TWI461491B - Dispersion, inkjet ink, and manufacturing the inkjet ink - Google Patents

Description

Dispersion and inkjet ink and method of forming same

This invention relates to glass pigments, and more particularly to the use of glass pigments in inkjet inks.

Glass pigments cannot be applied to low-viscosity slurries due to their large particles and high density. At present, the application of glass pigments still remains in traditional hand-painted creations and screen printing, such as low-resolution images such as church glass and escalator painting. With the development of modern technology, glass is inseparable from architecture and decoration, and people's quality requirements for full-color image glass have increased. If glass pigments are combined with digital printing technology, the quality of glass images can be greatly improved, and a new generation of products can be created and digital arts can be implemented in life.

At present, the research on glass pigments in various research units in the world only reveals how to effectively disperse micron-sized pigments (between 1 and 10 micrometers), but does not mention how to stably disperse submicron pigments (between 0.1 and 0.9 micrometers). In low viscosity paste. In addition, there is currently no solution to the problem of large color reduction of the color density of sub-micron pigments.

In summary, there is a need for new methods to disperse submicron glass pigment micropowders in low viscosity slurries.

An embodiment of the present invention provides a glass pigment micropowder comprising: 100 parts by weight of a flux; and 25 to 100 parts by weight of an inorganic pigment, wherein the particle size distribution of the glass pigment micropowder after grinding and dispersing is between 50 nm and 800 nm The average particle diameter of the glass pigment fine powder is between 100 nm and 300 nm.

An embodiment of the present invention provides a dispersion comprising: 100 parts by weight of the glass pigment fine powder of the first application of claim 1; 20 to 80 parts by weight of a dispersant; and 100 to 900 parts by weight of a solvent.

An embodiment of the present invention provides an inkjet ink comprising: the above dispersion; 1 to 15 parts by weight of the resin; 1 to 15 parts by weight of the cosolvent; and 1 to 15 parts by weight of the additive.

An embodiment of the present invention provides a method for forming an inkjet ink, comprising: mixing 100 parts by weight of a flux with 25 to 100 parts by weight of an inorganic pigment and sintering to form a glass pigment block; and pulverizing the glass pigment block to form The glass pigment fine particles are further ball-milled with 100 parts by weight of the glass pigment fine particles, 20 to 80 parts by weight of the dispersing agent, and 100 to 900 parts by weight of the solvent to form a dispersion containing the glass pigment fine powder, wherein the glass pigment in the dispersion liquid The particle size distribution of the fine powder is between 50 nm and 800 nm, and the average particle diameter of the glass pigment fine powder in the dispersion is between 100 nm and 300 nm; and mixing 100 parts by weight of the dispersion, 1 to 15 parts by weight of the resin And 1 to 15 parts by weight of the cosolvent, and 1 to 15 parts by weight of the additive to form an inkjet ink.

An embodiment of the invention provides a method of forming an inkjet ink. First, 100 parts by weight of the flux is mixed with 25 to 100 parts by weight of the inorganic pigment and sintered to form a glass pigment block. In an embodiment of the invention, the flux may be cerium oxide, aluminum oxide, lead oxide, zinc oxide, fluoride or The combination described. In an embodiment of the invention, the yellow inorganic pigment may be cadmium yellow (PY35, CI77205, CAS#12237-67-1), titanium nickel yellow (PY53, CI77788, CAS#8007-18-9).鐠Zirconium yellow (PY159, CI77997, CAS#68187-15-5), chrome titanium yellow (PY162, CI77896, CAS#68611-42-7; PY163, CI77897, CAS#68186-92-5), And 铋 yellow (PY184, CI771740, CAS #14059-33-7). Magenta inorganic pigments are iron red (PR101, CI77491, CAS#1317-60-8), cadmium red (PR108, CI77202, CAS#58339-34-7), lead chrome red (PR104, CI77605) , CAS #12656-85-8; PR105, CI77578, CAS #1314-41-6) and iron zirconium red (PR232, CI77996, CAS #68412-79-3). The Cyan inorganic pigments are cobalt blue (PB28, C.I. 77364, CAS #68187-40-6) and cobalt chrome blue (PB36, C.I.77343, CAS #68187-11-1). Black inorganic pigments are ferromanganese (PBK26, CI77494, CAS# 68186-94-7; PBK33, CI77537, CAS #75864-23-2), cobalt iron chrome black (PBK27, CI77502, CAS# 68186-97-0), copper chrome black (PBK28, CI77428, CAS #68186-91-4), ferrochrome black (PBK30, CI77504, CAS #71631-15-7) and titanium black (PBK35, CI77890 , CAS#70248-09-8). The white inorganic pigments are titanium white (PW6, CI77891, CAS #13463-67-7), zirconium white (PW12, CI77990, CAS #1314-23-4), and zinc white (PW4, CI77947, CAS#1314-13-2). The orange inorganic pigments are cadmium orange (PO20, C.I. 77199, CAS #12656-57-4) and orange chrome yellow (PO21, C.I.77601, CAS #1344-38-3). Green inorganic pigment is chrome green (PG17, CI77288, CAS#1308-38-9), cobalt green (PG19, CI77335, CAS#8011-87-8), cobalt chrome green (PG26, CI77344, CAS#68187-49-5), and cobalt titanium Green (PG50, CI77377, CAS#68186-85-6). If the amount of the inorganic pigment is too low, the color density of the pattern formed by the finally formed inkjet ink is too low. If the amount of the inorganic pigment is too high, it cannot be sintered with a flux to form a glass pigment block. For example, when the black inorganic pigment is copper chrome black (CAS #68186-91-4), the proper weight ratio of the flux to the black inorganic pigment is between 100:25 and 100:55. When the magenta inorganic pigment is cadmium red (CAS #58339-34-7), the proper weight ratio of flux to magenta inorganic pigment is between 100:25 and 100:50. When the yellow inorganic pigment is cadmium yellow (CAS #8007-18-9), the proper weight ratio of the flux to the yellow inorganic pigment is between 100:20 and 100:50. When the Cyan inorganic pigment is cobalt blue (CAS #68187-40-6), the proper weight ratio of the flux to the cyan inorganic pigment is between 100:35 and 100:55. When the white inorganic pigment is titanium white (CAS #13463-67-7), the proper weight ratio of the flux to the white inorganic pigment is between 100:25 and 100:65. When the Orange inorganic pigment is cadmium orange (CAS #12656-57-4), the proper weight ratio of the flux to the orange inorganic pigment is between 100:20 and 100:50. When the green inorganic pigment is cobalt titanium green (CAS #68186-85-6), the proper weight ratio of the flux to the green inorganic pigment is between 100:20 and 100:50. The temperature of the above-mentioned glass pigment co-firing block is between 600 ° C and 1200 ° C, and the co-firing time is between 15 and 120 minutes. If the co-firing temperature is too low and/or the co-firing time is too short, the glass frit cannot be effectively softened, and the inorganic after cooling The pigment will not be effectively co-fired with the glass frit. If the co-firing temperature is too high and/or the co-firing time is too long, the glass frit is excessively melted, and the inorganic pigment is allowed to settle and aggregate for a long time to cause a large inorganic pigment agglomerate. After cooling, the glass phase cannot be effectively coated and aggregated. Inorganic pigment agglomerates.

The glass pigment block is then comminuted to form glass pigment particles having a particle size between about 1 and 10 microns. Thereafter, 100 parts by weight of the glass pigment fine particles, 20 to 80 parts by weight of the dispersing agent, and 100 to 900 parts by weight of the solvent are ball-milled to form a dispersion containing the glass pigment fine powder. In one embodiment of the invention, the dispersant is a comb copolymer or block copolymer formed by copolymerization of an epoxy resin and an etheramine. In an embodiment of the invention, the epoxy resin may be a bisphenol A epoxy resin or an aliphatic epoxy resin (such as Oxirane, 2, 2'-(1,6-hexanediyl) bis-), and the etheramine may be Jeffamine. ® and the Surfonamine® series of L300, M600, B60, M1000, M2005 and M2070, and the copolymer has a weight average molecular weight of between 2,000 and 20,000 g/mole. If the weight average molecular weight of the copolymer is too high, the viscosity of the dispersion will be too high. If the weight average molecular weight of the copolymer is too low, the too short solvent end cannot effectively stabilize the glass inorganic pigment in the solvent. In another embodiment of the invention, the dispersing agent can be a commercial item such as 2050, 165 or 9250 available from BYK. If the amount of the dispersant is too low, the stable glass inorganic pigment cannot be effectively coated, and the glass inorganic pigment is liable to settle and aggregate. If the amount of the dispersant is too high, the viscosity of the dispersion is too high, and the glass inorganic pigment is easily reaggregated.

The solvent in the above ball milling step includes diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, and tetraethyl ethane. One of the glycol dimethyl ethers. If the amount of the solvent is too high, the color density of the pattern formed by the inkjet ink is lowered. If the amount of the solvent is too low, the fluidity of the inkjet ink is lowered and it cannot be applied to an ink jet machine.

After the above ball milling process, the glass pigment fine powder in the dispersion can be further reduced to a submicron order. In an embodiment of the invention, the glass pigment fine powder has a particle size distribution between 50 nm and 800 nm, and the glass pigment fine powder has an average particle diameter of between 100 nm and 300 nm. If the particle size of the glass pigment fine powder is too large (for example, on the order of micrometers), the sedimentation speed of the glass pigment is too fast, and it is easy to block the inkjet head. If the particle size of the glass pigment fine powder is too small, the color concentration of the color glass pigment will be greatly reduced.

Finally, 100 parts by weight of the above dispersion, 1 to 15 parts by weight of the resin, 1 to 15 parts by weight of the co-solvent and 1 to 15 parts by weight of the additive are mixed to form an inkjet ink. In an embodiment of the invention, the resin may be polyester (ARU 5550, available from Yongkeng Industry), polyurethane (5715, 5719 or 5705 from Innophos), polymethyl methacrylate (PMMA), or a combination thereof. To adjust the adhesion of the ink to the glass substrate and printability. If the amount of the resin is too high, the viscosity of the ink will be too high to allow ink to be ejected. If the amount of the resin is too low, the adhesion of the ink to the substrate may be poor. In one embodiment of the invention, the additive may be a leveling agent such as 355 from BYK, a wetting agent such as 334, 354, 410, 420, 430, or 430 from BYK or combinations thereof. If the amount of the additive is too high, the compatibility between the components in the ink is affected. If the amount of the additive is too low, good printability and corresponding ink setting and wetting effects cannot be achieved. In an embodiment of the invention, the co-solvent may be methyl acetate, ethyl acetate, n-propyl acetate, isobutanol, monomethyl Ethylene glycol acetate, γ-butyrolactone, diethylene glycol dimethyl ether, ethylene glycol butyl ether, tetraethylene glycol dimethyl ether, or a combination thereof to adjust ink into ink Dryness. In an embodiment of the invention, the co-solvent comprises at least two of diethylene glycol dimethyl ether, ethylene glycol butyl ether, and tetraethylene glycol dimethyl ether. For example, the cosolvent contains 0 to 30 parts by weight of diethylene glycol dimethyl ether, 5 to 15 parts by weight of ethylene glycol butyl ether, and 1 to 10 parts by weight of tetraethylene glycol dimethyl ether. In one embodiment of the invention, the finally formed inkjet ink has a viscosity of between 2 and 30 cps at 45 °C. If the viscosity of the inkjet ink is too low, the ink dots cannot be fixed on the substrate. If the viscosity of the inkjet ink is too high, the ink cannot be ejected.

Finally, the inkjet ink is sprayed onto the glass substrate, the solvent in the inkjet ink is removed, and after heating to 600 ° C to 850 ° C for 0.1 to 15 minutes, the ink film of the inkjet pattern is sintered into the glass base. Material, and achieve glass strengthening during the cooling process, and the resolution of the pattern is between 80dpi and 1550dpi. If the sintering temperature is too low and/or the sintering time is too short, the pigment cannot be sintered into the glass. If the sintering temperature is too high and/or the sintering time is too long, the glass substrate is excessively softened to cause bending. In one embodiment of the invention, the temperature of the step of removing the solution in the inkjet ink is about 50 ° C and the time is about 30 minutes.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

[Examples] Example 1

Different weight parts of black inorganic pigment (copper chrome black, purchased from Songjiang Industrial, part number: 10400), magenta inorganic pigment (cadmium red compound, purchased from Songjiang Industrial, part number: 10768), yellow inorganic pigment (cadmium yellow) Compound, purchased from Songjiang Industrial, part number: 10350), cyan inorganic pigment (chrome blue, oxide purchased from Songjiang Industrial, material number: 10294), white pigment inorganic pigment (titanium white, purchased from Songjiang Industrial, part number: 10900 Mixing with different weights of flux (yttria, alumina, lead oxide, zinc oxide, fluoride, glass powder (P8) purchased from Songjiang Industrial), placed in a high temperature furnace, heated to 800 °C, 1 After cooling for 1 hour, the glass pigment bulk was formed. The glass pigment blocks co-fired by the glass frit and the pigment powder are pulverized to form micron-sized (1 to 10 micron) particles, which are then ground and dispersed to form a submicron (0.1 to 900 micron) glass pigment dispersion (see The process described later is prepared by ink printing and directly printed on a glass substrate by a digital printing device. The printing pattern is heated to 50 ° C and maintained for 30 minutes to remove the solvent, and finally maintained at 700 ° C for 1 minute under high temperature sintering conditions. The pattern is shaped, and the color density (or brightness) of the different colors is shown in Table 1:

It can be seen from the first table that the appropriate weight ratio of the flux to the black inorganic pigment is between 100:25 and 100:55, and the flux and the magenta inorganic pigment are appropriate, with a color concentration greater than 1.0 or a whiteness greater than 65. The weight ratio is between 100:25 and 100:50, the appropriate weight ratio of flux to yellow inorganic pigment is between 100:20 and 100:50, and the appropriate weight ratio of flux to cyan inorganic pigment is between 100: Between 35 and 100:50, and the proper weight ratio of flux to white inorganic pigment is between 100:45 and 100:65.

Example 2

An epoxy resin was copolymerized with an etheramine to form a comb copolymer (bisphenol A epoxy resin BE188 and Jeffamine L300 copolymer) as a dispersing agent. Next, the black glass pigment bulk material (the process of which is described later) is initially pulverized to a fine powder of fine particles (1 to 10 μm), and then 50 parts by weight of a dispersant (BE188-L300 copolymer) and 100 parts by weight of a glass pigment fine powder are taken. 350 parts by weight of a solvent (γ-butyrolactone) was formed into a mixture having a solid content of 30%, and then placed in a ball mill (JBM- with a fixed filling rate of yttrium-stabilized zirconia grinding balls (particle size: 0.2 mm). B035, Fuxin Nano Technology), the ball milling process was carried out at different ball milling speeds for 11 hours to form a dispersion. The ball milling results are shown in Table 2:

As can be seen from the second table, an appropriate ball milling speed is 2400 rpm.

In order to confirm whether the grinding ball filling rate is appropriate, the ball grinding speed was fixed at 2400 rpm, and the grinding ball filling rate was adjusted. The results are shown in Table 3. The parameters such as the dispersant/pigment weight ratio, solvent type and amount ratio, grinding ball type, ball mill, and ball milling time are the same as those corresponding to the second table.

As can be seen from the third table, the appropriate ball filling rate was 47%.

In order to confirm whether the solid content was appropriate, the ball milling speed was fixed at 2400 rpm and the grinding ball filling rate was fixed at 47%, and the amount of the solvent was changed to adjust the solid content of the dispersion. The results are shown in Table 4. The parameters such as the type of grinding ball, the ball mill, and the ball milling time are the same as those corresponding to the third table.

As can be seen from the fourth table, an appropriate solid content is 30%.

Example 3

The glass pigment of the flux/inorganic pigment weight ratio which is optimal in color concentration (or brightness) in Table 1 and different dispersing agents such as BYK-2050, BYK-165, and Deqian Enterprise-Element 9850 was placed in a ball mill to form a dispersion with the ball milling parameters described above. The average particle diameter, particle size distribution index (PDI), and particle size (D95, D100) of the glass pigment in the dispersion are shown in Tables 5-7.

As can be seen from Tables 5-7, the dispersion process allows the glass pigment to be refined to sub-micron levels.

Example 4

The dispersions of different colors in the seventh table of Example 3 were added to a cosolvent (diethylene glycol dimethyl ether, ethylene glycol butyl ether, and tetraethylene glycol dimethyl ether), a resin (ARU 5550) and a wetting agent ( After BYK355), an inkjet ink was formed, the composition of which is shown in Table 6.

The inkjet ink was sprayed on a glass substrate, and the printing pattern was heated to 50 ° C for 30 minutes to remove the solvent, and finally the ink jet pattern was sintered into a glass substrate under high temperature sintering conditions of 700 ° C. The physical properties of the inkjet ink are such that the viscosity (cps) at 45 ° C is between 2 and 30, the surface tension (dyne/cm) is between 23 and 30, the average particle diameter (nm) of the glass pigment fine powder, and after sintering. The inkjet ink color density (density) is shown in Table 9.

As is apparent from the ninth table, the glass pigment which is refined to the submicron order can be stably dispersed in the inkjet ink to form a pattern having a high color density.

Comparative example 1

Different weight parts of black inorganic pigment (copper chrome black, purchased from Songjiang Industrial, part number: 10400), magenta inorganic pigment (cadmium red compound, purchased from Songjiang Industrial, part number: 10768), yellow inorganic pigment (cadmium yellow) Compound, purchased from Songjiang Industrial, part number: 10350), cyan inorganic pigment (chrome blue, oxide purchased from Songjiang Industrial, material number: 10294), white pigment inorganic pigment (titanium white, purchased from Songjiang Industrial, part number: 10900 ) Mixing different weight parts of flux (yttrium oxide, aluminum oxide, lead oxide, zinc oxide, fluoride, glass powder (P8) purchased from Songjiang Industrial), directly adding different dispersing agents such as BYK-2050, BYK- 165, and Deqian Enterprise-Element 9850 was placed in a ball mill to form a dispersion with the above ball milling parameters. Since the inorganic pigment micropowder and the flux are not co-fired in advance, the surface of the inorganic pigment and the flux are different in the grinding stabilization stage, and the dispersant is not easily effective and stabilizes the dispersion of the inorganic pigment micropowder and the flux, so that the formed The dispersion could not reach a stable dispersion, so the stable particle size of the fine powder in the dispersion could not be measured.

Then, the above dispersion is added to a cosolvent (diethylene glycol dimethyl ether, ethylene glycol butyl ether, and tetraethylene glycol dimethyl ether), a resin (ARU 5550) and a wetting agent (BYK355) to form an inkjet ink. . However, the above inkjet ink is liable to cause clogging of the ink jet head The inkjet ink is sprayed on the glass substrate, and the printing pattern is heated to 50 ° C for 30 minutes to remove the solvent, and finally sintered at 700 ° C. The condition was allowed to stand for 1 minute, but the inorganic pigment in the printed pattern could not be effectively burned into the glass plate. It can be seen from experiments that the independent flux and the inorganic pigment have different specific gravity, which causes the sedimentation speed of the two to be different, so that the flux and the inorganic pigment cannot be uniformly distributed in the dispersion and the inkjet ink, so that the flux can not completely cover the inorganic pigment at the end. . In other words, in the present application, the flux and the inorganic pigment are co-fired into a block, and then the co-fired block is pulverized and dispersed to form an inkjet ink, which is superior to the conventional method of directly mixing the flux and the inorganic pigment.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (11)

A dispersion comprising: 100 parts by weight of a glass pigment fine powder; 20 to 80 parts by weight of a dispersant; and 100 to 900 parts by weight of a solvent, wherein the glass pigment fine powder comprises: 100 parts by weight of a flux; and 10 to 100 parts by weight of an inorganic pigment, wherein the glass pigment fine powder has a particle size distribution of between 50 nm and 800 nm, and the glass pigment fine powder has an average particle diameter of between 100 nm and 300 nm, wherein the dispersant is an epoxy resin and A comb copolymer or block copolymer formed by copolymerization of ether amines. The dispersion according to claim 1, wherein the flux comprises cerium oxide, aluminum oxide, lead oxide, zinc oxide, fluoride, or a combination thereof. The dispersion according to claim 1, wherein the inorganic pigment comprises a yellow pigment, a red pigment, a blue pigment, a black pigment, a white pigment, an orange pigment, or a green pigment, wherein the yellow pigment comprises cadmium yellow, Titanium nickel yellow, yttrium zirconium yellow, chrome titanium yellow, or yttrium yellow, the red pigment includes iron red, cadmium red, lead chrome red, or iron zirconium red, the blue pigment includes cobalt blue or cobalt chrome blue, the black pigment Including manganese iron black, cobalt iron chromium, copper chromium black, chrome black, or titanium black, the white pigment includes titanium white, zirconium white or zinc white, the orange pigment includes cadmium orange or orange chrome, and the green pigment Including chrome green, cobalt green, Cobalt chrome green, or cobalt titanium green. The dispersion according to claim 1, wherein the solvent comprises diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, and tetraethylene One of the alcohol dimethyl ethers. An inkjet ink comprising: a dispersion as described in claim 1; 1 to 15 parts by weight of a resin; 1 to 15 parts by weight of a co-solvent; and 1 to 15 parts by weight of an additive. The inkjet ink of claim 5, wherein the resin comprises polyester, polyurethane, polymethyl methacrylate or a combination thereof. The inkjet ink according to claim 5, wherein the cosolvent comprises a cosolvent of at least two of diethylene glycol dimethyl ether, ethylene glycol butyl ether, and tetraethylene glycol dimethyl ether. The inkjet ink of claim 5, wherein the additive comprises a leveling agent, a wetting agent, or a combination thereof. A method for forming an inkjet ink, comprising: mixing 100 parts by weight of a flux with 25 to 100 parts by weight of an inorganic pigment, and co-firing to form a glass pigment block; pulverizing the glass pigment block to form a glass pigment a micropowder, which further comprises 100 parts by weight of the glass pigment fine powder, 20 to 80 parts by weight of a dispersing agent, and 100 to 900 parts by weight of a solvent ball mill to form a dispersion containing a glass pigment fine powder, wherein the glass in the dispersion The particle size distribution of the pigment micropowder is between 50 nm and 800 nm, and the glass pigment micropowder in the dispersion The average particle diameter is between 100 nm and 300 nm; and 100 parts by weight of the dispersion, 1 to 15 parts by weight of the resin, 1 to 15 parts by weight of the co-solvent and 1 to 15 parts by weight of the additive are mixed to form a Inkjet ink. The method for forming an inkjet ink according to claim 9, wherein 100 parts by weight of the flux is mixed with 25 to 100 parts by weight of the inorganic pigment and co-fired to form a co-firing temperature of the glass pigment block. It is between 600 ° C and 1200 ° C and the co-firing time is between 15 minutes and 120 minutes. The method for forming an inkjet ink according to claim 9, further comprising: after spraying the inkjet ink on a substrate, removing the solvent in the inkjet ink and sintering to form a pattern, wherein the sintering temperature Between 600 ° C and 850 ° C, and the sintering time is between 0.1 minutes and 15 minutes.