINIC ACID ESTER, titanate, quinhydrones, hexadecyl trimethoxy amine bromide, X 2073 or above-mentioned substance.Effect is apparent that hexadecyl trimethoxy amine bromide most.
Positive progressive effect of the present invention is:
(1) described RFID printing has advantages such as electric conductivity height, cohesive strength height, stable electrical properties with electrically conductive ink.High energy surface at metal, pottery, glass and polymkeric substance all has good printing.
(2) adopt novel conductive filler material nano silver wire, it is too high to have solved in the conventional conductive printing ink filler content greatly, shortcomings such as cohesive strength difference.
(3) preparation method of the present invention is simple, and starting material are easy to get, and preparation condition is not harsh.
Embodiment
The present invention can further describe through following embodiment.
Embodiment 1: mix according to the quality weighing epoxy resin that provides in the table 2, epoxy toughness properties-correcting agent, adhesion promotor, rheology control agent and with them.The blended mode is a mechanical stirring, and stir speed (S.S.) is 1000 rev/mins, and the time is 10 minutes.The mixed fillers, stuffing surface modification agent, the thinner that under whipped state, in mixture, add load weighted nano silver wire and Nano silver grain then successively.Add and finish continued stirring 10 minutes.Even back to be mixed adds solidifying agent and curing catalyst in mixture, mechanical stirring changed mixture in the high speed shear mixing machine over to after 5 minutes mixes, and mixing rate is 2000 rev/mins, and the time is 30s.The jelly that the mixing process of repetition in the high speed shear mixing machine obtains mixing for 3 times is electrically conductive ink.
The preparation of the specimen of electrically conductive ink cohesive strength is carried out according to standard A STM1002-01; The copper base material that at first will be used to test is cleaned with ETHYLE ACETATE and is deoiled; Then glue is applied to and needs the agglutinating surface; Two copper sheets are closed up, be put in the curing oven after the employing metal holder is fixed, condition of cure is 120 degree 30 minutes.Sample cooling back after waiting to solidify is tested on tension testing machine and is obtained the concrete data of cohesive strength.The test of the specific conductivity of electrically conductive ink is carried out according to standard GBT12966-91, the preparation of sample be with ink coats at a length of a film 50mm, on the sheet glass of wide 20mm, treat that the printing ink levelling solidifies to be placed in the curing oven to be cured.Condition of cure is 120 degree 30 minutes.Carry out the surface resistivity test with four resistance appearance behind the sample cool to room temperature after waiting to solidify.
Cohesive strength, surface resistivity and surface resistivity stability test result according to the filling nano silver wire electrically conductive ink of embodiment 1 preparation list in table 1.Can find out that by data in the table average surface resistivity of electrically conductive ink reaches 10
-4Ω cm, under the room temperature on the copper coin cohesive strength reach 13MPa, through 80 ℃, the variation that 80% humidity ageing environment is handled surface resistivity after 500 hours is no more than 15%.
Embodiment 2～11
According to table 2 ingredients listed and consumption, weighing epoxy resin, epoxy toughness properties-correcting agent, adhesion promotor, rheology control agent etc. also mix them.The blended mode is a mechanical stirring, and stir speed (S.S.) is 1000 rev/mins, and the time is 10 minutes.Under whipped state, in mixture, add load weighted conductive filler material, stuffing surface modification agent, thinner then successively.Add and finish continued stirring 10 minutes.Even back to be mixed adds solidifying agent and curing catalyst in mixture, mechanical stirring changed mixture in the high speed shear mixing machine over to after 5 minutes mixes, and mixing rate is 2000 rev/mins, and the time is 30s.The jelly that the mixing process of repetition in the high speed shear mixing machine obtains mixing for 3 times is conductive ink composition.
Claims (10)
1. conductive ink composition is used in a radio frequency identification system printing, and components based on weight percentage is calculated, and forms as follows:
2%～10% at least a epoxy resin;
5～10% epoxy resin toughness properties-correcting agent;
30%～50% reactive diluent;
2%～4% solidifying agent;
The curing catalyst of 1%～1.5% weight;
The conductive filler material of 30～50% weight;
10%～30% organic solvent;
The flowing additive of 0～1.5% weight, adhesion promotor, rheological control agent and stuffing surface modification agent; The preparation method of said conductive filler material is: (1) is that 1: 2 AgNO3 mixes with PVP with the ratio of amount of substance, in the ultrasonic water bath of 100～300W, slowly adds it is dissolved fully; (2) in mixing solutions, adding volume is the terepthaloyl moietie of 3 times of mixing solutionss, thorough mixing; (3) this solution is transferred in the 1.5GHz household microwave oven heats, microwave power is adjusted into 100w, microwave treatment 3～4min; (4) after question response finishes; The mixture that obtains is cooled to room temperature; The acetone that in mixture, adds volume and be 3～4 times of volume of mixture is in order to flush away terepthaloyl moietie and excessive PVP, and supersound process 2min then is with mixture spinning 2min under 10000 rev/mins of speed; (5) solid after separating adds deionized water wash again, and supersound process, spinning repeat pressed powder that 5 above-mentioned steps obtain and place the mixture that obtains nano silver wire and Nano silver grain behind the dry 6h of vacuum drying oven.
2. conductive ink composition as claimed in claim 1 is characterized in that: said epoxy resin is chloropharin deutero-solid or liquid epoxies, and each molecule of this epoxy resin on average has 1～11 hydroxyl to add terminal epoxy groups.
3. conductive ink composition as claimed in claim 1 is characterized in that: solidifying agent is a hexamethoxy methyl cyanuramide.
4. conductive ink composition as claimed in claim 1 is characterized in that: curing catalyst is the mixture of tosic acid, two nonyl naphthalene disulfonic acids, Witco 1298 Soft Acid, oxalic acid, toxilic acid, Cyclamic Acid, phosphoric acid, alkyl phosphate, phthalic acid, vinylformic acid or above-mentioned substance.
5. the described conductive ink composition of claim 1, it is characterized in that: said conductive filler material is the mixture of nano silver wire and Nano silver grain, wherein the weight ratio of nano silver wire and Nano silver grain is 8: 2～9: 1.
6. conductive ink composition as claimed in claim 1 is characterized in that: said epoxy resin toughness properties-correcting agent is the mixture of nucleocapsid structure rubber toughening agent, paracril, thiorubber, urethane, poly ether imide or above-mentioned substance.
7. conductive ink composition as claimed in claim 6 is characterized in that: said epoxy resin toughness properties-correcting agent is the nucleocapsid structure rubber toughening agent.
8. conductive ink composition as claimed in claim 1 is characterized in that: said reactive diluent is the glycidyl ether resin that contains bis-epoxy functional group, three epoxy-functionals or Fourth Ring oxygen functional group.
9. conductive ink composition as claimed in claim 1; It is characterized in that: said organic solvent comprises dipropylene glycol methyl ether, ETHYLE ACETATE, ethyl carbitol, diglyme, Trivalin SF, Ethyl carbitol acetate ester, diethylene glycol monobutyl ether, acetate of butyl carbitol, acetone, methylethylketone, pimelinketone, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, trihydroxymethylpropanyltri diglycidyl ether; The mixture of neopentylglycol diglycidyl ether, 1,4 butanediol diglycidyl ether or above-mentioned substance.
10. conductive ink composition as claimed in claim 1 is characterized in that: flowing additive is silicon polymer, vinylformic acid/ethyl acrylate multipolymer, the hydroxyalkyl ammonium salt of the phosphate ester acid of ketoxime or the mixture of above-mentioned substance; Adhesion promotor is the mixture of 3-chloropropylmethyldimethoxysilane, 3-cyclohexyl-amino methyl dimethoxy silane, 3-mercapto propyl group diethoxy silane, 3-mercapto propyl group methyl dimethoxysilane or above-mentioned substance; The rheological control agent is an aerosil; The stuffing surface modification agent is the mixture of SULPHOSUCCINIC ACID ESTER, titanate, quinhydrones, hexadecyl trimethoxy brometo de amonio, X 2073 or above-mentioned substance.
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| CN 201010133151 CN101921505B (en) | 2010-03-25 | 2010-03-25 | Conductive printing ink composite for printing of wireless radio frequency identification devices (RFID) |
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| EP3591012A1 (en) | 2018-07-05 | 2020-01-08 | Chung-Ping Lai | Conductive ink for use in manufacturing radio frequency identification (rfid) tag antenna and method for manufacturing rfid tag antenna |
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