JP4822422B2 - Marking method and ink - Google Patents

Marking method and ink Download PDF

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JP4822422B2
JP4822422B2 JP2006065105A JP2006065105A JP4822422B2 JP 4822422 B2 JP4822422 B2 JP 4822422B2 JP 2006065105 A JP2006065105 A JP 2006065105A JP 2006065105 A JP2006065105 A JP 2006065105A JP 4822422 B2 JP4822422 B2 JP 4822422B2
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ink
mark
inorganic pigment
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printing
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JP2007238400A (en
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成造 尾畑
英明 柘植
久範 横山
幸太 細野
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岐阜県
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  The present invention relates to a marking method and an ink, and more particularly to a marking method for a ceramic product used / manufactured at a high temperature, and an ink suitable for the method.

  Generally, an industrial product is often marked with a production number, a model number, a lot number, a company seal, a company name logo, or the like. And it has been attempted to perform such marking on various ceramic products used / manufactured at high temperatures. Here, ceramic products used / manufactured at high temperatures include refractories for firing such as mortars and shelves, ceramic tubes used as core tubes and protective tubes, ceramic filters for high temperature dust collection, ICs, etc. A ceramic electronic material such as an alumina substrate for a circuit can be exemplified. Refractories for firing such as mortars and shelves are jigs that are used to protect the firing objects and efficiently stack them in the firing furnace when firing ceramics, building materials, electronic parts, etc. It is.

  As a marking method for such a ceramic product, a stamp printing method is generally used in which a high-viscosity ink is applied to a rubber mold and an object is stamped. Also, a method of screen-printing a mark with a glassy material paste on an alumina substrate and attaching the substrate to an object (see Patent Document 1), a surface of a labeling substrate by a marking material in which glass frit is added to a noble metal powder A method of printing a mark on the object and affixing the mark to an object (see Patent Document 2), a method of forming a printing ribbon or sheet with an ink containing an inorganic compound and glass frit, and performing thermal transfer or imprint printing on the object ( Patent Document 3), and a method of forming a mark by irradiating an electronic component composed of a ceramic sintered body with a laser beam and then heat-treating (see Patent Document 4) has been proposed.

Japanese Utility Model Publication No. 62-144203 JP-A-6-58679 Japanese Examined Patent Publication No. 7-45258 JP 2005-150636 A

  However, the stamp printing method is suitable for printing a large number of simple, single marks such as company seals and company name logos. There is a problem that it is not suitable for printing the mark. In addition, when stamping many types of marks according to the object, it is currently printed manually while replacing the rubber mold, which has a problem that the labor is heavy and the production cost increases. It was. In addition, since work takes time, there is a problem that marking cannot be performed on the production line of the product to be printed.

  In addition, the screen printing method (Patent Document 1) can print marks that are complicated to some extent, but requires a plate making process, and a large number of plate making is not necessary in order to deal with many kinds of marks. In addition to increasing the labor burden and the required time, there is a problem that costs increase.

  Furthermore, in the method of marking using a glassy material (Patent Documents 1 to 3), generally, when heated to 1000 ° C. or higher, the glass component melts and the mark disappears. In addition, the evaporation of heavy metal components such as alkali metal components and lead contained in the glass contaminates the product to be fired, thereby deteriorating the characteristics and damaging the firing furnace. In particular, the refractories for firing, furnace materials, high-temperature dust collection filters, and the like as described above are repeatedly used at high temperatures, and such problems are significant.

  In addition, the method of marking on a substrate and attaching it to a product (Patent Literature 1 and Patent Literature 2) or the method of marking via a printing ribbon sheet (Patent Literature 3) results in indirect printing, and the substrate is attached. There is a problem that the number of steps for marking increases, such as a step of making and a step of manufacturing a ribbon, and it takes time and effort. Furthermore, although the marking method using laser light (Patent Document 4) can directly mark an object, since it requires a laser light irradiation device, there is a problem that the equipment becomes large and the production cost increases.

  Therefore, in view of the above circumstances, the present invention can provide a ceramic product with a mark that does not easily disappear or fade even at high temperatures, and even a complicated mark or multiple types of marks can be easily shortened. It is an object to provide a marking method capable of marking in time and an ink suitable for the method.

  The marking method according to the present invention includes: an inorganic pigment that develops color by firing at a temperature of 1000 ° C. or higher and 1700 ° C. or lower, containing 15 wt% or more and 34 wt% or less with respect to the total composition amount. A mark including at least one of letters, numbers, symbols, symbols, and identification codes is created as a digital image by preparing an ink to which a dispersant of 1 wt% to 1.6 wt% is added. An image forming step, an ink jet printing step of performing ink jet printing of the mark on a ceramic body by ejecting the ink based on the digital image, and the ceramic body on which the mark is ink jet printed are 1000 ° C. or higher and 1700 ° C. or lower. And a baking step of baking at a temperature ”.

  Examples of the “ceramic body” include an unheated molded body, a calcined body obtained by calcining the molded body at a temperature lower than the firing temperature, and a sintered body obtained by calcining the molded body or the calcined body. The molding method of the molded body is not particularly limited, and examples thereof include pressure molding, extrusion molding, injection molding, and cast molding. Ceramic products manufactured by firing this ceramic body include mortars used for the purpose of protecting the objects to be fired and efficiently stacking them in the firing furnace when firing ceramics and electronic parts. Refractories for firing such as shelves, sheaths, boats and crucibles, furnace materials such as refractory bricks used for furnace walls and hearths, ceramic tubes used as core tubes and protective tubes, IC circuit boards, etc. Examples thereof include ceramic electronic materials, magnetic materials such as ferrite cores, ceramic filters for high-temperature dust collection, and the like.

  “Marks that include at least one of letters, numbers, symbols, designs, and identification codes” include manufacturing numbers, model numbers, lot numbers, company seals and company name logos, identification codes such as barcodes and two-dimensional symbols, Examples include photographs and design patterns.

  The printing machine used for “inkjet printing” is not particularly limited. For example, a printing system using a piezoelectric method using a piezoelectric element or a thermal method using a heating element is used as a head method for ejecting ink. Can be used. Further, the printing object is not limited to a flat printed surface. For example, even if the printing object is tubular or cylindrical, it is possible to perform inkjet printing directly by performing control to rotate the object with respect to the ejected ink.

  Further, in ordinary ink jet printing, organic pigment ink or organic dye ink is used. In the present invention, “inorganic pigment” having generally high heat resistance is used as a coloring material of ink. Here, “inorganic pigments that develop color by firing at a temperature of 1000 ° C. or more and 1700 ° C. or less” are cobalt, cobalt-aluminum, cobalt-iron-aluminum, and antimony-tin as pigments that develop blue, black, and brown colors. And oxides such as titanium, aluminum, tin, and zinc can be illustrated as pigments that develop white and yellow colors. it can. As will be described later, colored rare earth oxides such as neodymium, praseodymium, holmium, and erbium can also be used. In addition, it is preferable to use blue, black and brown pigments when the ceramic product is light-colored and to use white and yellow pigments when it is dark.

  In order for the printed mark to be difficult to disappear or fade, the mark needs to be printed in a dark color. Here, even if the inorganic pigment concentration of the ink is low, the mark can be darkened by, for example, reciprocating the head many times at the same position and overprinting. Time will increase. In the case of water-based ink, if the concentration of the inorganic pigment is low, the solvent contained in the ink cannot be completely dried after printing, and the ink spreads on the surface of the printing object and the mark becomes unclear. . For this reason, low-density ink is not suitable for marking a mark that is required to have high definition, such as difficult to read with an identification code such as a complex barcode. In addition, since the low-density ink has a low viscosity, inorganic pigment particles having a large specific gravity are likely to settle, the sedimentation stability is lowered, and the long-term storage stability is poor.

  On the other hand, when the concentration of the inorganic pigment is increased in order to make the mark darker, the particles of the inorganic pigment tend to aggregate and become difficult to disperse well in the ink, and nozzle clogging due to the aggregated particles tends to occur. Further, the increase in the viscosity of the ink makes it difficult to eject the ink from the nozzle. Furthermore, the addition of a dispersant can increase the concentration of the inorganic pigment to a certain extent while maintaining good dispersibility. However, if the amount of the dispersant is too large, aggregation tends to occur.

  Therefore, as a result of earnest research on the ink having a high concentration of inorganic pigment while maintaining a state in which the dispersibility of the particles of the inorganic pigment is good and hardly agglomerates and can be satisfactorily discharged from the nozzle of the ink jet printer, 0 It was found that the inorganic pigment concentration can be increased to 15 wt% or more and 34 wt% or less by adding a dispersant of 1 wt% or more and 1.6 wt% or less. Here, the addition amount of the dispersing agent is expressed as a mass percentage with respect to the inorganic pigment of the organic component that disappears by firing excluding the solvent component.

  As the “dispersant”, known organic dispersants used for inorganic pigments and ceramic powders can be used, and one or a plurality of types of anionic, cationic, and nonionic dispersants can be used. Can be appropriately selected. Specifically, stearates, alginates, carboxylates, naphthalenesulfonates, polyoxyethylene sorbitan mononolate, polycarboxylates, polyacrylates, polyoxyethylene fatty acid salts, alkylbenzenesulfonates, Organic salts such as alkylsulfosuccinates, organics such as methylcellulose and ethylcellulose, and acids such as oxalic acid and acetic acid can be used.

  The “firing step” is a step of firing the inorganic pigment in the ink. When the ceramic body is a formed body or a calcined body, it can also serve as a step of firing the ceramic body. Here, the firing temperature is set to a temperature suitable for firing the inorganic pigment and the ceramic body in the range of 1000 ° C. to 1700 ° C. Then, through the baking process at a high temperature of 1000 ° C. or higher and 1700 ° C. or lower, the attached mark has heat resistance that can withstand the high temperature up to the baking temperature. Note that the firing atmosphere is not particularly limited, and can be appropriately set according to the firing object, such as an oxidizing atmosphere, a reducing atmosphere, or a vacuum atmosphere.

  The ink preparation process, the image creation process, the ink jet printing process, and the baking process do not have to be performed continuously as a series of processes. There may be a long period of time between each process, such as when printing using a created digital image. Further, there is no prior relationship between the ink preparation step and the image creation step, and both steps may be performed simultaneously.

  Therefore, according to the present invention, generally, an inorganic pigment having high heat resistance is used as a coloring material for ink, and is fired at a high temperature of 1000 ° C. to 1700 ° C. It is possible to give a stable mark that is unlikely to disappear or fade at a high temperature to a ceramic product that is repeatedly used at a high temperature, such as a dust filter. In addition, since inorganic pigments are generally excellent in corrosion resistance, they are applied even if they are subjected to harsh environments such as plasma irradiation and ultraviolet irradiation in the manufacturing process, such as ceramic substrates for IC circuits. The mark is stable and difficult to disappear or fade.

  In addition, by adding a dispersant of 0.1 wt% or more and 1.6 wt% or less as an organic component to the inorganic pigment, an inorganic ink is obtained while forming an ink that is less likely to cause agglomerated particles, excellent sedimentation stability, and nozzle clogging. The concentration of the pigment can be increased to a certain high concentration of 15 wt% or more and 34 wt% or less. This makes it possible to apply a dark color mark to the ceramic body by applying an ink jet printing technique to the inorganic pigment-based ink.

  In this way, by applying inkjet printing technology to the marking on the ceramic body, it is not necessary to create a mark prototype like stamp printing or screen printing, reducing the number of processes and labor and cost, Efficient marking can be performed. In addition, marking can be performed using an ink jet printer having a simple configuration without requiring a large facility.

  In inkjet printing, since a technology for printing based on digital images processed using word processor software, CAD software, image editing software, etc. on a computer has already been established, it is easy to create new marks for marking. Can be created. In particular, even complex digital images can be easily created on a computer, making it possible to add complex marks to ceramic bodies. For example, complex information such as barcodes and two-dimensional symbols A large amount of identification code can be printed.

  In addition, it is possible to modify and change off-the-shelf marks very easily by digital processing on a computer, so it is possible to change marks quickly in response to changes in ceramic product specifications. . Also in the inkjet printing process, it is possible to easily set and change the type of marks to be printed, the number of prints, the order of printing, etc. by computer control. Multiple kinds of marks can be given.

  Further, since the ink concentration (inorganic pigment concentration) can be set to a certain high concentration of 15 wt% or more and 34 wt% or less, even if the number of times the head is reciprocated at the same position during overprinting is reduced, it is dark and clear. Can be printed easily. Thereby, the time required for marking can be shortened.

  Furthermore, by making the printing process an inkjet printing process that can be easily controlled by a computer, the marking process can be automated and incorporated into a production line for ceramic products. In particular, according to the present invention, as described above, since the required time for marking is short due to the high concentration of ink, the ceramic body is formed in a short time of about several seconds to several tens of seconds in general pressure molding or extrusion molding. It is possible to incorporate a marking process into the manufacturing process.

  Further, the marking method according to the present invention may be “the inorganic pigment has an average particle diameter of 10 nm to 100 nm”. Here, the average particle diameter is based on the dynamic light scattering method.

  Therefore, according to the present invention, even if the inorganic pigment has a large specific gravity, the dispersibility of the inorganic pigment particles in the ink is improved by using fine particles having an average particle diameter of 10 nm to 100 nm. It will be a thing. Moreover, marking with high reproducibility (quality stability) can be performed using an ink having excellent sedimentation stability and a more uniform composition. In addition, by using an ink that hardly causes precipitation or aggregation of inorganic pigments even during long-term storage, nozzle clogging is less likely to occur during ink jet printing, and ink can be ejected better. The average particle diameter of the inorganic pigment is more preferably 80 nm or less.

  Next, the ink according to the present invention contains “an inorganic pigment that develops color by firing at a temperature of 1000 ° C. to 1700 ° C.” in an amount of 15 wt% to 34 wt% based on the total composition amount. As a dispersant, 0.1 wt% or more and 1.6 wt% or less of a dispersant is added.

  Therefore, according to the present invention, the ink is suitable for marking and decorating a ceramic body fired at a high temperature of 1000 ° C. or higher and 1700 ° C. or lower. In addition, even if the ceramic product obtained by firing the ceramic body to which this ink is applied is repeatedly used at high temperatures, or manufactured and used in harsh environments such as plasma irradiation, it will disappear and fade. It is an ink that can be applied with a stable mark that is difficult to perform.

  Furthermore, since it is prepared as an ink suitable for inkjet printing while increasing the inorganic pigment concentration, it is suitable for the marking method of the present invention described above. The ink of the present invention can also be applied to printing methods other than inkjet printing, such as using a paintbrush or brush and drawing directly on the ceramic body. The printing object may be an object other than the ceramic body.

  As an effect of the present invention, it is possible to mark ceramic products with marks that do not easily disappear or fade even at high temperatures, and marking that can be easily and quickly performed even for complex marks and multiple types of marks. A method and an ink suitable for the method can be provided.

  Hereinafter, a marking method and an ink according to an embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a flowchart showing the steps in the marking method of the present embodiment, FIG. 2 is an explanatory view schematically showing the outline of the marking method of FIG. 1, and FIG. 3 shows the inorganic pigment concentration of the ink of the present embodiment. FIG. 4 is a graph showing an example of the relationship between the apparent viscosity and FIG. 4 is a graph showing an example of the relationship between the dispersant concentration of the ink of this embodiment and the apparent viscosity. In the present embodiment, a case where a porous ceramic molded body is used as the ceramic body is illustrated.

  In the marking method 1 of the present embodiment, as shown mainly in FIG. 2, the ink 2, the porous ceramic molded body 10 to be marked, word processor software and image processing software are installed, and letters, numbers, symbols, A computer 5 capable of creating a digital image 11 as a basis of a mark 21 including at least one of a design and an identification code, and a head electrically connected to the computer 5 and having a nozzle 7 based on the digital image 11 6 is performed mainly using an ink jet printer (not shown) that discharges the ink 2 from 6 and a firing furnace (not shown) that fires the ceramic molded body 10 on which the mark 21 is printed.

  Each process in the marking method 1 of this embodiment is demonstrated mainly based on FIG. First, an inorganic pigment that develops color at 1000 ° C. or more and 1700 ° C. or less is set to 15 wt% or more and 34 wt% or less with respect to the total composition amount, and a dispersant is added to the inorganic pigment as an organic component in an amount of 0.1 wt% or more and 1.6 wt% or less. Ink 2 is prepared by mixing by an appropriate mixing method such as ball milling (ink preparation step S1). In this embodiment, an inorganic pigment having an average particle size of 10 nm to 100 nm is used. The apparent viscosity of the ink 2 that can be favorably ejected from the nozzle 7 can be set as a certain index, and it is desirable that the apparent viscosity is 5 mPa · s or more and 10 mPa · s or less. Here, the apparent viscosity is a value measured using a rotational viscometer at a temperature of 25 ° C. and a shear rate of 1000 to 3000 / s.

  At this time, the solvent may be an aqueous solvent or a non-aqueous solvent, but in the present embodiment, an aqueous solvent is used in consideration of the working environment. Here, when an aqueous solvent is used, a drying inhibitor can be added for the purpose of preventing drying at the nozzle tip. The drying inhibitor preferably has hydrophilicity that can be mixed with water and has a small effect on the viscosity. Alcohols such as ethyl alcohol and ethylene glycol; ethers such as ethylene glycol monoethyl ether; Acetone alcohol and 2-pyrrolidone can be exemplified. Furthermore, other additives such as a wetting agent, a surfactant, and an anti-settling agent may be added depending on the purpose of adjusting the sedimentation property and surface tension of the inorganic pigment particles. However, excessive addition of these additives causes an increase in the viscosity of the ink and a significant decrease in the surface tension, which may result in an ink that is not suitable for inkjet printing. More desirably, the addition amount is 0.5 wt% or less.

  On the other hand, the digital image 11 which becomes the basis of the mark 21 to be printed on the ceramic molded body 10 is created using the computer 5 (image creation step S2). Here, the mark 21 is, for example, a manufacturing number, a model number, a lot number, a company seal or a company name logo, an identification code such as a barcode or a two-dimensional symbol, and a design pattern. It can be newly created by image processing software. Alternatively, the existing digital image 11 or digital data read from an external device such as a digital camera or a scanner can be used to process and edit the digital image 11. Note that the order after the ink preparation step S1 and the image creation step S2 does not necessarily have to be in the above order, and both steps may be performed simultaneously in the reverse order.

  And based on the created digital image 11, the ink 2 is discharged from the nozzle 7 of the head 6 of an inkjet printer, and the mark 21 is inkjet-printed on the ceramic molded body 10 (inkjet printing process S3). At this time, the type of the mark 21 to be printed, the number of prints, and the print according to the type and number of the ceramic molded body 10 based on the program stored in the computer 5 in advance by computer control or based on the input of the operator. You can set the order. Thereby, for example, products with different model numbers can be mixed and marked automatically on the same line, or individual identification codes can be marked for each product.

  In the present embodiment, a piezo-type ink jet printer capable of simultaneously discharging ink from a plurality of nozzles and printing at high speed is used. In particular, a shear type piezo method is preferable in which ink is ejected by shear deformation of a piezoelectric element and the ink can be ejected even when the viscosity of the ink is relatively high. Further, the mark 21 to be printed can be darkened by reciprocating the head 6 a plurality of times at the same position during printing, but in this embodiment, the concentration of the inorganic pigment is increased to 15 wt% or more. Therefore, the dark mark 21 can be printed with a small number of reciprocations such as several times.

  In the present embodiment, a mesh-like filter having a diameter of 5 to 10 μm is provided between the nozzle 7 and an ink introducing portion (not shown) to the nozzle 7. Thereby, even if coarse particles are mixed in the ink 2, they are not introduced into the nozzle 7, and the nozzle 7 can be prevented from being clogged.

  Moreover, as for the marking location in the ceramic molded object 10, when the ceramic sintered compact 20 by which the ceramic molded object 10 was baked is actually used, it is desirable to select the location which does not affect use. For example, in the case of a square mortar or a shelf board, it is possible to mark a flat portion on the side surface or the lower surface. When a non-planar portion such as a high-temperature dust collection filter or a ceramic tube is to be printed, the ceramic molded body 10 is rotated with respect to the path of the ink discharged from the nozzle 7, or the nozzle 7 or the actuator By controlling the ceramic molded body 10 to be displaced relative to the ejection direction of the ink 2, it is possible to perform ink jet printing directly.

  Next, the ceramic formed body 10 that has been ink-jet printed is introduced into a firing furnace and fired at a temperature of 1000 ° C. or higher and 1700 ° C. or lower (firing step S4). Thereby, the inorganic pigment in the ink 2 is baked, and a stable mark 21 is formed even at a high temperature. Further, the firing step S4 of the present embodiment also serves as a step of firing the ceramic molded body 10 to obtain the ceramic sintered body 20. In this case, the firing temperature is set in accordance with the ceramic molded body 10 and can be set to 1300 ° C. or higher for a baking refractory such as a mortar or a shelf, and 1500 ° C. or higher for an alumina molded body.

  In addition, each said process can be integrated in the manufacturing line of ceramic products. For example, an ink jet printing step S3 can be provided between the forming step for producing the ceramic molded body 10 and the firing step S4. As a result, at the stage of manufacture, the ceramic product is already provided with the mark 21, which is more efficient than the case of marking after manufacture.

  Therefore, according to the marking method 1 and the ink 2 of the present embodiment, the inorganic pigment having high heat resistance is used as the coloring material of the ink 2 and is used at a high temperature by baking at a high temperature of 1000 ° C. or higher and 1700 ° C. or lower. It is possible to give a stable mark 21 that is not easily lost or discolored at a high temperature to the ceramic product.

  In addition, in the ink preparation step S1, an inorganic pigment that has conventionally been difficult to apply to ink jet printing due to its large specific gravity is used. Since the ink 2 that is less likely to be clogged is prepared, the ceramic molded body 10 can be marked with an inorganic pigment-based ink by applying an inkjet printing technique. In this embodiment, since the inorganic pigment is a fine particle having an average particle diameter of 10 nm or more and 100 nm or less, the ink 2 has better dispersibility, better settling stability, and is less likely to clog the nozzle 7. Prepared.

  Furthermore, in the digital image creation step S2, a new mark 21 can be easily created, and corrections and changes can be easily made to the ready-made mark 21. Thereby, according to the kind of ceramic molded object 10, it becomes possible to provide many types of marks 21. FIG. Also, the digital image 11 that is the basis of the complicated mark 21 can be easily created. For example, a complicated identification code having a large amount of information such as a barcode or a two-dimensional symbol can be used as the mark 21.

  In addition, in the inkjet printing step S3, the type, number of prints, printing order, etc. of the marks 21 to be printed can be easily set by computer control. Corresponding to the body 10, various kinds of marks 21 can be marked.

  In addition, since inkjet printing can be applied to the marking on the ceramic molded body 10, there is no need to create a mark prototype, the marking process can be simplified, and marking can be performed efficiently. Also, the equipment for printing becomes simple.

  Next, FIG. 3 shows an example of the relationship between the inorganic pigment concentration and the apparent viscosity of the ink, and FIG. 4 shows an example of the relationship between the added amount of the dispersant and the apparent viscosity of the ink. Here, cobalt-aluminum oxide having an average particle diameter of 50 nm is used as the inorganic pigment, a predetermined amount of the inorganic pigment and a predetermined amount of organic pigment dispersed in the inorganic pigment in water and an anti-drying agent 80:20 solvent. The apparent viscosity measured with a rotational viscometer (HAKKE VT-550: NV rotor, shear rate 2000 / s) is shown for an ink prepared by adding an agent and mixing by a ball mill for 3 days. In FIG. 3, the dispersant addition amount is a constant value of 1.1 wt% as an organic content with respect to the inorganic pigment, and in FIG. 4, the inorganic pigment concentration is a constant value of 20 wt%.

  In addition, a membrane filter having a diameter of about 5 μm, which has the same hole diameter as that of the filter provided between the nozzle 7 and the ink introduction part of the ink jet printer, is used to filter the ink prepared for each concentration. The presence of aggregated particles that could not pass through the filter was confirmed. The results of this filtration test are also shown in FIGS. Here, A is a case where ink passes through the filter well and there is no residue on the filter, B is a case where a residue that does not pass through the filter is confirmed on the filter, and C is that the ink hardly passes through the filter. Shows the case.

  As shown in FIG. 3, the apparent viscosity increases with an increase in the inorganic pigment concentration of the ink. When the inorganic pigment concentration becomes 26 wt% or more, residual matter is confirmed on the filter, and the particles are aggregated in the ink. It was thought that it was starting to occur. Further, as shown in FIG. 4, the increase in the apparent viscosity when the amount of the dispersant added was increased from 1.1 wt% to 1.65 wt% was slight, but the amount of the dispersant added was 1. When it exceeds 65 wt%, the apparent viscosity greatly increased. Further, when the added amount of the dispersant was 1.65 wt%, a slight residue was confirmed on the filter. However, when the added amount was 2.1 wt%, the filter was clogged and the ink was filtered. It became impossible. Thereby, even if there was too much addition amount of a dispersing agent, it caused the inorganic pigment particle to aggregate, and it was thought that 1.6 wt% or less is suitable for the addition amount.

  Below, the marking method of this embodiment and the specific example of the marking which applied the ink are demonstrated based on Example 1 thru | or Example 4. FIG.

<Ink preparation conditions>
Inorganic pigment Cobalt-aluminum oxide Average particle size of inorganic pigment 50nm
Inorganic pigment concentration 20.3wt%
Dispersant addition amount 1.1wt%
Solvent Water: Anti-drying agent = 80: 20
Mixing conditions Ball mill, 3day
<Ink characteristics>
Apparent viscosity 7.5 mPa · s (HAKKE rotational viscometer VT-550: NV rotor, shear rate 2000 / s)
Surface tension 35mN / m (Kyowa Scientific surface tension meter ESB-V, well-helmy method)

  The prepared ink did not cause precipitation or phase separation even after long-term storage. Further, as a result of the same filtration test as described above, it was considered that the ink passed through the filter well, and the aggregation of the inorganic pigment particles did not occur. Using this ink, a cordierite shelf board (fired refractory) molded body (corresponding to a ceramic molded body) by a share type piezo-type inkjet printing machine (Affect KEGON) with a resolution of 360 dpi, The serial number as a mark was printed directly. The printing speed at this time was 100 mm / s, printing was performed 6 times, and the time required for one printing was about 2 seconds. No nozzle clogging occurred during printing, and ink jet printing could be performed satisfactorily. The shelf-shaped molded body on which the mark was printed was fired at 1350 ° C. for 1 hour to obtain a blue colored mark. Further, even when the fired shelf board (corresponding to a ceramic sintered body) was used at 1250 ° C., there was no problem such as disappearance of the mark.

<Ink preparation conditions>
Inorganic pigment Cobalt-iron-aluminum oxide Average particle size of inorganic pigment 50 nm
Inorganic pigment concentration 22wt%
Dispersant addition amount 0.7wt%
Solvent Water: Anti-drying agent = 80: 20
Mixing conditions Ball mill, 3day
<Ink characteristics>
Apparent viscosity 13.5 mPa · s (HAKKE rotational viscometer VT-550: NV rotor, shear rate 2000 / s)
Surface tension 34mN / m (Kyowa Scientific surface tension meter ESB-V, well-helmy method)

  The prepared ink did not cause precipitation or phase separation even after long-term storage. Further, as a result of the same filtration test as described above, it was considered that the ink passed through the filter well, and the aggregation of the inorganic pigment particles did not occur. Using this ink, the production number as a mark was directly printed on a cordierite shelf molded body by the same ink jet printer as in Example 1. The printing speed at this time was 200 mm / s, printing was performed 8 times, and the time required for one printing was about 1.5 seconds. No nozzle clogging occurred during printing, and ink jet printing could be performed satisfactorily. By baking the molded body of the shelf board on which the mark was printed at 1350 ° C. for 1 hour, a mark colored in a slightly brownish black was obtained. Further, even when the fired shelf board was used at 1250 ° C., there was no problem such as disappearance of the mark.

  Using the same ink as in Example 2, the barcode and two-dimensional symbol as a mark were directly printed on an alumina molded body (corresponding to a ceramic molded body) by the same inkjet printer as in Example 1. The printing speed at this time was 100 mm / s, printing was performed 6 times, and the time required for one printing was about 2 seconds. The nozzle 7 was not clogged during printing, and ink jet printing could be performed satisfactorily. The alumina molded body on which the mark was printed was baked at 1550 ° C. for 1 hour, but a slight blue bleed due to diffusion was observed, but a dark bar code and a two-dimensional symbol that developed a bluish black color. was gotten. Even when this alumina sintered body (corresponding to a ceramic sintered body) was used at 1500 ° C., there was no problem such as disappearance of the mark.

<Ink preparation conditions>
Inorganic pigments Holmium oxide Average particle size of inorganic pigments 60nm
Inorganic pigment concentration 26wt%
Dispersant addition amount 0.6wt%
Solvent Water: Anti-drying agent = 87: 13
Mixing conditions Ball mill, 3day
<Ink characteristics>
Apparent viscosity 5.7 mPa · s (HAKKE rotational viscometer VT-550: NV rotor, shear rate 2000 / s)
Surface tension 34mN / m (Kyowa Scientific surface tension meter ESB-V, well-helmy method)

  The prepared ink did not cause precipitation or phase separation even after long-term storage. Further, as a result of the same filtration test as described above, the ink passed through the filter well, and aggregation of inorganic pigment particles was not confirmed. Using this ink, the barcode and the two-dimensional symbol were directly printed on the alumina molded body by the same ink jet printer as in Example 1. The printing speed at this time was 100 mm / s, printing was performed 6 times, and the time required for one printing was about 2 seconds. No nozzle clogging occurred during printing, and ink jet printing could be performed satisfactorily. The alumina molded body on which the mark was printed was baked at 1550 ° C. for 1 hour to obtain a yellow-colored barcode and a two-dimensional symbol. At this time, no color bleeding due to diffusion was observed. Even when the obtained alumina sintered body was used at 1500 ° C., there was no problem such as disappearance of the mark. In addition, the mark of the present Example exhibited yellow under sunlight or an incandescent lamp, and exhibited a clear pink color under a three-wavelength fluorescent lamp.

  In the above-described embodiment, the case where the porous ceramic molded body 10 is used as a printing target is illustrated, but a dense ceramic molded body or ceramic sintered body can also be used as a printing target. In this case, when an ink using an aqueous solvent is applied, the dense substrate is poor in water absorption, and the printed mark is likely to bleed. For this reason, by previously coating the surface of the substrate with a water-absorbing material such as silica gel or PVA, the printed ink is absorbed, and even if printing is performed at high speed, bleeding does not easily occur. By doing so, for example, the ceramic body can be marked with an ink using an inorganic pigment that develops color at a temperature lower than the firing temperature of the ceramic body. Below, the specific example which marks a ceramic sintered compact is demonstrated based on Example 5. FIG.

<Ink preparation conditions>
Inorganic pigment Antimony-tin oxide Average particle size of inorganic pigment 30nm
Inorganic pigment concentration 34.0wt%
Addition amount of dispersant 0.1wt%
Solvent Water: Anti-drying agent = 85: 15
Mixing conditions Ball mill, 3day
<Ink characteristics>
Apparent viscosity 8.8 mPa · s (HAKKE rotational viscometer VT-550: NV rotor, shear rate 2000 / s)
Surface tension 35mN / m (Kyowa Scientific surface tension meter ESB-V, well-helmy method)

  The prepared ink did not cause precipitation or phase separation even after long-term storage. Further, as a result of the same filtration test as described above, it was considered that the ink passed through the filter well, and the aggregation of the inorganic pigment particles did not occur. Using this ink, a barcode as a mark was directly printed on a dense alumina substrate (ceramic sintered body) by the same ink jet printer as in Example 1. At this time, the surface of the alumina substrate was previously coated with PVA so that the ink did not bleed onto the surface of the alumina substrate. The printing speed at this time was 100 mm / s, printing was performed four times, and the printing time for one time was about 2 seconds. No nozzle clogging occurred during printing, and ink jet printing could be performed satisfactorily. The alumina substrate on which the mark was printed was baked at 1200 ° C. for 1 hour to obtain a black colored mark. Even when this alumina substrate was used at 1200 ° C., there was no problem such as disappearance of the mark. In addition, the mark of a present Example has electroconductivity, and it was possible to supply with electricity.

  As shown in Example 1 to Example 5 above, any ink can be discharged well from the nozzles of an ink jet printer, and the cordierite-quality firing refractory, alumina molded body, or alumina substrate In addition, the mark could be directly ink-jet printed. Then, by firing at a high temperature of 1200 ° C. to 1550 ° C. thereafter, the mark was vividly colored and became a stable mark that did not disappear or fade even when used at a high temperature thereafter.

  In Example 3, some blurring of the mark was observed as described above. This is presumably because the atoms of the elements constituting the inorganic pigment diffused into the alumina because the alumina compact was fired at an extremely high temperature of 1550 ° C. On the other hand, as shown in Example 4, when holmium oxide was used as the inorganic pigment, the alumina molded body was baked at 1550 ° C. as the printing object as in Example 3. A clear mark free from bleeding due to diffusion was obtained. This was thought to be due to the fact that the ionic radius of the rare earth element was large, so that it was difficult to diffuse and dissolve in alumina. Other colored rare earth oxides such as praseodymium oxide, erbium oxide and neodymium oxide are also considered to be usable in the same manner.

  In addition, in Example 4 in which holmium oxide was used as the inorganic pigment, the marks after firing exhibited color rendering properties that produced different colors under light sources having different wavelengths. This is because the three-wavelength fluorescent lamp has a light emission peak near 540 nm, whereas holmium oxide has a large absorption peak near that wavelength, so that the green color is absorbed and the color becomes reddish. It is done. In this way, the yellow mark, which is difficult to see under sunlight or white light, emerges in a bright pink color when irradiated with a fluorescent lamp, so it is considered useful as a mark having a stealth function. It is done.

  Further, in Example 5, an antimony-tin oxide having a color development temperature of up to 1250 ° C., which is lower than that, is applied to an alumina sintered body usually fired at a high temperature of 1500 ° C. or higher. Could be used as a marking. Furthermore, since the obtained mark has conductivity, it is expected to develop into a new application by marking a ceramic body having electrical insulation. In addition, in Example 5, the inorganic pigment concentration was increased to 34.0 wt% by the addition of a dispersant having a low concentration of 0.1 wt%.

  The present invention has been described with reference to preferred embodiments. However, the present invention is not limited to these embodiments, and various modifications can be made without departing from the spirit of the present invention as described below. And design changes are possible.

  For example, the solvent for preparing the ink is not limited to the aqueous solvent shown in the present embodiment, and a non-aqueous organic solvent can also be used. Examples of such an organic solvent include aromatics such as toluene, xylene and benzene, polyhydric alcohols such as butyl alcohol, and acetone. It is also possible to use a UV curable resin solvent composed of an ultraviolet absorber or a photopolymerization initiator. In this case, since the ink is cured in a short time by ultraviolet irradiation, the marking can be speeded up. Further, since it is not necessary to dry the printed ink, it is possible to mark the dense ceramic body by directly discharging the ink. In addition, since the UV curable resin component disappears in the firing step, there is no fear of affecting the ceramic product after firing.

  Furthermore, the inorganic pigment is not limited to those exemplified in this embodiment. For example, iron oxide is desirable in that it has fewer problems with respect to the environment than inorganic pigments containing heavy metal elements such as cobalt, chromium, and manganese. Note that inorganic pigments using iron oxide are colored brown in an oxidizing atmosphere and black in a reducing atmosphere, and are suitable for marking light ceramic products.

It is a flowchart which shows the process in the marking method of one Embodiment of this invention. It is explanatory drawing which shows the outline | summary of the marking method of FIG. 1 typically. It is a graph which shows an example of the relationship between the inorganic pigment density | concentration of the ink of this embodiment, and an apparent viscosity. It is a graph which shows an example of the relationship between the dispersing agent density | concentration and the apparent viscosity of the ink of this embodiment.

Explanation of symbols

1 Marking Method 2 Ink 5 Computer 6 Head 7 Nozzle 10 Ceramic Molded Body (Ceramic Body)
11 Digital image 20 Ceramic sintered body 21 Mark

Claims (3)

  1. An inorganic pigment that develops color by firing at a temperature of 1000 ° C. or more and 1700 ° C. or less is contained in an amount of 15 wt% or more and 34 wt% or less with respect to the total composition amount. An ink preparation step of preparing an ink to which a dispersant of
    An image creation step of creating a mark including at least one of letters, numbers, symbols, designs, and identification codes as a digital image;
    An ink jet printing step of ejecting the ink based on the digital image and ink jet printing the mark on the ceramic body;
    And a firing step of firing the ceramic body on which the mark is inkjet printed at a temperature of 1000 ° C. or higher and 1700 ° C. or lower.
  2.   The marking method according to claim 1, wherein the inorganic pigment has an average particle diameter of 10 nm to 100 nm.
  3. Containing 15 wt% or more and 34 wt% or less of an inorganic pigment that develops color by firing at a temperature of 1000 ° C or more and 1700 ° C or less
    An ink, wherein a dispersant having a solid content of 0.1 wt% or more and 1.6 wt% or less is added to the inorganic pigment.
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KR101296245B1 (en) 2011-09-27 2013-08-13 (주) 더몰론코리아 Printing method using the ink for ceramic surface layers

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SE516696C2 (en) 1999-12-23 2002-02-12 Perstorp Flooring Ab Process for the production of surface elements which comprises a decorative upper layer and surface elements prepared determined in accordance with the method
JP6159173B2 (en) * 2013-06-27 2017-07-05 株式会社ミマキエンジニアリング Manufacturing method and printing apparatus for heat-resistant member with picture
JP2016043550A (en) * 2014-08-21 2016-04-04 株式会社ミマキエンジニアリング Inorganic pigment printing method
IT201600078993A1 (en) * 2016-07-27 2018-01-27 Salmon Trade Spare Parts And Services S R L Plant for the production of ceramic tiles

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JPH08253358A (en) * 1995-03-15 1996-10-01 Enogushiyou Yamaka Shoten:Kk Painting of ceramics, etc.
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JP2003246690A (en) * 2002-02-25 2003-09-02 Fuji Photo Film Co Ltd Method of manufacturing ceramic body with picture
JP4368640B2 (en) * 2002-08-23 2009-11-18 セーレン株式会社 Inkjet printing method on inorganic substrate
JP4075864B2 (en) * 2004-06-14 2008-04-16 株式会社Inax Decorative ceramic body, manufacturing method thereof and glaze preparation

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