CN113527948A - Conductive ink for pad printing process and preparation method thereof - Google Patents

Conductive ink for pad printing process and preparation method thereof Download PDF

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Publication number
CN113527948A
CN113527948A CN202010317538.0A CN202010317538A CN113527948A CN 113527948 A CN113527948 A CN 113527948A CN 202010317538 A CN202010317538 A CN 202010317538A CN 113527948 A CN113527948 A CN 113527948A
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stirring
conductive ink
printing process
pad printing
process according
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江海涵
朱庆明
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SHANGHAI BAOYIN ELECTRONIC MATERIALS Ltd
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SHANGHAI BAOYIN ELECTRONIC MATERIALS Ltd
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Priority to PCT/CN2021/086305 priority patent/WO2021213190A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0042—Degasification of liquids modifying the liquid flow
    • B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/01—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with flat filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/70—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention relates to a conductive ink for a pad printing process and a preparation method thereof, which comprises the steps of pouring saturated polyester resin, thermoplastic polycarbonate resin, dibasic ester and propylene glycol monomethyl ether acetate into a dissolving kettle, controlling the stirring speed of the dissolving kettle at 2500rpm/min, stirring at a high speed for 5-6 h, heating the reaction kettle to 70 ℃, adding flake graphite, reacting for 3h, and discharging while the reaction is hot to obtain a composite carrier; sequentially adding the prepared composite carrier, polyethylene wax, dimethyl siloxane, a silane coupling agent, fumed silica, a mixture of nano spherical silver powder and flake silver powder and a solvent into a material barrel according to the mass percentage; high-speed stirring machine, circulating grinding, vacuum filtering; and canning the vacuum-filtered material, and stirring in a homogenizer for 3-5 min. The invention has the advantages of good degumming rate, good wear resistance, good conductivity and the like.

Description

Conductive ink for pad printing process and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to conductive ink for a pad printing process and a preparation method thereof.
Background
Conductive inks are widely used in the fields of printed circuits, semiconductor packaging, solar cells, and the like. Conductive silver paste and conductive carbon paste are the most widely used series of products in conductive ink, and these products are usually printed on a planar substrate by means of screen printing and then dried to form a conductive path. With the development of the electronic industry, the conventional screen printing process has developed a pad printing process because it cannot print on a special-shaped object. The pad printing process belongs to one of special printing modes. It can print figures and images on the surface of irregular shaped objects through colloid transfer printing, and is becoming an important special printing. For example, the surface electronic circuit printing of many electronic products such as mobile phone antennas, PCB board connectors, instruments and intelligent wear is completed by pad printing. After the conductive ink is transferred on the application fields, the base material has excellent conductive performance. Unlike screen printing conductive ink, the drying speed of pad printing conductive ink is faster, which is the most prominent characteristic of pad printing conductive ink. At the same time, pad printing conductive inks are susceptible to factors such as temperature, humidity, and static electricity. Therefore, weatherability is also a consideration in designing conductive inks for pad printing. The rate of ink degumming of the conductive ink for the pad printing process needs to be more than 98%, and the diffusivity of printing precision needs to be controlled within 10%. In addition, because the thermal deformation temperature of the printed substrate is low, the curing is required to be completed at low temperature (less than or equal to 120 ℃). After the conductive ink is transferred, it is also required to have excellent conductivity, rubbing resistance and weather resistance. Besides meeting the weather resistance conditions, the low-temperature conductive ink has higher and higher environmental protection requirements on products, and the existing common low-temperature conductive ink only has the requirements on conductivity and adhesive force and cannot meet the requirements on all degumming rates and friction resistance. At the present stage, the conductive ink for the pad printing process still has the defects of poor ink degumming head rate, substandard friction resistance and poorer conductive performance, so the research and development of the product have great significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the conductive ink for the pad printing process, which has the advantages of good degumming rate, good wear resistance and good conductivity, and the preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: the conductive ink for the pad printing process comprises the following components in parts by weight:
Figure BDA0002460116940000021
the silver flake powder has the average particle size of 4-6 mu m, is flaky, has good dispersibility in an ink system and excellent conductivity, has good hardness and low cost, and is about 50% lower than the cost of ink prepared from pure silver powder;
the average particle diameter of the nano spherical silver powder is 200-300nm, the purity is more than 99.95 percent, the nano spherical silver powder is spherical, and the specific surface area is 25m2/g-40m2G, volume density of 0.8-1.0g/cm3. The nano silver powder has low apparent density and good fluidity, has good filling effect and further promotes the conductivity.
The saturated polyester resin is linear saturated copolyester with high molecular weight, the molecular weight of the saturated copolyester is 20000g/mol, the glass transition temperature is 65-70 ℃, the softening temperature is 155 ℃, and the density is 1.25g/cm3(ii) a The high molecular resin has good hardness and flexibility and strong adhesive force to a base material.
The density of the thermoplastic polycarbonate resin is 1.18 to 1.22g/cm3Linear expansion coefficient of 3.8X 10-5cm/DEG C, and the heat distortion temperature is 135 ℃; the polycarbonate is colorless and transparent, heat-resistant, impact-resistant and flame-retardant at BI level, has good mechanical properties at common use temperature, has good impact resistance, high refractive index and good processability compared with the same property of polymethyl methacrylate, and has UL 94V-0 level flame retardant property without additives.
The dibasic ester is high-purity MDBE and is a mixture of dimethyl succinate, dimethyl glutarate and dimethyl adipate; the content is more than 99 percent, the water content is less than 0.1 percent, the solvent is an environment-friendly high boiling point solvent, the boiling range is 196-225 ℃, the average molecular weight is 159, the freezing point is-20 ℃, and the dibasic ester has excellent dissolubility, can promote the ink to have good leveling property and improve the gloss.
The molecular formula of the propylene glycol monomethyl ether acetate is C6H12O3The colorless hygroscopic liquid has special smell, is a non-polluted solvent with multiple functional groups, has the molecular weight of 132.16, the melting point of-87 ℃, the boiling point of 146 ℃ and the density of 0.96, is colorless transparent liquid, and can improve the strength of a coating film.
The polyethylene wax has the density of 0.93-0.98, the molecular weight of 3500, the melting point of 100 ℃, can be well dissolved with polyethylene, polypropylene, polyethylene wax acid, ethylene propylene rubber and butyl rubber, can improve the fluidity of the polyethylene, the polypropylene and the ABS and the demoulding performance of polymethyl methacrylate and polycarbonate, and has stronger internal lubricating effect compared with PVC and other external lubricants. The action principle is as follows: the polyethylene wax is dissolved in the solvent at high temperature (about 100 ℃ C.) -140 ℃ C., and is precipitated when being cooled to normal temperature, exists in the coating in a microcrystalline form, is favorable for storage of the coating due to the thixotropy, and can migrate to the surface layer of the coating in the volatilization process of the solvent after the coating is constructed and applied, and finally forms a wax-up surface layer with other components of the coating.
The molecular formula of the dimethyl siloxane is C2H8Si with the melting point of-150 ℃ and the boiling point of-20 ℃, and the defoaming agent with excellent performance can enable the spreading performance of the surface of the printing ink to be more excellent and form a firm film layer.
The average particle size of the fumed silica is 30nm, and the specific surface area is 180-220m2(iv)/g, purity > 99.8%, apparent density 30-60g/L, hydrophobic fumed silica for non-aqueous inks.
The average grain diameter of the flake graphite is 30-50nm, the purity is more than 99.9 percent, and the specific surface area is 180m2/g-200m2(g), tap density 2-2.5g/cm3And flaky black powder. The powder surface is treated, so that the powder has good dispersibility, and certain conductivity and friction resistance are increased in an ink coating。
A preparation method of conductive ink for a pad printing process comprises the steps of carrier configuration, material preparation, high-speed dispersion, three-roller grinding, filtration, finished product detection, homogeneous stirring, canning and the like, and specifically comprises the following steps:
(1) carrier configuration
Pouring saturated polyester resin, thermoplastic polycarbonate resin, dibasic ester serving as a solvent and propylene glycol methyl ether acetate (the mass ratio of the dibasic ester to the propylene glycol methyl ether acetate is 5:1) into a dissolving kettle, controlling the stirring speed of the dissolving kettle at 1500-2500rpm/min, stirring at a high speed for 5-6 h, heating the reaction kettle to 70 ℃, adding flake graphite, reacting for 3h, and discharging while hot to obtain a composite carrier; finally, the carrier is detected, and is taken out if the carrier is completely dissolved, and the dispersion time can be properly prolonged if undissolved powder particles still exist. After the dissolution was completed, the final carrier was filtered through a 250 mesh stainless steel net.
(2) Ingredients
In the step of batching, an electronic scale of a Mettler BBA211 model is used as a weighing tool and matched with a recording component, an operator can add raw materials of corresponding codes according to a display value of a panel, and the precision is controlled to be one ten thousandth. Sequentially adding the composite carrier prepared in the step (1), polyethylene wax, dimethyl siloxane, a silane coupling agent, fumed silica, a mixture of nano spherical silver powder and flake silver powder, and a solvent (the solvent is residual dibasic ester and propylene glycol monomethyl ether acetate) into a material barrel according to mass percentage;
(3) dispersing and grinding
Moving the material barrel to a high-speed stirrer, uniformly stirring the materials at a high speed, adding the materials into a three-roll grinder for circular grinding, and carrying out high-speed stirring again when the silver paste is rolled for one time; circulating for many times until the fineness of the material is less than or equal to 10 mu m;
(4) vacuum filtration
The vacuum filtration is carried out by adopting a stainless steel net with 250-400 meshes, and the main function is to separate large-particle impurities generated in the grinding process;
(5) homogenizing and stirring
And canning the vacuum-filtered material, and stirring in a homogenizer for 3-5 min.
Lowering the stirring head of the high-speed stirrer to a position 2cm away from the bottom of the material barrel, wherein the frequency of the high-speed dispersing stirrer is 75Hz, and the stirring time is 10-15 min; the judgment method for the uniform dispersion of the materials is to observe that the whole ink is silver gray slurry without silver powder particles, and then the ink is uniformly dispersed.
The cycle times of the dispersed grinding in the step (3) are three times, and the roller gap between the fast roller and the middle roller in the three-roller grinding machine is continuously and gradually controlled, the roller gap is controlled to be 0.3mm-0.35mm during the first grinding, the roller gap is controlled to be 0.25-0.3mm during the second grinding, and the roller gap is controlled to be 0.2-0.25mm during the third grinding.
And (4) the equipment adopted by the vacuum filtration comprises a vacuum pump and a stainless steel material cylinder connected with the vacuum pump, a stainless steel mesh with the size of 250-400 meshes is arranged above the stainless steel material cylinder, a vacuum pump switch is firstly turned on during use, then the dispersed conductive silver paste is continuously poured on the stainless steel mesh, and the silver paste is continuously paved by a rubber scraper so that the conductive silver paste is quickly filtered into the built-in stainless steel material cylinder.
And (5) defoaming and preventing the silver powder from settling, wherein the homogenized conductive ink is very fine and uniform, the vacuum degree is set to be 0.08-0.12 MPa when the homogenized conductive ink is used, and the canned conductive ink is put into a homogenizer to be stirred for 3-5 min. The conductive ink for the pad printing process after being homogenized and stirred can be directly taken out of a warehouse and filled.
The silver conductive ink adopts the flaky silver powder (with the average particle size of 4-6 microns) as a main solid phase, can have excellent conductivity after being cured into a film, and adopts the nano spherical silver powder (with the average particle size of about 250 nm) as a solid filling phase, so that gaps formed by the nano silver powder can be further filled, and the conductivity and the adhesive force of the conductive ink are enhanced; the saturated polyester resin is used as a main binding phase, so that the adhesive force and the flexibility are strong, and the wide adaptability to different printing base materials is enhanced; the thermoplastic polycarbonate resin is used as an auxiliary binding phase, so that the wear resistance is very high; the adoption of a stepped compound solvent phase (dibasic ester and propylene glycol monomethyl ether acetate) not only meets the environmental protection requirements of European Union ROSH and WEEE, but also can realize rapid curing and prevent the local expansion phenomenon of a printed pattern; polyethylene wax is used as an anti-settling agent, so that the anti-settling property can be enhanced, the storage time of the product can be prolonged, and the influence effect on the electrical conductivity is small due to the linear structure; the conductive graphite is used as the lubricant after film formation, so that the hardness of the lubricity enhanced film layer after film formation of the conductive ink can be effectively increased. The home-made vacuum filter is adopted, so that the screen printing effect of a client can be effectively simulated, and impurities generated in the preparation of the conductive ink are filtered; the homogeneous stirrer can defoam the conducting ink effectively and mix the material fully to reach higher fineness and homogeneity.
Compared with the prior art, the invention has the following advantages:
through the formula design of the ink coating, different raw materials are screened and compounded to prepare the conductive ink for the pad printing process. The silver conductive ink has the advantages that the flaky silver powder (with the average particle size of 4-6 mu m) is used as a main solid phase, the silver conductive ink can have excellent conductivity after being cured into a film, and the nano spherical silver powder (with the average particle size of about 250 nm) is used as a solid filling phase, so that gaps formed by the nano silver powder can be further filled, and the conductivity and the adhesive force of the conductive ink are enhanced; the saturated polyester resin is used as a main binding phase, so that the adhesive force and the flexibility are strong, and the wide adaptability to different printing base materials is enhanced; the thermoplastic polycarbonate resin is used as an auxiliary binding phase, so that the wear resistance is very high; the adoption of a stepped compound solvent phase (dibasic ester and propylene glycol monomethyl ether acetate) not only meets the environmental protection requirements of European Union ROSH and WEEE, but also can realize rapid curing and prevent the local expansion phenomenon of a printed pattern; polyethylene wax is used as an anti-settling agent, so that the anti-settling property can be enhanced, the storage time of the product can be prolonged, and the influence effect on the electrical conductivity is small due to the linear structure; the conductive graphite is used as the lubricant after film formation, so that the hardness of the lubricity enhanced film layer after film formation of the conductive ink can be effectively increased. The home-made vacuum filter is adopted, so that the screen printing effect of a client can be effectively simulated, and impurities generated in the preparation of the conductive ink are filtered; the homogeneous stirrer can defoam the conducting ink effectively and mix the material fully to reach higher fineness and homogeneity.
The obtained conductive ink has the advantages of degumming head rate of 100%, friction resistance of more than 600 times and good conductivity, so that the research and development significance of the product is great.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Examples 1 to 5
A preparation method of conductive ink for a pad printing process comprises the following components and ingredients shown in Table 1. Wherein the saturated polyester resin and the thermoplastic polycarbonate resin are used as binding phases, and the formula is as follows: firstly, adding saturated polyester resin and thermoplastic polycarbonate resin into a reaction kettle, gradually heating to 50 ℃, and then dropwise adding dibasic ester and propylene glycol methyl ether acetate according to the proportion of 5:1 and heating to melt to prepare the modified polycarbonate resin; the used nano spherical silver powder is ultrafine powder, and the average particle size is 300-500 nm.
TABLE 1
Name of Material Example 1 Example 2 Example 3 Example 4 Example 5
Flake silver powder 5.5 5.4 5.3 5.2 5.1
Nano spherical silver powder 1.5 1.6 1.7 1.8 1.9
Saturated polyester resin 1.0 1.0 1.0 1.0 1.0
Thermoplastic polycarbonate resin 0.7 0.7 0.7 0.7 0.7
Dibasic acid esters 1 1 1 1 1
Third twoAlcohol methyl ether acetate 0.2 0.2 0.2 0.2 0.2
Polyethylene wax 0.02 0.02 0.02 0.02 0.02
Dimethylsiloxane 0.02 0.02 0.02 0.02 0.02
Silane coupling agent 0.01 0.01 0.01 0.01 0.01
Fumed silica 0.03 0.03 0.03 0.03 0.03
Flake graphite 0.02 0.02 0.02 0.02 0.02
Adding saturated polyester resin and polycarbonate resin into a reaction kettle according to the formula proportion, gradually heating to 50 ℃, then adding dibasic ester and propylene glycol methyl ether acetate into the reaction kettle in a dropwise manner according to the ratio of 5:1, wherein the dropwise adding time is 1.5h, and continuously reflecting for 3h after the dropwise adding is finished. And then, heating the reaction kettle to 70 ℃, adding the flake graphite into the reaction kettle, reacting for 3 hours, discharging while the flake graphite is hot to obtain the polyurethane resin and polycarbonate resin composite carrier, and storing in a dark place. In the step of batching, an electronic scale of a Mettler BBA211 model is used as a weighing tool and matched with a recording component, an operator can add raw materials of corresponding codes according to a display value of a panel, and the precision is controlled to be one ten thousandth. The sequence of ingredient weighing is as follows: adding a saturated polyester resin and polycarbonate resin composite carrier → adding polyethylene wax, dimethyl siloxane, a silane coupling agent and fumed silica → adding a mixture of nano spherical silver powder and flake silver powder → adding a solvent.
After weighing, moving the material barrel to a high-speed disperser platform, then starting a switch of the high-speed disperser, lowering the stirring head to a position of 2cm from the barrel bottom, starting a variable frequency switch to 60Hz, and continuously stirring for 3min after setting timing. And then moving the material barrel to a three-roller grinding machine platform, wherein four cycles are needed for rolling of the three-roller grinding machine, and the high-speed dispersion step is needed to be carried out once again every time the silver paste is rolled. And then continuously and gradually controlling the gap between a fast roller and a middle roller of the three-roller grinding machine, wherein the roller gap for grinding the low-temperature conductive silver paste for the first time is 0.3mm, the roller gap for the second time is 0.25mm, and the roller gap for the third time is controlled to be 0.2 mm. And moving the material barrel reaching the fineness of less than 10um to a vacuum filtering platform, installing a 400-mesh stainless steel net above the filter and completely filtering the printing ink. And (4) detecting the semi-finished product completely filtered by a detection department, homogenizing and stirring after the semi-finished product reaches the enterprise standard, setting the vacuum degree to be 0.12Mpa, and then putting the silver paste filled into the tank into a homogenizer to stir for 3 min. The properties of the conductive inks for the pad printing process are shown in table 2.
TABLE 2
Figure BDA0002460116940000071
Figure BDA0002460116940000081
Examples 6 to 10
The components and contents (wt%) of the conductive ink for pad printing process described in the following examples are shown in Table 3:
TABLE 3
Figure BDA0002460116940000082
Figure BDA0002460116940000091
The conductive ink for the pad printing process in each of the above examples was prepared by the following method:
(1) carrier configuration
Pouring saturated polyester resin, thermoplastic polycarbonate resin, dibasic ester serving as a solvent and propylene glycol methyl ether acetate (the mass ratio of the dibasic ester to the propylene glycol methyl ether acetate is 5:1) into a dissolving kettle, controlling the stirring speed of the dissolving kettle at 1500-2500rpm/min, stirring at a high speed for 5-6 h, heating the reaction kettle to 70 ℃, adding flake graphite, reacting for 3h, and discharging while hot to obtain a composite carrier; finally, the carrier is detected, and is taken out if the carrier is completely dissolved, and the dispersion time can be properly prolonged if undissolved powder particles still exist. After the dissolution was completed, the final carrier was filtered through a 250 mesh stainless steel net.
(2) Ingredients
In the step of batching, an electronic scale of a Mettler BBA211 model is used as a weighing tool and matched with a recording component, an operator can add raw materials of corresponding codes according to a display value of a panel, and the precision is controlled to be one ten thousandth. Sequentially adding the composite carrier prepared in the step (1), polyethylene wax, dimethyl siloxane, a silane coupling agent, fumed silica, a mixture of nano spherical silver powder and flake silver powder, and a solvent (the solvent is residual dibasic ester and propylene glycol monomethyl ether acetate) into a material barrel according to mass percentage;
(3) dispersing and grinding
Moving a material barrel to a high-speed stirrer, reducing the stirring head of the high-speed stirrer to the position of 2cm from the bottom of the material barrel, uniformly stirring the material at a high speed with the frequency of 75Hz and the stirring time of 10-15 min, and finally observing that the whole ink is silver gray slurry and has no silver powder particles, uniformly dispersing, adding a three-roll grinder to carry out circular grinding for three times, and continuously and gradually controlling the roll gap between a fast roll and a middle roll in the three-roll grinder, wherein the roll gap is controlled to be 0.3mm-0.35mm during the first grinding, the roll gap is controlled to be 0.25-0.3mm during the second grinding, the roll gap is controlled to be 0.2-0.25mm during the third grinding, and the high-speed stirring is required again after each rolling of silver paste; circulating for many times until the fineness of the material is less than or equal to 10 mu m;
(4) vacuum filtration
The vacuum filtration is carried out by adopting a stainless steel net with 250-400 meshes, and the main function is to separate large-particle impurities generated in the grinding process; the equipment that vacuum filtration adopted includes the vacuum pump and rather than the stainless steel material section of thick bamboo of being connected, and 250-plus 400 mesh stainless steel nets are installed to this stainless steel material section of thick bamboo top, open the vacuum pump switch earlier during the use, and the electrically conductive silver thick liquid that finishes of dispersion is constantly emptyd afterwards on the stainless steel net to constantly paving the silver thick liquid with the rubber scraper blade, make it filter in built-in stainless steel material section of thick bamboo fast.
(5) Homogenizing and stirring
And canning the vacuum-filtered material, and stirring in a homogenizer for 3-5 min. The homogenizing and stirring effects mainly include defoaming and preventing the silver powder from settling, the homogenized conductive ink is very fine and uniform, the vacuum degree is set to be 0.08-0.12 MPa when the conductive ink is used, and the canned ink is put into a homogenizer and stirred for 3-5 min. The conductive ink for the pad printing process after being homogenized and stirred can be directly taken out of a warehouse and filled.
TABLE 4
Figure BDA0002460116940000101
Figure BDA0002460116940000111

Claims (10)

1. The conductive ink for the pad printing process is characterized by comprising the following components in parts by weight:
Figure FDA0002460116930000011
2. the conductive ink for pad printing process according to claim 1, wherein the average particle size of the silver flakes is 4 to 6 μm;
the average particle diameter of the nano spherical silver powder is 200-300nm, the purity is more than 99.95 percent, the nano spherical silver powder is spherical, and the specific surface area is 25m2/g-40m2G, volume density of 0.8-1.0g/cm3。
3. The conductive ink for pad printing process according to claim 1, wherein the saturated polyester resin is a high molecular weight linear saturated copolyester having a molecular weight of 20000g/mol, a glass transition temperature of 65-70 ℃, a softening temperature of 155 ℃ and a density of 1.25g/cm3；
The density of the thermoplastic polycarbonate resin is 1.18 to 1.22g/cm3Linear expansion coefficient of 3.8X 10-5cm/DEG C, and the heat distortion temperature is 135 ℃;
the dibasic ester is high-purity MDBE and is a mixture of dimethyl succinate, dimethyl glutarate and dimethyl adipate;
the molecular formula of the propylene glycol monomethyl ether acetate is C6H12O3Colorless hygroscopic liquid has special smell and is a non-polluted solvent with multiple functional groups.
4. The conductive ink for pad printing process according to claim 1, wherein the polyethylene wax has a density of 0.93-0.98, a molecular weight of 3500, and a melting point of 100 ℃;
the molecular formula of the dimethyl siloxane is C2H8Si, melting point-150 ℃, boiling point-20 ℃;
the average particle size of the fumed silica is 30nm, and the specific surface area is 180-220m2The purity is more than 99.8 percent and the apparent density is 30 to 60 g/L.
5. The conductive ink for pad printing process according to claim 1, wherein the graphite flakes have an average particle size of 30 to 50nm, a purity of > 99.9%, and a specific surface area of 180m2/g to 200m2(g), tap density 2-2.5g/cm3And flaky black powder.
6. A method for preparing the conductive ink for the pad printing process according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) carrier configuration
Pouring saturated polyester resin, thermoplastic polycarbonate resin, dibasic ester and propylene glycol monomethyl ether acetate into a dissolving kettle, controlling the stirring speed of the dissolving kettle at 2500rpm/min, stirring at a high speed for 5-6 h, heating the reaction kettle to 70 ℃, adding flake graphite, reacting for 3h, and discharging while the reaction is hot to obtain a composite carrier;
(2) ingredients
Sequentially adding the composite carrier prepared in the step (1), polyethylene wax, dimethyl siloxane, a silane coupling agent, fumed silica, a mixture of nano spherical silver powder and flake silver powder and a solvent into a material barrel according to mass percentage;
(3) dispersing and grinding
Moving the material barrel to a high-speed stirrer, uniformly stirring the materials at a high speed, adding the materials into a three-roll grinder for circular grinding, and carrying out high-speed stirring again when the silver paste is rolled for one time; circulating for many times until the fineness of the material is less than or equal to 10 mu m;
(4) vacuum filtration
Vacuum filtering with a stainless steel net of 250 and 400 meshes;
(5) homogenizing and stirring
And canning the vacuum-filtered material, and stirring in a homogenizer for 3-5 min.
7. The preparation method of the conductive ink for the pad printing process according to claim 1, wherein the stirring head of the high-speed stirrer in the step (3) is lowered to a position 2cm away from the bottom of the material barrel, the frequency of the high-speed dispersion stirrer is 75Hz, and the stirring time is 10-15 min; the judgment method for the uniform dispersion of the materials is to observe that the whole ink is silver gray slurry without silver powder particles, and then the ink is uniformly dispersed.
8. The method of preparing a conductive ink for pad printing process according to claim 1, wherein the number of cycles of the dispersive grinding in step (3) is three, and the roll gap between the fast roll and the medium roll of the three-roll grinder is controlled to be gradually increased, wherein the roll gap is controlled to be 0.3mm to 0.35mm in the first grinding, 0.25 to 0.3mm in the second grinding, and 0.2 to 0.25mm in the third grinding.
9. The method for preparing the conductive ink for the pad printing process according to claim 1, wherein the equipment adopted in the vacuum filtration in the step (4) comprises a vacuum pump and a stainless steel material cylinder connected with the vacuum pump, a stainless steel mesh with the size of 250-400 meshes is arranged above the stainless steel material cylinder, when the method is used, a switch of the vacuum pump is firstly turned on, then the dispersed conductive silver paste is continuously poured on the stainless steel mesh, and a rubber scraper is used for continuously paving the silver paste to rapidly filter the conductive silver paste into the built-in stainless steel material cylinder.
10. The method for preparing the conductive ink for the pad printing process according to claim 1, wherein the vacuum degree in the material tank before the homogeneous stirring in the step (5) is 0.08-0.12 MPa.
CN202010317538.0A 2020-04-21 2020-04-21 Conductive ink for pad printing process and preparation method thereof Pending CN113527948A (en)

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