WO2020052188A1 - 一种打印墨水及其制备方法和打印机 - Google Patents

一种打印墨水及其制备方法和打印机 Download PDF

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Publication number
WO2020052188A1
WO2020052188A1 PCT/CN2019/072877 CN2019072877W WO2020052188A1 WO 2020052188 A1 WO2020052188 A1 WO 2020052188A1 CN 2019072877 W CN2019072877 W CN 2019072877W WO 2020052188 A1 WO2020052188 A1 WO 2020052188A1
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WIPO (PCT)
Prior art keywords
printing
pigment
organic solvent
printing ink
glass frit
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PCT/CN2019/072877
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English (en)
French (fr)
Inventor
山本泰弘
汤振华
Original Assignee
广州精陶机电设备有限公司
御国色素株式会社
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Publication of WO2020052188A1 publication Critical patent/WO2020052188A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/17—Ink jet characterised by ink handling
    • B41J2/175—Ink supply systems ; Circuit parts therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
    • B41J2/38—Preheating, i.e. heating to a temperature insufficient to cause printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • This patent relates to the field of printing ink, and more particularly, to a printing ink, a method for preparing the same, and a printer.
  • the use of glass as a decorative plate can be widely seen in daily life, especially in the interior decoration industry and the advertising industry. It is generally to produce various delicate patterns on the surface of the glass plate.
  • patterns can be generated by decals on the glass plate, but the adhesive tape layer for decals is easy to fall off and damaged, resulting in poor product durability and weatherability.
  • most of the traditional methods for printing patterns on the surface of glass plates are screen printing or pad printing. Although this process can effectively fix the patterns on the glass surface, they need to be made in advance. Transferring the pattern and drying the film, the monochromatic printing can be completed through tedious processes such as making stencils. It is obviously inefficient for multi-color printing, and it is difficult to achieve personalized small batch production.
  • inkjet products with glass as the base material will have more advantages than inkjet products with ceramics as the base material, and glass can improve its own hardness through tempering, and its product quality can be improved. Better.
  • the surface of the glass plate has no pores, and its smoothness is much higher than that of the ceramic plate.
  • the ink slips because it is difficult to adsorb on the glass surface, and the pattern is not easy to accurately position.
  • the printed pattern is deviated and the dimensional accuracy and position accuracy of the pattern on the glass plate are low.
  • the rough nature of the surface of the ceramic plate is actually conducive to ink absorption and precise positioning of the pattern.
  • the above problem illustrates that the prior art glass inkjet process scheme still has defects after drawing on the ceramic inkjet process scheme.
  • the inks in the prior art often have the defects of fast drying and moisturizing. It is either insufficiently moisturizing and causing poor ejection and clogging of the nozzles. Technical issues are improved.
  • this patent provides printing ink for inkjet printers.
  • the printing ink has both the moisturizing property flowing through the nozzle process and the drying property to the surface of the printing medium. Excellent continuous printing performance, can be smoothly ejected from the print head, and form a high-quality pattern on the printing medium;
  • another object of the present invention is to provide a pattern that can be printed on a glass-based printing medium without a glass layer Printing ink that forms a pattern on the print media.
  • a printing ink includes an inorganic pigment, a glass frit, a dispersant, a resin, and an organic solvent.
  • the organic solvent includes at least two solvents, organic solvent A and organic solvent B, and is measured according to ASTM-D3539 at 25 ° C and 1 atm. The value of the relative evaporation rate is 100 for butyl acetate, 10 to 1000 for organic solvent A, and 0.1 to 9 for organic solvent B.
  • Inorganic pigments include black pigments, yellow pigments, blue pigments, One or more of red pigment, green pigment, and white pigment; the particle size of the inorganic pigment and glass frit is 200 ⁇ 1000nm.
  • the inorganic pigment is not particularly limited, but from the viewpoint that discoloration and discoloration are unlikely to occur during firing, it is preferable to use a composite oxide-based inorganic pigment.
  • the colors of printing ink can be black, yellow, blue, red, green, white, pink, purple, gold, silver and other colors. However, it is more preferable to use black, yellow, blue, and red. , Green, and white are used as primary colors to mix and match to create a variety of colors.
  • the inorganic pigments of the present invention include one or more of black pigments, yellow pigments, blue pigments, red pigments, green pigments, and white pigments. Composition of various color pigments.
  • the black pigment is preferably a composite oxide inorganic pigment such as an iron-based pigment or a chromium-based pigment. Iron-based pigments can express vivid black, which is difficult to discolor or fade after firing. More preferably, the black pigment includes one or more of iron oxide black, cobalt ferrite black, or manganese ferrite black. Among them, the blackness of iron oxide black is relatively high, which is more desirable.
  • the black pigment is preferably pigment black 28.
  • the yellow pigment is preferably a composite oxide inorganic pigment such as an antimony-based pigment or a zirconium-based pigment.
  • Antimony-based pigments can exhibit a bright yellow color, which is difficult to discolor or fade after firing.
  • zirconium-based pigments have slightly worse color rendering properties, but they are also used at high temperatures. It is difficult for discoloration or discoloration to occur, and more preferably, the yellow pigment includes hafnium zirconium yellow.
  • the yellow pigment is preferably pigment yellow 53 or pigment brown 24.
  • the blue pigment is preferably a complex oxide inorganic pigment such as a cobalt-based pigment.
  • the cobalt-based pigment can express a vivid blue color, and the pigment is difficult to change color or fade after firing. More preferably, the blue pigment includes Prussian blue Or more of Cobalt Blue and Cobalt Blue.
  • the blue pigment is preferably pigment blue 28.
  • the red pigment is preferably a composite oxide inorganic pigment such as an iron-based pigment or a tin-chromium-based pigment. These pigments can express vivid red or brown colors, and it is difficult to cause discoloration or discoloration after firing. More preferably, the red pigment includes iron oxide red. Most preferably, the red pigment is Pigment Red 101.
  • the green pigment is preferably a composite oxide inorganic pigment such as chrome oxide green or cobalt green. These pigments can express a vivid green color, and it is difficult to discolor or fade after firing. Most preferably, the green pigment is Pigment Green 50.
  • the white pigment is preferably a titanium dioxide inorganic pigment, which can express a vivid white color, and it is difficult to cause discoloration or discoloration after firing.
  • the weight percentage of the inorganic pigment of the present invention based on the weight of the printing ink is preferably 5 wt% or 7 wt% or 9 wt% or 11 wt% or 13 wt% or 15 wt% or 17 wt% or 19 wt% or 21 wt% or 23 wt% or 25 wt% or 5 ⁇ 25 wt%. If the weight percentage is less than 5 wt%, the color rendering performance is poor. It is necessary to increase the coating amount of the printing ink to achieve a concentration that meets the color rendering requirements. However, due to the different storage capacity of the printing ink for the inorganic material, some printing inks may It will overflow and cannot form the corresponding pattern. If the weight percentage exceeds 25 wt%, it is difficult for the printing ink to maintain its stability.
  • a glass frit is added to the printing ink of the present invention to give the printing ink adhesion to the surface of a printing medium.
  • Glass frit contains silica as the main component, and additives can be added during use according to the purpose of use.
  • Materials that can be added to the printing ink as additives include lithium carbonate, sodium carbonate, potassium carbonate, lead oxide, bismuth oxide, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, titanium oxide, and natural feldspar, vermiculite, A mixture of borax, porcelain clay, etc. These materials can be used alone or in combination.
  • the dispersant of the present invention is preferably a polymer dispersant, and may be added alone or in a mixed form.
  • the dispersant may be selected polymer dispersant on the market, such as: Japan Lubrizol Corporation produced Hyperdispersants SOLSPERSE11200, SOLSPERSE13640, SOLSPERSE16000, SOLSPERSE17000, SOLSPERSE18000, SOLSPERSE20000, SOLSPERSE24000, SOLSPERSE26000, SOLSPERSE27000, SOLSPERSE28000, SOLSPERSE32000, SOLSPERSE36000, SOLSPERSE39000, SOLSPERSE56000, SOLSPERSE71000; Wetting and dispersing agent DISPERBYK142 produced by BYK Japan KK; DISPERBYK160, DISPERBYK161, DISPERBYK162, DISPERBYK163, DISPERBYK166, DISPERBYK170, DISPERBYK180, DISPERBYK182, DISPERBYK 184, DISPERBYK2 pigments; DISPERBYK2, Inc.
  • the above-mentioned SOLSPERSE17000, SOLSPERSE24000, SOLSPERSE28000, SOLSPERSE32000, SOLSPERSE39000, SOLSPERSE56000, DISPERBYK2150, or DISPERBYK2155 are preferable as the polymer dispersant.
  • adding resin can increase the viscosity of the printing ink, prevent the printing ink from overflowing when a pattern is formed on the printing medium, and ensure the accuracy of the pattern Degree and print quality.
  • the resin can be selected from commercially available polysaccharide thickeners, thickening resins and derivatives thereof.
  • Polysaccharide thickeners include Xanthan Gum (KELZAN), Waylan Gum, Palm Gum, Succinoglycan, Guar Gum, Locust Bean Gum, Pullulan, Dextran, Dextrin, Xanthan Gum , Tara gum, Jiadi gum, arabinogalactan gum, acacia gum, linseed gum and its derivatives, pectin, starch, carrageenan, agar, alginic acid, gelatin, casein, glucomannan, Carrageenan, benzylidene sorbitol and benzylidene xylitol, RHEOZAN (manufactured by Rhone-Poulenc Chimie), or Diutan Gum (manufactured by CP Kelco).
  • KELZAN Xanthan Gum
  • Thickening resins include cellulose-based cellulose compounds such as carboxyethyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, and water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone.
  • a cellulose compound, a vinyl compound, an acrylic resin, or a poly (meth) acrylic compound is used. More preferably, cellulose compounds and acrylic resins are used.
  • the weight percentage of the resin in the printing ink can be appropriately adjusted according to the thickening property and pseudoplasticity of the resin.
  • the viscosity of the printing ink at 20 ° C is preferably from 2.0 to 30 mPa ⁇ s, more preferably from 5.0 to 25 mPa ⁇ s, and most preferably from 10 to 20 mPa ⁇ s from the viewpoint of ejection performance.
  • the above-mentioned viscosity value was measured by a rotary viscometer TVE-35 manufactured by Toki Sangyo Co., Ltd.
  • the added amount of the resin is preferably 0.05% by weight to 5.0% by weight.
  • the viscosity of the printing ink ranges from 10 to 20 mPa ⁇ s.
  • any resin can be used, for example, the viscosity when adding 0.5% by weight of ethyl cellulose to the printing ink is 15 mPa ⁇ s.
  • the resin used in the printing ink of the present invention is preferably a resin with a residual amount of less than 5% at 450 ° C. If the residual amount exceeds 5%, it is easy to retain ash after firing, leaving a burn mark on the surface of the printing medium, and the desired result cannot be obtained. Design pattern. It is particularly preferable to add a cellulose-based compound or an acrylic resin as the resin in the printing ink of the present invention.
  • Each of the organic solvents used in the printing ink of the present invention has a predetermined evaporation rate, and therefore, excellent continuous ejection stability and pattern formation property can be obtained.
  • the organic solvent includes organic solvent A and organic solvent B
  • the evaporation rate of butyl acetate is 100
  • the relative evaporation rate of organic solvent A measured at 25 ° C and 1 atm according to ASTM-D3539 is 10 ⁇ 1000.
  • the relative evaporation rate of the organic solvent B is 0.1 to 9, the effect is more obvious.
  • the organic solvent B containing a relatively slow evaporation rate can suppress the clogging of the nozzle; secondly, because the organic solvent A containing a relatively fast evaporation rate is contained, when the printing ink is sprayed onto the surface of the printing medium, most of the solvent is volatilized and the printing Increased ink viscosity, suppresses the spread of printing ink, so as to obtain high-quality pattern performance.
  • the two or more organic solvents used in the printing ink of the present invention include an organic solvent A having a relative evaporation rate of 10 to 1000 at 25 ° C and 1 atm, and a relative evaporation rate of 0.1 to 9 at 25 ° C and 1 atm.
  • the weight ratio of the organic solvent A contained in the mixed organic solvent is preferably more than that of the organic solvent B.
  • the organic solvent A is preferably an alcohol solvent such as methanol (190), ethanol (150), isopropanol (150), 3-methoxybutanol (10), acetone (560), methyl ethyl ketone (370), Ketone solvents such as methyl isobutyl ketone (110), ether solvents such as tetrahydrofuran (800), glycol ether solvents such as propylene glycol monomethyl ether (70) and propylene glycol-n-propyl ether (20), ethyl acetate Esters (610), isobutyl acetate (150), and other ester solvents, ethylene glycol monomethyl ether acetate (30), propylene glycol monomethyl ether acetate (30), and 3-methoxybutyl acetate ( 30) Ethylene glycol monoacetate solvents.
  • diol ether solvents and ethylene glycol monoacetate solvents are particularly preferred.
  • the organic solvent B is preferably a polyhydric alcohol solvent such as 1,3-butanediol, propylene glycol-n-butyl ether (7), dipropylene glycol monomethyl ether (3), diethylene glycol monoethyl ether, and dipropylene glycol-n-propyl ether.
  • Glycol ether solvents such as dipropylene glycol-n-butyl ether (1), ethylene glycol butyl ether acetate, diethylene glycol monoethyl ether acetate (1), diethylene glycol mono Ethylene glycol acetate solvents such as butyl ether acetate, glycerol triacetate, and the like.
  • diol ether solvents and ethylene glycol acetate solvents are particularly preferred.
  • the organic solvent A and the organic solvent B at least one of the solvents can be selected.
  • a solvent having a low viscosity is preferable, and a solvent in a range of 1 to 20 mPa ⁇ s is preferably selected.
  • additives such as surface tension adjuster, frequency adjuster, specific resistance adjuster, heat stabilizer, antioxidant, anti-reducing agent, preservative, defoamer, and wetting agent can be added to the printing ink as needed.
  • the printing ink of the present invention is obtained by mixing the above materials, and then dispersing the mixture by using a disperser such as a roller mill, a ball mill, a colloid mill, a jet mill, a bead mill, and a sand mill, and then filtering the mixture.
  • a disperser such as a roller mill, a ball mill, a colloid mill, a jet mill, a bead mill, and a sand mill, and then filtering the mixture.
  • the inorganic pigment and the glass frit are pre-mixed with the organic solvent and the dispersant, respectively, and then dispersed with a disperser such as a sand mill or a microbead mill to obtain a dispersion liquid, and in these dispersion liquids.
  • a printing ink can be prepared by adding a resin for adjusting viscosity, an auxiliary agent for adjusting surface tension, and the like, and filtering.
  • the printing ink produced in the above steps is sprayed onto a printing medium such as a glass plate or a ceramic plate by an inkjet nozzle to form a pattern.
  • a printing medium such as a glass plate or a ceramic plate by an inkjet nozzle
  • the solvent needs to be dried, and then the temperature is selected according to the material of the printing medium. (For example, for glass plates, the recommended firing temperature is about 700 ° C, and for ceramic plates, the recommended firing temperature is about 850 ° C). Firing is performed to burn off the dispersant and resin components contained in the printing ink, and make the printing ink The glass frit contained in it is melted, so that the design pattern formed by the printing ink can be tightly printed on the printing medium.
  • Another object of the present invention is to provide a printer to which the above-mentioned printing ink is applied.
  • the printer is sequentially provided with a preheating zone, a heat preservation zone, and a printing zone.
  • the printer includes a conveying platform penetrating the preheating zone, the heat preservation zone, and the printing zone.
  • a printing module located above the conveying platform in the printing area, the printing module is provided with an inkjet system, a control system, an ink supply system that stores and supplies the printing ink to the inkjet system, and controls the inkjet system ink jetting temperature
  • the temperature T1 of the preheating zone is 80 ⁇ 100 ° C
  • the temperature T2 of the heat preservation zone is 60 ⁇ 80 ° C.
  • the printer is further provided with a printing medium cleaning area connected to the preheating area, and the printing medium cleaning area is provided with a printing medium cleaning machine for cleaning the printing medium.
  • the components of the printing ink of the present invention include at least two types of organic solvents with significantly different relative evaporation rates.
  • the organic solvent A having a large relative evaporation rate provides the ink with a pattern.
  • the fast-drying property ensures the accuracy of the formed pattern.
  • the relative evaporation speed is relatively small.
  • Organic solvent B provides the moisturizing property of the ink as it passes through the nozzle, ensuring the ink has proper fluidity, and prevents the nozzle from being blocked.
  • the printer provided by the present invention is provided with a temperature control system in the printing module to ensure that the ink has a lower temperature before being ejected from the nozzle to prevent the evaporation of the organic solvent in the ink and cause the viscosity of the ink
  • the print head is clogged so as to ensure the smoothness of the ejection.
  • the printing medium passes through the printer's preheating zone and heat preservation zone in sequence, and finally enters the printing zone. After the preheating and heat preservation, the printing medium has a temperature and the ink reaches the printing medium. The surface will absorb the heat from the printing medium to promote the volatilization of organic solvents. Ensure the accuracy of the pattern.
  • FIG. 1 is a schematic diagram of a printer.
  • a printing ink includes inorganic pigment, glass frit, dispersant, resin, and organic solvent.
  • inorganic pigment is pigment black 28 having a particle size in the range of 200 to 1000 nm; glass frit has a particle size in the range of 200 to 1000 nm.
  • the organic solvent includes organic solvent A and organic solvent B.
  • Organic solvent A is propylene glycol monomethyl ether (70), and organic solvent B is propylene glycol-n-butyl. Ether (7);
  • the method for preparing the printing ink includes the following steps:
  • pigment dispersion liquid After pre-mixing with 5 wt% dispersant, 40 wt% inorganic pigment and remaining weight percentage of organic solvent A, dispersing with a stirrer to obtain a pigment dispersion with a weight percentage of 40 wt% of the inorganic pigment
  • the average particle diameter of the organic pigment particles in the pigment dispersion was 300 nm.
  • the average particle diameter is obtained by diluting the dispersion to a specified concentration (within the load index of the tester in the range of 3 to 5) using a nanometer particle size analyzer NANO-Flex manufactured by MICROTRACK.
  • glass frit dispersion The same as the preparation of the pigment dispersion, the glass frit is used instead of the inorganic pigment to perform the micronization treatment, and a glass frit dispersion with a glass frit weight percentage of 40 wt% is prepared. At this time, The average particle size of the glass frit particles in the glass frit dispersion was 450 nm.
  • Preparation of printing ink 25% by weight of a pigment dispersion liquid, 50% by weight of a glass frit dispersion liquid, 20% by weight of an organic solvent B, and a remaining weight percentage of resin are mixed to obtain a printing ink.
  • the viscosity of the printing ink is 10 to 20 mPa ⁇ s
  • the surface tension is 20.0 to 30.0 mN / m
  • the maximum particle diameter is less than 3 ⁇ m, and preferably 1 ⁇ m.
  • the prepared printing ink was printed using the following printer.
  • a printer to which the above-mentioned printing ink is applied the printer is sequentially provided with a preheating zone, a heat preservation zone, and a printing zone, including a conveying platform penetrating the preheating zone, the heat preservation zone, and the printing zone, and is provided in the printing zone.
  • a printing module located above the conveying platform, the printing module is provided with an inkjet system, a control system, an ink supply system that stores and supplies the printing ink to the inkjet system, and a temperature that controls the inkjet temperature of the inkjet system.
  • the temperature T1 of the preheating zone is 80 ⁇ 100 ° C
  • the temperature T2 of the heat preservation zone is 60 ⁇ 80 ° C.
  • Printing accuracy test Use the above printer and ink to print. After the ink is dried, measure the diameter of each ink dot, calculate the average ink dot diameter and record the measurement results in Table 1. It should be noted that when the average ink dot diameter is 0.4 ⁇ 0.8mm, it can be drawn normally.
  • Residual test take 10ml of ink and pour it on a 5 ⁇ m stainless steel filter, make the ink pass through the filter by its own gravity, observe the residue on the filter after 20 seconds, wash the filter to observe whether there is residue on the filter, and test The results are reported in Table 1. It should be noted that the residual amount after 20 seconds is less than 5%, and the residual amount after washing is less than 1%, indicating that the ink residual test is good.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the inorganic pigment is Pigment Yellow 53, and the others are the same as in Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the inorganic pigment is Pigment Brown 24, and others are the same as Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the inorganic pigment is Pigment Blue 28, and others are the same as Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the inorganic pigment is Pigment Green 50, and others are the same as Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the inorganic pigment is titanium dioxide, and the others are the same as those of Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the dispersant is SOLSPERSE 28000, and the others are the same as in Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the dispersant is SOLSPERSE32000, and the others are the same as in Embodiment 1.
  • Example 1 The difference between this embodiment and Example 1 is that the dispersant is DISPERBYK 2150, and the others are the same as in Example 1.
  • Example 1 The difference between this embodiment and Example 1 is that the resin is polyvinylpyrrolidone, and the others are the same as in Example 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the resin is an acrylic resin, and the others are the same as Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the resin is a poly (meth) acrylic compound, and the others are the same as in Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the organic solvent A is propylene glycol-n-propyl ether (20), and the others are the same as those of Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the organic solvent A is ethylene glycol monomethyl ether acetate (30), and the others are the same as those of Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the organic solvent A is 3-methoxybutyl acetate (30), and the others are the same as those of Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the organic solvent B is dipropylene glycol-n-propyl ether (2), and the others are the same as Embodiment 1.
  • the organic solvent B is diethylene glycol monoethyl ether acetate (1), and the others are the same as those of Embodiment 1.
  • the method for preparing the printing ink includes the following steps:
  • pigment dispersion liquid After pre-mixing with 6 wt% dispersant, 50 wt% inorganic pigment and remaining weight percentage of organic solvent A, dispersing with a mixer to obtain a pigment dispersion with a weight percentage of 50 wt% of the inorganic pigment
  • the average particle diameter of the organic pigment particles in the pigment dispersion was 400 nm.
  • the average particle diameter is obtained by diluting the dispersion to a specified concentration (within the load index of the tester in the range of 3 to 5) using a nanometer particle size analyzer NANO-Flex manufactured by MICROTRACK.
  • glass frit dispersion liquid Similar to the preparation of pigment dispersion liquid, glass frit is used instead of inorganic pigments to carry out micronization treatment to prepare a glass frit dispersion with a glass frit weight percentage of 50 wt%. At this time, The average particle size of the glass frit particles in the glass frit dispersion was 550 nm.
  • Preparation of printing ink 40% by weight of pigment dispersion, 30% by weight of glass frit dispersion, 28% by weight of organic solvent B, and the remaining weight percent of resin are mixed to obtain printing ink.
  • the viscosity of the printing ink is 10 to 20 mPa ⁇ s
  • the surface tension is 20.0 to 30.0 mN / m
  • the maximum particle diameter is less than 3 ⁇ m, and preferably 1 ⁇ m.
  • the method for preparing the printing ink includes the following steps:
  • pigment dispersion liquid After pre-mixing with 6 wt% dispersant, 50 wt% inorganic pigment and remaining weight percentage of organic solvent A, dispersing with a mixer to obtain a pigment dispersion with a weight percentage of 50 wt% of the inorganic pigment
  • the average particle diameter of the organic pigment particles in the pigment dispersion was 400 nm.
  • the average particle diameter is obtained by diluting the dispersion to a specified concentration (within the load index of the tester in the range of 3 to 5) using a nanometer particle size analyzer NANO-Flex manufactured by MICROTRACK.
  • glass frit dispersion liquid Similar to the preparation of pigment dispersion liquid, glass frit is used instead of inorganic pigments to carry out micronization treatment to prepare a glass frit dispersion with a glass frit weight percentage of 50 wt%. At this time, The average particle size of the glass frit particles in the glass frit dispersion was 550 nm.
  • Preparation of printing ink 30% by weight of pigment dispersion, 40% by weight of glass frit dispersion, 29% by weight of organic solvent B, and the remaining weight percent of resin are mixed to obtain printing ink.
  • the viscosity of the printing ink is 10 to 20 mPa ⁇ s
  • the surface tension is 20.0 to 30.0 mN / m
  • the maximum particle diameter is less than 3 ⁇ m, and preferably 1 ⁇ m.
  • the method for preparing the printing ink includes the following steps:
  • pigment dispersion liquid After premixing with 4% by weight of a dispersant, 25% by weight of an inorganic pigment, and the remaining weight percentage of organic solvent A, the mixture is dispersed with a stirrer to obtain a pigment dispersion of 25% by weight of the inorganic pigment
  • the average particle diameter of the organic pigment particles in the pigment dispersion was 280 nm.
  • the average particle diameter is obtained by diluting the dispersion to a specified concentration (within the load index of the tester in the range of 3 to 5) using a nanometer particle size analyzer NANO-Flex manufactured by MICROTRACK.
  • glass frit dispersion liquid Similar to the preparation of pigment dispersion liquid, glass frit is used instead of inorganic pigments to carry out micronization treatment to prepare a glass frit dispersion with a glass frit weight percentage of 25 wt%. At this time, The average particle size of the glass frit particles in the glass frit dispersion was 420 nm.
  • Preparation of printing ink 20% by weight of pigment dispersion, 40% by weight of glass frit dispersion, 36% by weight of organic solvent B, and the remaining weight percent of resin are mixed to obtain printing ink.
  • the viscosity of the printing ink is 10 to 20 mPa ⁇ s
  • the surface tension is 20.0 to 30.0 mN / m
  • the maximum particle diameter is less than 3 ⁇ m, and preferably 1 ⁇ m.
  • the method for preparing the printing ink includes the following steps:
  • pigment dispersion liquid After pre-mixing with 8 wt% dispersant, 65 wt% inorganic pigment and remaining weight percentage of organic solvent A, dispersing with a stirrer to obtain pigment dispersion with 65 wt% inorganic pigment weight percentage
  • the average particle diameter of the organic pigment particles in the pigment dispersion was 480 nm.
  • the average particle diameter is obtained by diluting the dispersion to a specified concentration (within the load index of the tester in the range of 3 to 5) using a nanometer particle size analyzer NANO-Flex manufactured by MICROTRACK.
  • glass frit dispersion liquid The same as the preparation of pigment dispersion liquid, the glass frit is used instead of the inorganic pigment to perform the miniaturization treatment, and a glass frit dispersion liquid having a glass frit weight percentage of 65wt% is prepared.
  • the average particle size of the glass frit particles in the glass frit dispersion was 580 nm.
  • printing ink 38.5 wt% pigment dispersion liquid, 46.1 wt% glass frit dispersion liquid, 14.9 wt% organic solvent B, and the remaining weight percentage of resin are mixed to obtain a printing ink.
  • the viscosity of the printing ink is 10 to 20 mPa ⁇ s
  • the surface tension is 20.0 to 30.0 mN / m
  • the maximum particle diameter is less than 3 ⁇ m, and preferably 1 ⁇ m.
  • Example 1 The difference between this comparative example and Example 1 is that the organic solvent A is methyl ester (1040), and the test results are recorded in Table 2. The others are the same as in Example 1. Since the selected solvent dries too fast, drying occurs on the head and the re-ejectability decreases.
  • Example 1 The difference between this comparative example and Example 1 is that the organic solvent B is ethylene glycol monomethyl ether acetate (30), and the test results are recorded in Table 2. The others are the same as in Example 1. It is equivalent to this comparative example that does not contain organic solvent B, and the drying speed is accelerated, and drying occurs at the nozzle soon, resulting in poor ejection properties.
  • the organic solvent B is ethylene glycol monomethyl ether acetate (30)
  • Table 2 The others are the same as in Example 1. It is equivalent to this comparative example that does not contain organic solvent B, and the drying speed is accelerated, and drying occurs at the nozzle soon, resulting in poor ejection properties.
  • Example 1 The difference between this comparative example and Example 1 is that the organic solvent A is dipropylene glycol-n-propyl ether (2), and the test results are recorded in Table 2. The others are the same as in Example 1. Equivalent to this comparative example, which does not contain organic solvent A, and the drying speed is slow, so that no drying occurs at the nozzle, and the ejection is good, but because the drying speed is slower during printing, the ink dots diffuse when they reach the surface of the printing medium. This phenomenon affects print quality.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that an existing printer is used for printing and measurement, and the others are the same as Embodiment 1.

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Abstract

一种打印墨水、墨水的制备方法以及打印机。打印墨水包括无机颜料、玻璃熔块、分散剂、树脂和有机溶剂，有机溶剂包括有机溶剂A和B至少两种溶剂，在25℃、1atm条件下依据ASTM-D3539测得的相对蒸发速度的值，以醋酸丁酯的值为100，有机溶剂A的值为10~1000，有机溶剂B的值为0.1~9。制备方法为无机颜料和玻璃熔块分别与有机溶剂和分散剂预混合，分散后添加树脂混合均匀过滤。打印机顺序设置有预热区、保温区和打印区，贯穿这三个区的输送平台和设置在打印区的位于输送平台上方的打印模组。

Description

一种打印墨水及其制备方法和打印机 技术领域
本专利涉及打印墨水领域，更具体地，涉及一种打印墨水及其制备方法和打印机。
 背景技术
用玻璃作为装饰板在日常生活中可以广泛见到，特别是在室内装修行业和广告行业尤为常见，其一般是在玻璃板表面制作各种精美的图案。然而，在玻璃板表面制作图案的方式有多种，例如可以通过在玻璃板上贴花的方式生成图案，但是贴花用的胶纸层容易脱落和受损，导致产品耐用和耐候程度较差。为了弥补上述缺陷，传统工艺对玻璃板表面印刷图案的工艺方法大多数是通过丝网印刷或移印技术，虽然该种工艺可以让图案有效地固定在玻璃表面，但是均都需要预先制成待转移图案并晒制菲林，通过制作网板等繁琐的工艺才能完成单色印刷，对多色彩的印刷显然存在效率低下的弊端，也难以实现个性化的小批量生产。
为了弥补上述技术缺陷，现有技术中出现一种借鉴了陶瓷喷绘打印的技术方案，其原理与传统打印机彩色喷绘的技术类似，通过结合计算机控制技术控制喷头，在玻璃板表面喷绘出所需要的图案，这种喷绘方法效率极高。同时，值得一提的是，上述的陶瓷打印技术虽然工作效率高，但是由于打印的基料为陶瓷，陶瓷材料本身就含有多种不同的物质成分，在打印过程中会由于高温而与墨水产生化学反应，从而会导致喷绘在陶瓷上的墨水颜色失真，相比之下，玻璃的成分主要是二氧化硅，化学性质稳定，在高温下不容易与墨水产生化学反应，从而打印出来的图案颜色几乎不会失真，效果更好，因此，在理论上，以玻璃作为基料的喷绘产品会比陶瓷作为基料的喷绘产品更有优势，并且玻璃可以通过钢化处理提高自身硬度，其产品质量能更高一筹。但是，在实际生产上，玻璃板表面没有孔隙，其光滑度远远高于陶瓷板，在喷头高速喷绘的过程中，墨水因难以吸附在玻璃表面而产生滑移，图案也不容易精准定位，导致打印出来的图案有所偏差和玻璃板上的图案尺寸精度和位置精度偏低，在这一点上，陶瓷板表面的粗糙特质却反而有利于墨水的吸附和图案的精准定位。上述问题说明了，现有技术的玻璃喷绘工艺方案借鉴了陶瓷喷绘工艺方案后，仍然存在缺陷。
此外，现有技术中的墨水往往存在快速干燥性与保湿性难以兼顾的缺陷，要么保湿性不够造成喷吐不畅，喷头堵塞；要么干燥性欠缺，难以保证图案的打印精度，因此有必要针对上述技术问题进行改进。
 技术问题
有鉴于此，本专利为克服上述现有技术所述的至少一种不足，提供喷墨打印机用的打印墨水，该打印墨水兼顾流经喷头过程的保湿性和达到打印介质表面的干燥性，具有优异的连续喷绘性能，可以流畅地从喷头喷出，并在打印介质上形成高质量的图案；本发明的另一个目的在于提供既能够在玻璃材质的打印介质上打印图案又能在没有玻璃层的打印介质上形成图案的打印墨水。
 技术解决方案
为了解决上述存在的技术问题，本专利采用下述技术方案：
一种打印墨水，包括无机颜料、玻璃熔块、分散剂、树脂和有机溶剂，其中，有机溶剂包括有机溶剂A和有机溶剂B至少两种溶剂，在25℃、1atm条件下依据ASTM-D3539测得的相对蒸发速度的值，以醋酸丁酯的值为100，有机溶剂A的值为10~1000，有机溶剂B的值为0.1~9；无机颜料包括黑色颜料、黄色颜料、蓝色颜料、红色颜料、绿色颜料、白色颜料中的一种或多种；无机颜料和玻璃熔块的粒径为200~1000nm。
本发明对无机颜料没有特别限定，但是从烧制时不易发生褪色和变色的角度来看，最好使用复合氧化物类无机颜料。
打印墨水的颜色可以直接使用黑色、黄色、蓝色、红色、绿色、白色、粉色、紫色、金、银等各种各样的颜色，但是，更理想的是以黑色、黄色、蓝色、红色、绿色、白色作为原色进行组合调配出丰富多彩的颜色，本发明的无机颜料包括黑色颜料、黄色颜料、蓝色颜料、红色颜料、绿色颜料、白色颜料中的一种或多种，下面详细记述各种颜色的颜料的成分。
黑色颜料优选铁系颜料或铬系颜料等复合氧化物类无机颜料。铁系颜料可以表现鲜艳的黑色，该颜料经烧制后很难发生变色或褪色。更优选地，所述黑色颜料包括氧化铁黑、钴铁氧体黑或锰铁氧体黑中的一种或多种，其中，氧化铁黑的黑度较高，较为理想。所述黑色颜料最好选用颜料黑28。
黄色颜料优选锑系颜料或锆系颜料等复合氧化物类无机颜料。锑系颜料可表现鲜艳的的黄色，该颜料经烧制后很难发生变色或褪色，而锆系颜料与锑系颜料相比较，虽然显色性能稍微差一些，但是它即使在高温条件下也很难发生变色或褪色，更优选地，所述黄色颜料包括镨锆黄。所述黄色颜料最好选用颜料黄53或颜料棕24。
蓝色颜料优选钴系颜料等复合氧化物类无机颜料，钴系颜料可表现鲜艳的蓝色，该颜料经烧制后很难发生变色或褪色，更优选地，所述蓝色颜料包括普鲁士蓝、钴蓝、钴铝蓝中一种或多种。所述蓝色颜料最好选用颜料蓝28。
红色颜料优选铁系颜料或锡铬系颜料等复合氧化物类无机颜料，这些颜料能够表现鲜艳的红色或棕色，并且经烧制后很难发生变色或褪色。更优选地，所述红色颜料包括氧化铁红。最优选地，所述红色颜料为颜料红101。
绿色颜料优选氧化铬绿或钴绿等复合氧化物类无机颜料，这些颜料能够表现鲜艳的绿色，并且经烧制后很难发生变色或褪色。最优选地，绿色颜料为颜料绿50。
白色颜料优选二氧化钛无机颜料，可表现鲜艳的白色，经烧制后很难发生变色或褪色。
本发明无机颜料基于打印墨水的重量百分数优选5wt%或7 wt%或9 wt%或11 wt%或13 wt%或15 wt%或17 wt%或19 wt%或21 wt%或23 wt%或25 wt%或5~25 wt%。如果重量百分数小于5 wt%，显色性能差，需要增加打印墨水的涂布量以达到符合显色要求的浓度，但是由于无机材质的打印介质对打印墨水的容纳容量不同，有的打印墨水可能会溢出而无法形成相应的图案。如果重量百分数超过25 wt%，则打印墨水难以保持自身的稳定性。
本发明打印墨水中添加了玻璃熔块以赋予打印墨水印刷到打印介质表面时的粘附性。玻璃熔块以二氧化硅为主要成分，可根据使用目的在使用时添加助剂。可作为助剂添加到打印墨水中的材料有碳酸锂、碳酸钠、碳酸钾、氧化铅、氧化铋、碳酸钡、碳酸锶、碳酸钙、碳酸镁、氧化钛、以及天然的长石、珪石、硼砂、瓷土等的混合物，这些材料既可单独使用也可混合使用。
为了使无机颜料或无机颜料和玻璃熔块更好的分散到打印墨水中，本发明的分散剂优选高分子分散剂，可以以单独或混合的形式添加。
分散剂可以选用市面上销售的高分子分散剂，例如：日本路博润株式会社生产的超分散剂SOLSPERSE11200、SOLSPERSE13640、SOLSPERSE16000、SOLSPERSE17000、SOLSPERSE18000、SOLSPERSE20000、SOLSPERSE24000、SOLSPERSE26000、SOLSPERSE27000、SOLSPERSE28000、SOLSPERSE32000、SOLSPERSE36000、SOLSPERSE39000、SOLSPERSE56000、SOLSPERSE71000；BYK Japan KK生产的润湿分散剂DISPERBYK142；DISPERBYK160、DISPERBYK161、DISPERBYK162、DISPERBYK163、DISPERBYK166、DISPERBYK170、DISPERBYK180、DISPERBYK182、DISPERBYK184、DISPERBYK190、DISPERBYK2150、DISPERBYK2155；味之素株式会社生产的颜料分散剂AJISPER PB711、AJISPER PA111、AJISPER PB811、AJISPER PB821、AJISPER PB822、AJISPER PW911；共荣社化学工业株式会社生产的FLOWLEN DOPA-15Ｂ、FLOWLEN  DOPA-22、FLOWLEN DOPA-17、FLOWLEN TG-730Ｗ、FLOWLEN G-00、FLOWLEN TG-720Ｗ等。
从残渣残留量及分散稳定性的角度来看，高分子分散剂优选上述的SOLSPERSE17000、SOLSPERSE24000、SOLSPERSE28000、SOLSPERSE32000、SOLSPERSE39000、SOLSPERSE56000、DISPERBYK2150或者DISPERBYK2155。
此外，通过向打印墨水中添加树脂发展其假塑性以获得良好的喷吐稳定性，同时，添加树脂可以增加打印墨水的粘稠性，防止在打印介质上形成图案时打印墨水溢出，保证图案的精确度和喷绘质量。
树脂可以选用市面上销售的多糖类增稠剂、增稠树脂及其衍生物。多糖类增稠剂包括黄原胶（KELZAN）、韦兰胶、棕榈胶、琥珀酰聚糖、瓜尔豆胶、刺槐豆胶、普鲁兰多糖、葡聚糖、糊精、黄蓍胶、塔拉胶、佳迪胶、阿拉伯半乳聚糖胶、阿拉伯树胶、亚麻籽胶及其衍生物、果胶、淀粉、卡拉胶、琼脂、海藻酸、明胶、酪蛋白、葡甘露聚糖、角叉菜胶、苯亚甲基山梨糖醇以及苯亚甲基木糖醇、RHEOZAN（Rhone-Poulenc Chimie生产）、Diutan Gum（CP Kelco生产）中的一种或多种。
增稠树脂包括羧乙基纤维素、乙基纤维素、羟乙基纤维素、羧甲基纤维素等纤维胶性质的纤维素类化合物、聚乙烯醇、聚乙烯吡咯烷酮等水溶性聚合物组成的乙烯基类化合物、醇酸树脂、丙烯酸树脂、苯乙烯马来酸共聚物、纤维素衍生物、聚乙烯吡咯烷酮、聚乙烯醇、聚（甲基）丙烯酸类化合物、聚醚改性氨基甲酸酯化合物、疏水基改性聚氧乙烯聚氨酯共聚物等聚氨酯化合物，聚酰胺蜡胺盐等聚酰胺类化合物、聚氨酯尿素类化合物性质的尿素类化合物等。海藻酸烷基酯类、甲基丙烯酸的烷基酯等酯类化合物、聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、乙烯基吡咯烷酮／乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯共聚物、聚丙烯酰胺、聚N-乙烯基乙酰胺、N-乙烯基乙酰胺树脂以及衍生物等。最好是使用纤维素类化合物、乙烯基类化合物、丙烯酸树脂、聚（甲基）丙烯酸类化合物。更好的则使用纤维素化合物和丙烯酸树脂。
打印墨水中树脂的重量百分数可以根据树脂的增稠性和假塑性进行适当的调整。打印墨水在20℃下的粘度，从喷吐性能的角度出发，优选2.0~30mPa·s，更优选5.0~25mPa·s，最优选10~20mPa·s。上述粘度值由东机产业株式会社制造的旋转粘度计TVE-35测得。
如果树脂的添加量过大，则残留量增加，甚至出现喷吐不顺畅的现象。树脂添加量优选重量百分数为0.05wt％~5.0wt％，此时打印墨水的粘度范围在10~20mPa·s之间。只要树脂的重量百分数及打印墨水的粘度落入上述范围内，可以使用任何树脂，例如，将0.5wt％的乙基纤维素添加至打印墨水时的粘度为15mPa·s。
在本发明的打印墨水中使用的树脂优选在450℃环境下残渣量低于5%的树脂，如果残渣量超过5%烧制后容易残留灰分，在打印介质表面留下焦印，无法得到所希望的设计图案。特别优选纤维素类化合物或丙烯酸树脂作为本发明打印墨水中的树脂添加。
本发明的打印墨水所使用的有机溶剂，每种溶剂都有规定的蒸发速度，因而可以获得优异的连续喷吐稳定性和图案形成性。特别是当有机溶剂包括有机溶剂A 和有机溶剂B，以醋酸丁酯的蒸发速度为100，在25℃、1atm的条件下依据ASTM-D3539测定的有机溶剂A的相对蒸发速度为10~1000，有机溶剂B的相对蒸发速度为0.1~9时，效果更为明显。其理由如下：首先，含有相对蒸发速度慢的有机溶剂B可以抑制喷嘴的堵塞，其次，由于含有相对蒸发速度快的有机溶剂A，打印墨水喷印到打印介质表面时，大部分溶剂挥发，打印墨水粘度提高，抑制了打印墨水的扩散，从而获得优质的图案表现性能。
本发明的打印墨水所使用的2种以上的有机溶剂，含有在25℃、１ａｔｍ条件下相对蒸发速度为10~1000的有机溶剂Ａ，以及在25℃、１ａｔｍ条件下相对蒸发速度为0.1~9的有机溶剂Ｂ，按照质量标准，该混合有机溶剂中含有的有机溶剂Ａ的重量占比最好多于有机溶剂Ｂ。
有机溶剂A优选甲醇(190)、乙醇(150)、异丙醇(150)、3-甲氧基丁醇(10)等醇类溶剂，丙酮(560)、甲基乙基酮(370)、甲基异丁基酮(110)等酮类溶剂，四氢呋喃(800)等醚类溶剂，丙二醇单甲醚(70)、丙二醇-n-丙醚(20)等二元醇醚类溶剂，醋酸乙酯(610)、乙酸异丁酯(150)等酯类溶剂，乙二醇单甲醚乙酸酯(30)、丙二醇单甲醚乙酸酯(30)、3-甲氧基乙酸丁酯(30)等乙二醇单乙酸酯类溶剂。其中，特别优选二元醇醚类溶剂和乙二醇单乙酸酯类溶剂。
有机溶剂B优选1,3-丁二醇等多元醇类溶剂，丙二醇-n-丁醚(7)、二丙二醇单甲醚(3)、二乙二醇单乙醚、二丙二醇-n-丙醚(2)、二丙二醇-n-丁醚(1)等二元醇醚类溶剂，乙二醇丁基醚乙酸酯、二乙二醇单乙醚乙酸酯(1)、二乙二醇单丁醚乙酸酯等乙二醇乙酸酯类溶剂，甘油三乙酸酯等。其中，特别优选二元醇醚类溶剂和乙二醇乙酸酯类溶剂。
有机溶剂Ａ以及有机溶剂Ｂ可以分别选用上述溶剂中的至少1种。作为喷墨打印用的打印墨所使用的有机溶剂，优选低粘度的溶剂，最好选择1~20ｍＰａ・ｓ的范围内的溶剂。
本发明打印墨水在调整干燥速度后，除了适用喷墨打印外，也适用于丝网印刷和喷印印刷等。
根据需要，也可以在打印墨水中添加表面张力调节剂、频率调节剂、比电阻调节剂、热稳定剂、抗氧化剂、抗还原剂、防腐剂、消泡剂、润湿剂等各种助剂。
本发明的打印墨水是将上述材料进行混合，再用辊碾机、球磨机、胶体磨、喷射磨机、微珠磨机、砂磨机等分散机对上述混合物进一步分散后过滤而获得。具体而言，就是将无机颜料和玻璃熔块分别与所述的有机溶剂和分散剂预混合，再用砂磨机或微珠磨机等分散机进行分散得到分散液，并在这些分散液中添加调整粘度用的树脂和调整表面张力等的助剂，进行过滤，即可制备得到打印墨水。
由上述工序制作完成的打印墨水，由喷墨用喷嘴喷在玻璃板或陶瓷板等打印介质上，形成图案，为了不使形成的图案走样，需要对溶剂进行干燥，然后根据打印介质材质选择温度（例如，对于玻璃板，推荐烧制温度为700℃左右、而陶瓷板的推荐烧制温度为850℃左右）进行烧制，烧掉打印墨水中含有的分散剂以及树脂成分，并使打印墨水中含有的玻璃熔块熔化，由此可以使打印墨水形成的设计图案紧紧地印在打印介质上。
本发明的另一个目的在于提供一种应用上述打印墨水的打印机，所述打印机顺序设置有预热区、保温区和打印区，包括贯穿预热区、保温区、打印区的输送平台和设置在打印区的位于输送平台上方的打印模组，所述打印模组中设有喷墨系统、控制系统、储存并向喷墨系统供应所述打印墨水的供墨系统和控制喷墨系统墨水喷绘温度的温控系统，所述预热区的温度T1为80~100℃，所述保温区的温度T2为60~80℃。
所述打印机还设有与预热区相接的打印介质清洗区，所述打印介质清洗区中设有用于清洗打印介质的打印介质清洗机。
 有益效果
本专利与现有技术相比较有如下有益效果：本发明的打印墨水的成分中至少包括两种相对蒸发速度明显区别的有机溶剂，其中相对蒸发速度较大的有机溶剂A 提供了墨水形成图案时的快干性，从而保证了所形成的图案的精确性，相对蒸发速度较小有机溶剂B提供了墨水经过喷头时的保湿性，保证墨水具有适当的流动性，防止喷头被堵塞，从而保证了喷头的喷吐流畅性；相对应地，本发明提供的打印机在打印模组中设有温控系统，保证墨水从喷头喷出之前具有具有较低的温度，防止墨水中的有机溶剂蒸发导致墨水粘度剧增而堵塞喷头，从而保证喷吐的流畅性；打印时打印介质依次经过打印机的预热区、保温区，最后才进入打印区，经过预热和保温使得打印介质的具有温度，墨水达到打印介质表面时将会吸收来自打印介质的热量促进有机溶剂的挥发，从而保证了图案的精确性。
 附图说明
图1是打印机的结构示意图。
 本发明的最佳实施方式
下面结合具体实施例对本专利做进一步详细说明。
实施例1
一种打印墨水，包括无机颜料、玻璃熔块、分散剂、树脂和有机溶剂，其中，无机颜料为粒径在200~1000nm范围内的颜料黑28；玻璃熔块为粒径在200~1000nm范围内的二氧化硅；分散剂为SOLSPERSE24000；树脂为乙基纤维素；有机溶剂包括有机溶剂A和有机溶剂B，有机溶剂A为丙二醇单甲醚（70），有机溶剂B为丙二醇-n-丁醚（7）；
所述打印墨水的制备方法包括如下步骤：
S1.颜料分散液的制备：用5wt%的分散剂、40wt%的无机颜料和剩余重量百分数的有机溶剂A进行预混合后，用搅拌机进行分散，得到无机颜料的重量百分数为40wt%的颜料分散液，此时，颜料分散液中的有机颜料粒子的平均粒径为300nm。其平均粒径是在将分散液稀释至规定浓度（检测仪的负荷指数3~5的范围内）后用MICROTRACK公司生产的纳米粒度仪NANO-Flex检测得到的。
S2.玻璃熔块分散液的制备：与颜料分散液的制备相同，用玻璃熔块代替无机颜料进行微细化处理，制备得到玻璃熔块重量百分数为40wt%的玻璃熔块分散液，此时，玻璃熔块分散液中玻璃熔块粒子的平均粒径为450nm。
S3.打印墨水的制备：将25wt%的颜料分散液、50 wt%的玻璃熔块分散液、20 wt%的有机溶剂B以及剩余重量百分数的树脂混合制得打印墨水。此时，打印墨水的粘度为10~20mPa·s，表面张力为20.0~30.0mN/m，最大粒子粒径小于3μm，最好为1μm。
制得的上述打印墨水采用下述打印机进行打印。
如图1所示，一种应用上述打印墨水的打印机，所述打印机顺序设置有预热区、保温区和打印区，包括贯穿预热区、保温区、打印区的输送平台和设置在打印区的位于输送平台上方的打印模组，所述打印模组中设有喷墨系统、控制系统、储存并向喷墨系统供应所述打印墨水的供墨系统和控制喷墨系统墨水喷绘温度的温控系统，所述预热区的温度T1为80~100℃，所述保温区的温度T2为60~80℃。
测试方法：
1、打印精度测试：采用上述打印机及上述墨水进行打印，待墨水干燥后分别测量各墨点的直径，计算平均墨点直径并将测量结果记录在表1中。应当指出的是，平均墨点直径为0.4~0.8mm时处于能够正常绘制的状态。
2、保湿性能测试：在不清洗供墨系统和喷墨系统的前提下，暂停使用打印机，18小时后重新启动打印，查看是否出现断针情况并将测试结果记录在表1中。应当指出的是，18小时后重新启动打印出现断针的数量为5个以下说明墨水的保湿性能良好。
3、残留测试：取10ml墨水倒在5μm不锈钢过滤网上，使墨水依靠自身重力通过该过滤网，20秒后观察过滤网上的残留情况，将过滤网洗净观察过滤网上是否有残留，并将测试结果记录在表1中。应当指出的是，20秒后残留量少于5%、洗净后残留量少于1%说明墨水的残留测试良好。
 本发明的实施方式
实施例2
本实施例与实施例1的区别在于，所述无机颜料为颜料黄53，其他同实施例1。
实施例3
本实施例与实施例1的区别在于，所述无机颜料为颜料棕24，其他同实施例1。
实施例4
本实施例与实施例1的区别在于，所述无机颜料为颜料蓝28，其他同实施例1。
实施例5
本实施例与实施例1的区别在于，所述无机颜料为颜料绿50，其他同实施例1。
实施例6
本实施例与实施例1的区别在于，所述无机颜料为二氧化钛，其他同实施例1。
实施例7
本实施例与实施例1的区别在于，所述分散剂为SOLSPERSE28000，其他同实施例1。
实施例8
本实施例与实施例1的区别在于，所述分散剂为SOLSPERSE32000，其他同实施例1。
实施例9
本实施例与实施例1的区别在于，所述分散剂为DISPERBYK2150，其他同实施例1。
实施例10
本实施例与实施例1的区别在于，所述树脂为聚乙烯吡咯烷酮，其他同实施例1。
实施例11
本实施例与实施例1的区别在于，所述树脂为丙烯酸树脂，其他同实施例1。
实施例12
本实施例与实施例1的区别在于，所述树脂为聚（甲基）丙烯酸类化合物，其他同实施例1。
实施例13
本实施例与实施例1的区别在于，所述有机溶剂A为丙二醇-n-丙醚（20），其他同实施例1。
实施例14
本实施例与实施例1的区别在于，所述有机溶剂A为乙二醇单甲醚乙酸酯（30），其他同实施例1。
实施例15
本实施例与实施例1的区别在于，所述有机溶剂A为3-甲氧基乙酸丁酯（30），其他同实施例1。
实施例16
本实施例与实施例1的区别在于，所述有机溶剂B为二丙二醇-n-丙醚（2），其他同实施例1。
实施例17
本实施例与实施例1的区别在于，所述有机溶剂B为二乙二醇单乙醚乙酸酯（1），其他同实施例1。
实施例18
本实施例与实施例1的区别在于，所述打印墨水的制备方法包括如下步骤：
S1.颜料分散液的制备：用6wt%的分散剂、50wt%的无机颜料和剩余重量百分数的有机溶剂A进行预混合后，用搅拌机进行分散，得到无机颜料的重量百分数为50wt%的颜料分散液，此时，颜料分散液中的有机颜料粒子的平均粒径为400nm。其平均粒径是在将分散液稀释至规定浓度（检测仪的负荷指数3~5的范围内）后用MICROTRACK公司生产的纳米粒度仪NANO-Flex检测得到的。
S2.玻璃熔块分散液的制备：与颜料分散液的制备相同，用玻璃熔块代替无机颜料进行微细化处理，制备得到玻璃熔块重量百分数为50wt%的玻璃熔块分散液，此时，玻璃熔块分散液中玻璃熔块粒子的平均粒径为550nm。
S3.打印墨水的制备：将40wt%的颜料分散液、30 wt%的玻璃熔块分散液、28 wt%的有机溶剂B以及剩余重量百分数的树脂混合制得打印墨水。此时，打印墨水的粘度为10~20mPa·s，表面张力为20.0~30.0mN/m，最大粒子粒径小于3μm，最好为1μm。
实施例19
本实施例与实施例1的区别在于，所述打印墨水的制备方法包括如下步骤：
S1.颜料分散液的制备：用6wt%的分散剂、50wt%的无机颜料和剩余重量百分数的有机溶剂A进行预混合后，用搅拌机进行分散，得到无机颜料的重量百分数为50wt%的颜料分散液，此时，颜料分散液中的有机颜料粒子的平均粒径为400nm。其平均粒径是在将分散液稀释至规定浓度（检测仪的负荷指数3~5的范围内）后用MICROTRACK公司生产的纳米粒度仪NANO-Flex检测得到的。
S2.玻璃熔块分散液的制备：与颜料分散液的制备相同，用玻璃熔块代替无机颜料进行微细化处理，制备得到玻璃熔块重量百分数为50wt%的玻璃熔块分散液，此时，玻璃熔块分散液中玻璃熔块粒子的平均粒径为550nm。
S3.打印墨水的制备：将30wt%的颜料分散液、40 wt%的玻璃熔块分散液、29 wt%的有机溶剂B以及剩余重量百分数的树脂混合制得打印墨水。此时，打印墨水的粘度为10~20mPa·s，表面张力为20.0~30.0mN/m，最大粒子粒径小于3μm，最好为1μm。
实施例20
本实施例与实施例1的区别在于，所述打印墨水的制备方法包括如下步骤：
S1.颜料分散液的制备：用4wt%的分散剂、25wt%的无机颜料和剩余重量百分数的有机溶剂A进行预混合后，用搅拌机进行分散，得到无机颜料的重量百分数为25wt%的颜料分散液，此时，颜料分散液中的有机颜料粒子的平均粒径为280nm。其平均粒径是在将分散液稀释至规定浓度（检测仪的负荷指数3~5的范围内）后用MICROTRACK公司生产的纳米粒度仪NANO-Flex检测得到的。
S2.玻璃熔块分散液的制备：与颜料分散液的制备相同，用玻璃熔块代替无机颜料进行微细化处理，制备得到玻璃熔块重量百分数为25wt%的玻璃熔块分散液，此时，玻璃熔块分散液中玻璃熔块粒子的平均粒径为420nm。
S3.打印墨水的制备：将20wt%的颜料分散液、40 wt%的玻璃熔块分散液、36 wt%的有机溶剂B以及剩余重量百分数的树脂混合制得打印墨水。此时，打印墨水的粘度为10~20mPa·s，表面张力为20.0~30.0mN/m，最大粒子粒径小于3μm，最好为1μm。
实施例21
本实施例与实施例1的区别在于，所述打印墨水的制备方法包括如下步骤：
S1.颜料分散液的制备：用8wt%的分散剂、65wt%的无机颜料和剩余重量百分数的有机溶剂A进行预混合后，用搅拌机进行分散，得到无机颜料的重量百分数为65wt%的颜料分散液，此时，颜料分散液中的有机颜料粒子的平均粒径为480nm。其平均粒径是在将分散液稀释至规定浓度（检测仪的负荷指数3~5的范围内）后用MICROTRACK公司生产的纳米粒度仪NANO-Flex检测得到的。
S2.玻璃熔块分散液的制备：与颜料分散液的制备相同，用玻璃熔块代替无机颜料进行微细化处理，制备得到玻璃熔块重量百分数为65wt%的玻璃熔块分散液，此时，玻璃熔块分散液中玻璃熔块粒子的平均粒径为580nm。
S3.打印墨水的制备：将38.5wt%的颜料分散液、46.1wt%的玻璃熔块分散液、14.9wt%的有机溶剂B以及剩余重量百分数的树脂混合制得打印墨水。此时，打印墨水的粘度为10~20mPa·s，表面张力为20.0~30.0mN/m，最大粒子粒径小于3μm，最好为1μm。
表1 实施例1~22测试结果
实施例 平均墨点直径 重启后打印情况 残留情况
1 0.43mm 喷孔有2~3个断针 20s后残留2~4%，清洗后无残留
2 0.41mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
3 0.55mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
4 0.50mm 喷孔有3~5个断针 20s后残留5~6%，清洗后无残留
5 0.43mm 喷孔有1~2个断针 20s后残留1~2%，清洗后无残留
6 0.42mm 喷孔有2~3个断针 20s后残留5~6%，清洗后无残留
7 0.46mm 喷孔有2~3个断针 20s后残留2~4%，清洗后无残留
8 0.45mm 喷孔有2~4个断针 20s后残留3~4%，清洗后无残留
9 0.48mm 喷孔有2~3个断针 20s后残留2~4%，清洗后无残留
10 0.43mm 喷孔有2~4个断针 20s后残留2~3%，清洗后无残留
11 0.45mm 喷孔有2~3个断针 20s后残留2~3%，清洗后无残留
12 0.42mm 喷孔有1~2个断针 20s后残留1~3%，清洗后无残留
13 0.46mm 喷孔有2~3个断针 20s后残留2~3%，清洗后无残留
14 0.42mm 喷孔有2~3个断针 20s后残留2~3%，清洗后无残留
15 0.43mm 喷孔有2~4个断针 20s后残留2~3%，清洗后无残留
16 0.43mm 喷孔有1~2个断针 20s后残留2~3%，清洗后无残留
17 0.40mm 喷孔有1~2个断针 20s后残留2~3%，清洗后无残留
18 0.51mm 喷孔有3~5个断针 20s后残留2~4%，清洗后无残留
19 0.48mm 喷孔有2~4个断针 20s后残留2~4%，清洗后无残留
20 0.65mm 喷孔有1~2个断针 20s后残留1~2%，清洗后无残留
21 0.61mm 喷孔有3~5个断针 20s后残留3~5%，清洗后无残留
对比例1
本对比例与实施例1的区别在于，所述有机溶剂A为甲酯（1040），测试结果记录在表2中，其他同实施例1。由于所选择的溶剂的干燥速度过快，因此在头部发生干燥，再喷出性降低。
对比例2
本对比例与实施例1的区别在于，所述有机溶剂B为乙二醇单甲醚乙酸酯（30），测试结果记录在表2中，其他同实施例1。相当于本对比例不含有机溶剂B，干燥速度加快，很快在喷嘴处发生干燥，导致喷吐性不良。
对比例3
本对比例与实施例1的区别在于，所述有机溶剂A为二丙二醇-n-丙醚（2），测试结果记录在表2中，其他同实施例1。相当于本对比例不含有机溶剂A，干燥速度变慢，因而不会在喷嘴处发生干燥等情况，喷吐性良好，但由于喷绘时干燥速度变慢，墨点到达打印介质表面时会出现扩散的现象影响打印质量。
对比例4
本对比例与对比例1的区别在于，所述无机颜料为颜料黄53，其他同对比例1。
对比例5
本对比例与对比例2的区别在于，所述无机颜料为颜料黄53，其他同对比例2。
对比例6
本对比例与对比例3的区别在于，所述无机颜料为颜料黄53，其他同对比例3。
对比例7
本对比例与对比例1的区别在于，所述无机颜料为颜料棕24，其他同对比例1。
对比例8
本对比例与对比例2的区别在于，所述无机颜料为颜料棕24，其他同对比例2。
对比例9
本对比例与对比例3的区别在于，所述无机颜料为颜料棕24，其他同对比例3。
对比例10
本对比例与对比例1的区别在于，所述无机颜料为颜料蓝28，其他同对比例1。
对比例11
本对比例与对比例2的区别在于，所述无机颜料为颜料蓝28，其他同对比例2。
对比例12
本对比例与对比例3的区别在于，所述无机颜料为颜料蓝28，其他同对比例3。
对比例13
本对比例与对比例1的区别在于，所述无机颜料为颜料绿50，其他同对比例1。
对比例14
本对比例与对比例2的区别在于，所述无机颜料为颜料绿50，其他同对比例2。
对比例15
本对比例与对比例3的区别在于，所述无机颜料为颜料绿50，其他同对比例3。
对比例16
本对比例与对比例1的区别在于，所述无机颜料为颜料白6，其他同对比例1。
对比例17
本对比例与对比例2的区别在于，所述无机颜料为颜料白6，其他同对比例2。
对比例18
本对比例与对比例3的区别在于，所述无机颜料为颜料白6，其他同对比例3。
对比例19
本实施例与实施例1的区别在于，采用现有的打印机进行打印和测量，其他同实施例1。
表2 对比例1~19测试结果
对比例 平均墨点直径 重启后打印情况 残留情况
1 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
2 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
3 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
4 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
5 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
6 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
7 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
8 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
9 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
10 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
11 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
12 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
13 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
14 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
15 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
16 0.41mm 喷孔有15~16个断针 20s后残留2~4%，清洗后无残留
17 0.43mm 喷孔有9~10个断针 20s后残留2~4%，清洗后无残留
18 0.93mm 喷孔有1~2个断针 20s后残留2~4%，清洗后无残留
19 0.74mm 喷孔有4~6个断针 /
显然，本专利的上述实施例仅仅是为清楚地说明本专利所作的举例，而并非是对本专利的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本专利的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本专利权利要求的保护范围之内。

Claims (8)

  1. 一种打印墨水，其特征在于，包括无机颜料、玻璃熔块、分散剂、树脂和有机溶剂。
  2. 根据权利要求1所述的打印墨水，其特征在于，有机溶剂包括有机溶剂A和有机溶剂B至少两种溶剂，以醋酸丁酯的值为100，在25℃、1atm条件下依据ASTM-D3539测得，有机溶剂A的相对蒸发速度为10~1000，有机溶剂B的相对蒸发速度为0.1~9；无机颜料包括黑色颜料、黄色颜料、蓝色颜料、红色颜料、绿色颜料、白色颜料中的一种或多种；无机颜料和玻璃熔块的粒径为200~1000nm。
  3. 根据权利要求1或2所述的打印墨水，其特征在于，所述玻璃熔块的重量百分数为10~30wt%。
  4. 根据权利要求1或2所述的打印墨水，其特征在于，所述无机颜料的重量百分数为5~25wt%。
  5. 根据权利要求1或2所述的打印墨水，其特征在于，所述树脂的重量百分数为0.05~5wt%。
  6. 一种制备权利要求1~5所述打印墨水的方法，其特征在于，将所述无机颜料和玻璃熔块分别与有机溶剂和分散剂预混合，再用分散机进行分散得到分散液，然后添加所述树脂混合均匀后进行过滤，制备得到打印墨水。
  7. 一种应用权利要求1~6所述打印墨水的打印机，其特征在于，所述打印机顺序设置有预热区、保温区和打印区，包括贯穿预热区、保温区、打印区的输送平台和设置在打印区的位于输送平台上方的打印模组，所述打印模组中设有喷墨系统、控制系统、储存并向喷墨系统供应所述打印墨水的供墨系统和控制喷墨系统墨水喷绘温度的温控系统，所述预热区的温度T1为80~100℃，所述保温区的温度T2为60~80℃。
  8. 根据权利要求7所述的应用所述打印墨水的打印机，其特征在于，所述打印机还设有与预热区相接的打印介质清洗区，所述打印介质清洗区中设有用于清洗打印介质的打印介质清洗机。
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