• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention provides an inkjet ink with which a decorative part having a beautiful gloss can be accurately formed on an inorganic substrate. The inkjet ink disclosed herein contains: inorganic solids including an inorganic pigment and glass; and a photocurable monomer component. When the total volume of the inkjet ink is 100 vol%, the volume of the inorganic solids in the ink is at most 30 vol%, and when the total volume of the inorganic solids is 100 vol%, the volume of the glass is at least 78 vol%. Thereby, a beautiful image can be accurately depicted on an inorganic substrate while maintaining a high level of ejection properties and of gloss after firing.
    公开号:ES2858529A2
    申请号:ES202190049
    申请日:2019-12-27
    公开日:2021-09-30
    发明作者:Tomoshi Kumazawa；Hiromichi Hayashi；Yuuki Arakawa
    申请人:Noritake Co Ltd；
    IPC主号:
    专利说明:

    [0004] BACKGROUND OF THE INVENTION
    [0006] Technical field
    [0007] The present invention relates to an ink jet ink. Specifically, the present invention relates to an inkjet ink used for an inorganic base material to be baked. The present application claims the priority of Japanese Patent Application Laid-Open No. 2019-034700 filed on February 27, 2019, the full respective disclosure of which is incorporated herein by reference.
    [0009] Prior state of the art
    [0010] Conventionally, inkjet printing has been used as one of the printing methods for drawing a desired image, such as a pattern, a character, or the like, on a printing target. Inkjet printing is used in various fields because inkjet printing enables a high-precision image to be drawn by a simple and reasonable device. In recent years, the use of inkjet printing described above has been examined when drawing an image on an inorganic base material, such as a ceramic base material (for example, a ceramic, a ceramic tile), a glass base material, a metal base material or the like. Specifically, in the field of inorganic base material, conventionally, hand drawing, a plate printing or the like has been made by drawing a pattern, a character or the like. However, in view of the increased productivity, inkjet printing attracts attention because, unlike hand drawing, inkjet printing does not require specialized artisan techniques and, unlike plate printing, inkjet printing enables fast, on-demand printing.
    [0012] However, there is a wide scope for the improvement of inkjet printing in the field of inorganic base material. Because, it is difficult to apply an inkjet printing technique in other fields where paper, fabric or the like is a printing target in the field of inorganic base material as it is. For example, as for a product (inorganic product) that uses an inorganic base material, the Baking treatment is performed on an inorganic base material on which an image is drawn at 500 ° C or more (eg 500 ° C to 1200 ° C) in some cases. In this baking treatment, with the use of an inkjet ink used for paper, fabric or the like, there is a possibility that the pigments become discolored (or discolored) during the baking treatment. Therefore, an inkjet ink (inkjet ink for an inorganic base material) used for an inorganic base material to be baked must have a composition that considers baking. Examples of inkjet ink for an inorganic base material include the inks described in patent documents 1 and 2 or the like.
    [0014] A curved surface, recesses and protrusions, or the like, are formed on a surface of an inorganic base material that is a printing target in some cases. When trying to draw an image directly on a surface of an inorganic base material having a curved surface or the like, distortion of a line or the like occurs. As a result, the clarity of an image may be markedly reduced or the desired image may not be drawn. Therefore, when drawing an image on an inorganic base material having a curved surface or the like, a transfer paper can be used for an inorganic base material (which will also be referred to simply as "transfer paper" hereinafter). ). Specifically, the desired image is drawn on a transfer paper, the transfer paper is pasted while the transfer paper is curved according to the curved surface of the inorganic material or the like. As a result, the image of the transfer paper is transferred to the inorganic base material. When drawing an image on the transfer paper, screen printing has been used, but from the point of view of increasing productivity, the use of inkjet printing has been proposed in recent years. An example of a technique for forming transfer paper for an inorganic base material using inkjet printing is disclosed in Patent Document 3.
    [0016] LIST OF APPOINTMENTS
    [0017] PATENT DOCUMENT PATENT DOCUMENT 1: International Patent Publication No. W02007 / 80779
    [0018] PATENT DOCUMENT 2: Japanese Patent Publication Open for Public Inspection No. 2017-75251
    [0019] PATENT DOCUMENT 3: Japanese Patent Publication Open for Inspection Public # 2009-154419
    [0021] Brief description of the invention
    [0023] Problem to be solved by the invention
    [0024] As described above, in the field of inkjet ink for an inorganic base material, various inks have been proposed as described in patent documents 1 to 3. However, due to the increasing demand for quality of inorganic products in recent years, it is desired to develop an ink with which a more beautiful image can be drawn accurately.
    [0026] In view of the above, the present invention has been conceived, it is a primary object of the present invention to provide an ink for inkjet in which an image (decorative part) having a nice gloss can be accurately formed on a printing material. inorganic base. Another object of the present invention is to provide a method that enables an inorganic product having the decorative part to be stably produced (with excellent quality stability).
    [0028] Solution to the problem
    [0029] The present inventors focused on a glass component in an inkjet ink in order to form an image having a nice gloss on an inorganic base material. The glass component has the function of fixing an inorganic pigment on the surface of a base material by solidifying the glass component after being melted by firing. The present inventors conceived that by increasing the content of this glass, a surface of the inorganic pigment is suitably coated with the glass so that a nice gloss appears on the image after baking. However, when the content of the glass was actually increased, another problem arose in which the viscosity of the ink was greatly increased, the discharge performance of the discharge of an ink from an inkjet device was reduced, and it was difficult to draw an accurate image. In order to solve the problem described above, as a result of experiments and examinations repeatedly carried out by the present inventors, the present inventors found that an increase in the viscosity of the ink was not caused by an increase in the content of the glass but by a increase in the content of a complete inorganic solid part including the inorganic pigment and glass. Then, the present inventors found based on the finding that, with a total amount of the inorganic solid part relative to the total amount of ink removed to a certain amount or less, even When the content of the glass is increased, the viscosity of the ink can be kept at a low level. In addition, since there are many types of inorganic pigments and glass and their respective specific densities vary, the present inventors thought that it is not a "weight" of the inorganic solid part but a "volume" of the same that affects the viscosity of the ink, they came up with the idea of adjusting the respective amounts of the inorganic solid part and the glass in terms of volume percentage, and thus completed the present invention.
    [0031] An inkjet ink disclosed herein was designed based on the finding described above and is used for an inorganic base material on which it is to be based. Inkjet ink includes an inorganic solid part that includes an inorganic pigment and glass, and a monomer component that has light curability. In the inkjet ink disclosed herein, a volume of the inorganic solid part when the total volume of the inkjet ink is 100% by volume is 30% by volume or less, and a volume of the glass when the total volume of the inorganic solid part is 100% by volume is 78% by volume or more.
    [0033] As described above, in the inkjet ink disclosed herein, the content of the inorganic solid part in all the ink and the content of the glass in the inorganic solid part are appropriately adjusted in terms of volume. Therefore, according to the inkjet ink disclosed herein, gloss and discharge performance after baking can be achieved at a high level, and a beautiful image can be accurately drawn on the base material. inorganic.
    [0035] In a preferred aspect of the inkjet ink disclosed herein, the volume of the inorganic solid part when the total volume of the inkjet ink is 100% by volume is 5% by volume or more. Therefore, preferably, both gloss and color developing property can be achieved after baking.
    [0037] In a preferred aspect of the inkjet ink disclosed herein, the volume of the glass when the total volume of the inorganic solid part is 100% by volume is 91% by volume or less. Therefore, an image can be formed in which a preferable color development property is exhibited after baking.
    [0039] In a preferred aspect of the inkjet ink disclosed herein, the monomer component includes at least one monofunctional acrylate monomer that contains an acryloyl group or a methacryloyl group in a molecule, a monofunctional N-vinyl compound monomer in which a vinyl group is attached to a nitrogen atom (N) of a nitrogen-containing compound, and a polyfunctional monomer based on vinyl ether containing at least two vinyl ether groups in one molecule. Therefore, by using a photocurable monomer component including all three types of monomers, an image can be drawn which can be preferentially fixed on a surface of a printing target and which has excellent flexibility after fixing.
    [0041] In the aspect including the three types of monomers described above, a volume ratio of the monomer component when the total volume of the inkjet ink is 100% by volume is 44% by volume or more and 85% by volume. volume or less. Therefore, both a property of fixing to a surface of a printing target and flexibility after fixing can be achieved at a high level, and an image (decorative part) having an excellent gloss and a property of excellent color development after baking.
    [0043] In accordance with the present invention, there is provided a method for producing transfer paper for an inorganic base material used for an inorganic base material to be baked. The method of producing transfer paper for an inorganic base material includes depositing the ink for inkjet including the three types of monomers described above on the surface of a support by an inkjet device and irradiating the surface of the support with an ultraviolet ray to cure the ink for inkjet deposited on the surface of the support. According to the method for producing transfer paper for an inorganic base material, transfer paper can be produced for which a crack in an image (ink after curing) is preferably prevented from being generated when the transfer paper is curled.
    [0045] As another aspect of the present invention, a method of producing an inorganic product having a decorative part is provided. The method for producing an inorganic product includes depositing the inkjet ink disclosed herein on a surface of an organic base material and baking the inorganic base material in a condition where a higher baking temperature is established. within a range of 500 ° C to 1200 ° C. According to the method of producing an inorganic product, an inorganic product having a nice gloss and a precise decorative part (picture) can be produced.
    [0046] BRIEF DESCRIPTION OF THE DRAWINGS
    [0048] [FIG. 1] FIG. 1 is a cross-sectional view schematically illustrating a stirred sprayer used to produce an inkjet ink.
    [0050] [FIG. 2] FIG. 2 is a full view schematically illustrating an example of an ink jet device.
    [0052] [FIG. 3] FIG. 3 is a cross-sectional view schematically illustrating an ink jet head of the ink jet device of FIG. 2.
    [0054] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
    [0056] Preferred embodiments of the present invention will be described below. Note that matters other than those specifically mentioned in the present specification and necessary for the implementation of the present invention can be understood as design matters carried out by those skilled in the art, based on conventional technique in the field. The present invention can be implemented based on the contents disclosed in the present specification and general technical knowledge common in the field.
    [0058] 1. Inkjet ink
    [0059] An inkjet ink disclosed herein is an inkjet ink for an inorganic base material used for an inorganic base material to be baked. Inkjet ink includes at least an inorganic solid part and a monomeric component having photocurable (photocurable monomeric component). The inkjet ink components disclosed herein will be described below.
    [0061] (1) Inorganic solid part
    [0062] An inorganic solid part is a component that constitutes a base material of a printing layer (decorative part) after baking and includes an inorganic pigment and glass.
    [0064] (a) Inorganic pigment
    [0065] An inorganic pigment is added to develop a desired color on the surface of the base material after baking. The inorganic pigment can be an inorganic pigment that includes, for example, a metallic compound. Inorganic pigment has excellent heat resistance. Therefore, when the baking treatment at 500 ° C or more (for example, 500 ° C to 1200 ° C) is carried out on an inorganic base material with an ink deposited thereon, discoloration (or discoloration) of the pigment. Specific examples of the inorganic pigment include a composite metal compound that mainly contains at least one metal element selected from a group consisting of Cu, Mn, Zr, Ti, Pr, Cr, Sb, Ni, Co, Al, and Cd. In particular A compound metal oxide based on Zr (for example, ZrSi04) containing mainly Zr among these, can be preferably used from the viewpoint of heat resistance. For example, in general inkjet printing, inks of three colors, that is, cyan, yellow, and magenta, are combined to draw an image of a desired color. In a case where the above-described Zr-based composite metal oxide is used as an inorganic pigment, an inorganic pigment of each of the three colors described above can be obtained by doping a predetermined metal element to the Zr-based composite metal oxide. For example, ZrSi04-V (vanadium), ZrSi04-Pr (praseodymium) and ZrSi04-Fe (iron) are respective examples of a cyan colored Zr-based composite metal, yellow-colored Zr-based composite metal, and Magenta-colored Zr-based composite metallic, respectively.
    [0067] Depending on the inkjet device, in some cases, black and white inks are used in addition to the three colors described above. As the inorganic pigment used for black ink, for example, a composite metal compound based on FeCr (for example, spinel black) is preferably used. As the inorganic pigment used for the white color ink, for example, TIO2, ZrÜ2, ZnO, ZrSi04, or the like is preferably used.
    [0069] Note that, as an inorganic pigment in an inkjet ink disclosed herein, an inorganic pigment that can be used for an ink for an inorganic base material can be used without any particular limitation in a range in which the Effects of the present invention are not impaired, and the materials thereof are not limited to the materials described above.
    [0071] The inorganic pigment can normally be in particulate form. It is preferable that the particle diameter of the inorganic pigment in particle form is appropriately adjusted taking into account the diameter of a discharge port of an ink jet device which will be described later. When the particle diameter of the inorganic pigment is too large, the discharge port is likely to be clogged with the inorganic pigment, so that the ink discharge performance is likely to be reduced. The diameter of the general inkjet device is about 15 pm to 60 pm (for example 25 pm), and therefore it is preferable to spray the inorganic pigment so that the particle diameter D100 (maximum particle diameter) corresponding to 100% in cumulative number of a side where the particle diameter is less is 5 pm or less (preferably 1 pm or less). Note that, like the particle diameter D100 described above, a measured value based on the measurement of the particle size distribution by a dynamic light scattering method can be employed.
    [0073] The inorganic pigment can be inorganic particles distributed in a mixed state in the glass described below. The inorganic particles can be, for example, metallic nanoparticles. Examples of metallic nanoparticles include, for example, gold nanoparticles, silver nanoparticles, copper nanoparticles, platinum nanoparticles, titanium nanoparticles, palladium nanoparticles, or the like. Metallic nanoparticles have specific optical characteristics (eg, a strong photoabsorption band) for each from an ultraviolet region to a visible region due to surface plasmon resonance (SPR). For example, gold (Au) nanoparticles absorb light of a wavelength of around 530 nm (green light to light blue light) and have a bluish-red (red-violet) called "brown." Therefore, for example, in the case where a red or violet color ink is prepared, such as metallic nanoparticles, gold nanoparticles can be preferably used. As another example, silver (Ag) nanoparticles absorb light of a wavelength around 420 nm (blue light) and have a yellow color. Therefore, for example, in the case where an orange or yellow ink is prepared, such as metallic nanoparticles, silver nanoparticles can be preferably used.
    [0075] According to a preferred aspect, a particle diameter D5o of the metal nanoparticles is 5 nm or more, usually 100 nm or more, and, for example, 15 nm or more. According to another preferred aspect, a Dso particle diameter of the metal nanoparticles is about 80 nm or less, typically 50 nm or less, and, for example, 30 nm or less. By setting the particle diameter D5o in the range described above, an absorbance of a specific wavelength of the metal nanoparticles is increased, and an excellent color presentation can be achieved by adding inorganic particles in a small amount. Also, an accurate image can be drawn with little color unevenness.
    [0076] (b) Glass
    [0077] The glass melts when the inorganic base material is fired and solidifies by cooling thereafter, and thus the inorganic pigment described above is fixed on a surface of the base material. In the inkjet ink disclosed herein, such as glass, a material is used with which the inorganic pigment is coated after cooling and which causes a nice gloss to appear.
    [0079] Examples of glass that may have the properties described above include, for example, SÍO2-B2O3 based glass, SÍO2-RO based glass (RO is an oxide of a group 2 element, for example indicating MgO, CaO, SrO or BaO. The same applies hereinafter), SÍO2-RO-R2O2O is an oxide of an alkali metal element, for example, denoting LÍ2O, Na 20 , K2O, Rb2Ü, CS2O or Fr 20 . Specifically, glass based on LÍ2O. The same applies hereinafter), glass based on SÍO2-B2O3-R2O, glass based on SÍO2-RO-ZnO, glass based on Si 02 -R 0 -Zr 02 , glass based on SÍO2-RO-AI2O3, glass based in SÍO2-RO-BÍ2O3, glass based on SÍO2-R2O, glass based on Si 02 -Zn 0 , glass based on SÍO2-ZrÜ2, glass based on SÍO2-AI2O3, glass based on RO-R2O, glass based on RO-ZnO or similar. Note that these types of glass may contain, in addition to the main constituent components that appear in the names described above, one or two or more components. The glass can be crystallized glass containing crystals, as well as amorphous glass in general.
    [0081] In a preferred aspect, when all glass is 100% by mole, SIO2 occupies half (50% by mole) or more. A SIO2 ratio can be about 80% by mole or less. In the view of increasing the melting efficiency of the glass, a component, such as RO, R2O, B2O3, or the like, can be added. In a preferred aspect, when all glass is 100% by mole, RO occupies 0 to 35% by mole. In another preferred aspect, when all glass is 100% by mole, R2O occupies 0 to 10% by mole. In another preferred aspect, when all glass is 100% by mole, B2O3 occupies 0 to 30% by mole.
    [0083] Furthermore, in a preferred aspect, the glass is made up of multi-component glass containing four or more components (eg, five or more components). Therefore, physical stability increases. For example, a component, such as AI2O3, ZnO, CaO, ZrÜ2, or the like, can be added, for example, in a ratio of 1 mol% or more. Therefore, the chemical durability or wear resistance of the decorative part can be increased. On A preferred aspect, when all glass is 100% by mole, AI2O3 occupies 0 to 10% by mole. In a preferred aspect, when all glass is 100 mole%, Zr02 occupies 0 to 10 mole%.
    [0085] A preferred example of the glass disclosed herein is borosilicate glass having the following composition expressed in mole% in terms of oxide:
    [0086] SIO2 40 to 70% by mole (eg 50 to 60% by mole);
    [0087] B2O3 10 to 40% by mole (for example, 20 to 30% by mole);
    [0088] R2O (at least one of LÍ2O, Na20, K2O and Rb20) from 3 to 20% by moles (for example, from 5 to 10% by moles);
    [0089] AI2O3 from 0 to 20% by mole (for example, from 5 to 10% by mole);
    [0090] Zr02 from 0 to 16% by mole (for example, from 3 to 16% by mole);
    [0091] when all glass is 100% by mole. A ratio of SIO2 to a complete glass matrix of the borosilicate glass described above can be, for example, 40% by mole or more and usually 70% by mole or less, for example 65% by mole or less. A ratio of B2O3 to the entire glass matrix may be typically 10 mole% or more, for example 15 mole% or more, and usually 40 mole% or less, for example 35 mole% or less. A ratio of R2O to the entire glass matrix can be typically 3 mole% or more, for example 6 mole% or more, and usually 20 mole% or less, for example 15 mole% or less. In a preferred aspect, borosilicate glass contains, as R2O, LIO, Na20 and K2O. A ratio of LIO to the entire glass matrix can be, for example, 3 mole% or more and 6 mole% or less. A ratio of K2O to the entire glass matrix can be, for example, 0.5 mole% or more and 3 mole% or less. A ratio of Na20 to the entire glass matrix can be, for example, 0.5 mole% or more and 3 mole% or less. A ratio of AI2O3 to the entire glass matrix can be typically 3 mole% or more and typically 20 mole% or less, for example 15 mole% or less. A ratio of ZrÜ2 to the entire glass matrix can be usually 1% by mole or more and usually 10% by mole or less, for example 8% by mole or less.
    [0093] Furthermore, borosilicate glass may contain an additional component other than those described above. Examples of the additional component include, for example, BeO, MgO, CaO, SrO, BaO, ZnO, Ag20, TIO2, V2O5, FeO, Fe2Ü3, Fe3Ü4, CuO, CU2O, Nb20s, P2O5, La2Ü3, Ce02, BI2O3, Pb203, or similar in rust form. In general, borosilicate glass can contain the additional component in a ratio of 10% by mole or less in total when all glass is 100% by mole.
    [0094] Another example of the glass disclosed herein is glass whose 90 mole% or more has the following composition expressed in mole% in terms of oxide:
    [0095] SIO2 45 to 70% by mole (eg 50 to 60% by mole);
    [0096] Sn02 0.1 to 16% by mole (eg, 1 to 15% by mole);
    [0097] ZnO 1 to 15% by mole (eg, 4 to 10% by mole);
    [0098] RO (at least one of BeO, MgO, CaO, SrO and BaO) 15 to 35% by mole (eg 20 to 30% by mole);
    [0099] R2O (at least one of LÍ2O, Na20, K2O and RÓ2Ü) from 0 to 5% by moles (for example, from 1 to 15% by moles);
    [0100] B2O3 from 0 to 13% by mole (for example, from O to 1% by mole);
    [0101] when all glass is 100% by mole.
    [0103] A ratio of SIO2 to a complete glass matrix of the glass described above may be, for example, 50% by mole or more, and usually 65% by mole or less, for example, 60% by mole or less. A ratio of Sn02 to the entire glass matrix can be typically 0.5 mole% or more, for example 1 mole% or more, and usually 5.5 mole% or less, for example 5% by mole or less. A ratio of ZnO to the entire glass matrix can be typically 2 mole% or more, eg 4 mole% or more, and typically 12 mole% or less, eg 10 mole% or less. A ratio of RO to the entire glass matrix can be typically 18% by mole or more, for example 20% by mole or more, and usually 32% by mole or less, for example 30% by mole or less. An R 2 O ratio for the entire glass matrix can be about 0.1 mole% or more, for example 1 mole% or more, and, for example, 3 mole% or less. A ratio of B2O3 to the entire glass matrix can normally be 1% by mole or less and, for example, 0.1% by mole or less.
    [0105] Furthermore, the glass described above may contain an additional component other than those described above. Examples of the additional component include, for example, Ag20, AI2O3, ZrÜ2, TIO2, V2O5, FeO, Fe2Ü3, Fe3Ü4, CuO, CU2O, Nb20s, P2O5, La2Ü3, CeÜ2, BIO2O3, or the like in oxide form. In general, the glass can contain the additional component in a ratio of 10 mole% or less in total when all glass is 100 mole%.
    [0107] Note that it is preferable that a linear thermal expansion coefficient (average linear thermal expansion coefficient measured over a temperature region of 25 ° C to 500 ° C using a thermomechanical analyzer. The same applies below) of the glass is, for example, 4.0 x 10'6K'1 to 8.0 x 10'6K'1. Therefore, the difference in a shrinkage factor of a decoration target (inorganic base material) during baking is reduced, so that separation or cracking in the decorative part is less likely to occur. There is no particular limitation on the yield point of glass, but the yield point can be, for example, 400 ° C to 700 ° C. There is no particular limitation on a glass transition point (Tg value based on differential scanning calorimetry analysis. The same applies below) of glass, but the glass transition point can be, for example, 400 ° C at 700 ° C.
    [0109] The glass can normally be in the form of particles. A particle diameter of the particle-shaped glass affects the viscosity of the ink, and therefore, it is preferable to adjust the particle diameter appropriately taking into account the discharge performance of an ink from the inkjet device. Specifically, with the glass having a large particle diameter contained in the ink, the discharge port tends to clog and there is a likelihood that the discharge performance will be reduced. Therefore, it is preferable to control the particle diameter of the glass so that a maximum particle diameter (particle diameter D100 corresponding to 100% cumulative from a side where the particle diameter is smaller) of the glass is 1 pm or less (preferably 0.85 pm or less).
    [0111] (c) Content of the inorganic solid part
    [0112] In the inkjet ink disclosed herein, a volume ratio of the inorganic solid part when the total volume of the inkjet ink is 100% by volume is 30% by volume or less. The "volume of the inorganic solid part" refers to a total volume of the inorganic pigment and glass described above. There is a tendency that, as the volume of the inorganic solid part increases, the viscosity of the ink increases. Note that since there are various types of each of the inorganic pigment and glass contained in the inorganic solid part and the specific densities thereof vary, in this embodiment, the "volume" of the inorganic solid part, not a "weight" of it, it fits. As will be described in detail, in the inkjet ink disclosed herein, to make a nice gloss appear after baking, the content of the glass is increased. However, as described above, by making the volume ratio of the inorganic solid part to the total volume of the inkjet ink to be 30% by volume or less, the viscosity of the ink can be kept at a level low, although the content of the glass. Note that, from the viewpoint of reducing the viscosity of the ink and thus obtaining a more excellent discharge performance, the volume ratio of the inorganic solid part described above is preferably 28% by volume or less, plus preferably 25% by volume or less, even more preferably 23% by volume or less, and particularly preferably 20% by volume or less.
    [0114] Note that, from the viewpoint of achieving both an image brightness and a color development property after baking, a lower limit of the volume ratio of the inorganic solid part described above is preferably 1% by volume or more, more preferably 3% by volume or more, even more preferably 5% by volume or more, and in particular preferably 6% by volume or more.
    [0116] (d) Glass content
    [0117] As described above, in the inkjet ink disclosed herein, the ratio of glass volume to the total volume of the inorganic solid part is increased. Specifically, in the inkjet ink disclosed herein, the volume of the glass when the total volume of the inorganic solid part is 100% by volume is 78% by volume or more. Thus, an image (decorative part) can be formed which expresses a nice shine after baking. Note that, from a viewpoint of appearing a nice gloss, the volume ratio of the glass to the total volume of the inorganic solid part is preferably 80% by volume or more, more preferably 82% by volume or more, even more preferably 84% by volume or more, and particularly preferably 86% by volume or more. When the volume ratio of the glass increases too much, the content of the inorganic pigment is insufficient, and therefore, in the view of ensuring a preferable color developing property after baking, an upper limit of the volume ratio of the glass. glass is preferably 95% by volume or less, more preferably 93% by volume or less, even more preferably 91% by volume or less, and particularly preferably 90% by volume or less.
    [0119] As described above, in the inkjet ink disclosed herein, the volume ratio of the inorganic solid part to the total volume of the ink and the glass volume ratio to the total volume of the inorganic solid part are fit properly. Therefore, both a discharge property during printing and a gloss after baking can be achieved at a high level and thus a beautiful image. It can be accurately drawn on the inorganic base material.
    [0121] (2) Monomeric photocurable component
    [0122] The inkjet ink disclosed herein is a photocurable inkjet ink that contains a monomer component having photocurability. The "photocurable monomer component" in the present specification is typically liquid and refers to a material that contains at least one type of resin monomer component that polymerizes (lattice) and cures when irradiated with light (eg, a ray ultraviolet). As the photocurable monomer component, a monomer which can be used for a general photocurable ink can be used without any particular limitation in a range in which the effects of the present invention are not markedly altered.
    [0124] Preferred examples of the photo-curable monomer component include a photo-curable monomer component that includes (a) a monofunctional acrylate-based monomer, (b) a monofunctional N-vinyl compound monomer, and (c) a multi-functional vinyl ether-based monomer. The photocurable monomeric component, including the monomers of points (a) to (c) described above, has excellent fixation property (photocurability) to a printing target and therefore can be preferably used for various printing targets. . The photocurable monomer component including the monomers of (a) to (c) described above also has the advantage of excellent flexibility after photocuring and can therefore be used particularly preferably for a printing objective (for example, transfer paper for an inorganic base material) that needs to be curled when used.
    [0126] (a) Acrylate-based monofunctional monomer
    [0128] The acrylate-based monofunctional monomer is a compound that contains an acryloyl group (CH2 = CHCOO-) or methacryloyl group (CH2 = CCH3COO-) in one molecule.
    [0130] Because the monofunctional acrylate-based monomer is excellent in dispersibility of the inorganic solid part and an increase in ink viscosity can be suppressed, the monofunctional acrylate-based monomer can contribute to the preparation of an ink having a property discharge preferable. The monofunctional acrylate-based monomer has the characteristic of having relatively low hardness (high flexibility) after light curing among the monomers having light curability.
    [0131] Note that, from the viewpoint of further increasing the discharge property and flexibility, a volume ratio of the monofunctional acrylate-based monomer when a total volume of the photocurable monomer component is 100% by volume is preferably 40% in volume or more, more preferably 45% by volume or more, even more preferably 50% by volume or more, and particularly preferably 55% by volume or more, for example 60% by volume or more . On the other hand, the monofunctional acrylate-based monomer tends to have a relatively low photocurability and, therefore, in the view of ensuring a content of a monomer excellent in photocurability, which will be described later, the volume ratio of the monofunctional acrylate-based monomer is preferably 96% by volume or less, more preferably 90% by volume or less, even more preferably 85% by volume or less, and particularly preferably 80% by volume or less , for example, 78% by volume or less.
    [0133] Specific examples of the monofunctional acrylate-based monomer include, for example, benzyl acrylate, cyclic trimethylolpropane formal acrylate, phenoxyethyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, methoxyethyl acylate, cyclic acrylate acrylate, cycloheolbitol acrylate. (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methyl (meth) acrylate, ethylacrylate, propyl acrylate, acrylate butyl, pentyl acrylate, n-stearylacrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( 2-hydroxybutyl meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isoamyl acrylate, lauryl (meth) acrylate, octyl acrylate, isooctyl, isononyl acrylate, decyl acrylate, acri isodecyl late, tridecyl (meth) acrylate, isomistyl acrylate, isostearyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl-diglycol acrylate, 4-hydroxybutyl acrylate, methoxydiethyleneglycol acrylate, acrylate methoxydiethyleneglycol , 2- (2-ethoxyethoxy) ethyl acrylate, 2-ethylhexylcarbitol acrylate, phenoxyethoxyethyl acrylate or the like. One type of the (meth) acrylate compounds described above can be used alone or two or more types of the (meth) acrylate compounds described above can be used in combination. Among these, benzyl acrylate, phenoxyethyl acrylate and cyclic trimethylolpropane formal acrylate are particularly excellent in flexibility after light curing, and therefore, preferably, the generation of cracks can be prevented when the transfer paper is curled.
    [0135] (b) Monofunctional N-vinyl compound monomer
    [0136] A monofunctional N-vinyl compound monomer is a compound in which a vinyl group is attached to a nitrogen atom (N) of a nitrogen-containing compound. As used herein, the "vinyl group" refers to CH2 = CR1- (herein, R1 is a hydrogen atom or an organic group). The monofunctional monomer of N-vinyl compound has a high stretchability, and therefore the generation of a crack in a drawn image can be suppressed. The monofunctional N-vinyl compound monomer has excellent photocurability and has the function of increasing the surface fixing property of a printing target.
    [0138] Note that, from the viewpoint of further increasing the fixing property, a volume ratio of the monofunctional monomer of N-vinyl compound when the total volume of the photocurable monomer component is 100% by volume is preferably 2% in volume or more, more preferably 3% by volume or more, even more preferably 4% by volume or more, and in particular preferably 5% by volume or more. On the other hand, there is a tendency that when the monofunctional monomer of N-vinyl compound is added, the flexibility of the ink after curing is reduced. Therefore, in the case that the transfer paper for an inorganic base material is a printing target, the content of the monofunctional N-vinyl compound monomer is preferably small. In view of the above, the volume ratio of the monofunctional monomer of the N-vinyl compound is preferably 20% by volume or less, more preferably 17% by volume or less, even more preferably 15% by volume or less, and particularly preferably 13% by volume or less, for example 10% by volume or less.
    [0140] The N-vinyl compound monomer is represented, for example, by the following general formula (1).
    [0141] [Formula 1]
    [0142] CH2 = CR1-NR2R3
    [0144] In the above general formula (1), R1 is a hydrogen atom, an alkyl group of carbon number 1 to 4, a phenyl group, a benzyl group, or a halogen group. Among them, the hydrogen atom and the alkyl group of the number of carbon atoms 1 to 4 are preferable, and the hydrogen atom is particularly preferable. Each of R2 and R3 may be a group selected from a group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an alkoxy group, a alkoxy alkyl group, an alkylol group and an acetyl group (CH3CO-) each of which may have a substituent and an aromatic group. Note that R2 and R3 can be the same and can be different from each other. A total number of carbon atoms in the alkyl group, alkenyl group, alkynyl group, aralkyl group, alkoxy group, alkoxy alkyl group, alkylol group, and acetyl group, each of which may have a substituent , it can be from 1 to 20. The alkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the alkoxy group, the alkoxy alkyl group, the alkylol group and the acetyl group can be chain groups or cyclic groups, and they are preferably chain groups. The aromatic group can be an aryl group that can have a substituent. The total number of carbon atoms in the aromatic group is from 6 to 36. Examples of the substituent that each of the alkyl group, alkenyl group, alkynyl group, aralkyl group, alkoxy group, alkoxy alkyl group, alkylol group , the acetyl group and the aromatic group may possibly include, for example, a hydroxyl group, and a halogen atom, such as, a fluorine atom, a chlorine atom or the like. In the general formula (1) above, R2, and R3 can be joined together to form a cyclic structure.
    [0146] Preferred examples of the monofunctional N-vinyl compound monomer include N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-ninyl-3-morpholinone, N-vinyl piperidine, N-vinyl pyrrolidine, N-vinyl aziridine, N-vinyl azetidine, N-vinyl imidazole, N-vinyl morpholine, N-vinyl pyrazole, N-vinyl valerolactam, N-vinylcarbazole, N-vinyl phthalimide, N-vinyl formamide, N-vinyl acetamide, N-methyl- N-vinyl formamide, N-methyl-N-vinyl acetamide, or the like. Among them, N-vinyl-2-caprolactam has a high photocurability among monomers of monofunctional N-vinyl compounds, and can preferably enhance the surface-fixing property of a printing target.
    [0148] (c) Multifunctional monomer based on vinyl ether
    [0150] A vinyl ether-based multifunctional monomer is a compound that contains at least two vinyl ether groups in one molecule. As used herein, the "vinyl ether group" refers to -0-CH = CHR1 (where R1 is a hydrogen atom or an organic group). Multifunctional vinyl ether-based monomer containing at least two vinyl ether groups has a high light curing rate when irradiated with UV rays and has excellent light curing and thus has the function of increasing the fixing property to a surface. of a print target. Furthermore, the vinyl ether-based multifunctional monomer has a low hardness after light curing among the monomers having excellent light curing and excellent flexibility.
    [0151] Note that, from the viewpoint of achieving both the property of fixing to a printing target and flexibility after light curing, a volume ratio of the multifunctional monomer based on vinyl ether when the total volume of the monomeric component is 100% in volume is preferably 2% by volume or more, more preferably 5% by volume or more, even more preferably 7% by volume or more, and particularly preferably 10% by volume or more, for example, 15% by volume or more. On the other hand, there is a tendency that when the vinyl ether-based multifunctional monomer is added in excess, a further amount of the monofunctional acrylate-based monomer is reduced and the flexibility after light curing is reduced. Therefore, an upper limit of the volume ratio of the vinyl ether-based multifunctional monomer is preferably 40% by volume or less, more preferably 35% by volume or less, even more preferably 30% by volume or less, and particularly preferably 25% by volume or less, for example 20% by volume or less.
    [0153] Preferred examples of the vinyl ether based multifunctional monomer include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, dipropylene glycol divinyl ether, , polypropylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonadiol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether or the like. Among these, diethylene glycol divinyl ether, triethylene glycol divinyl ether and 1,4-cyclohexane dimethanol divinyl ether can achieve both the surface fixing property of a base material and flexibility after light curing at a high level, and thus therefore, they are particularly preferred.
    [0155] Note that in the case where the photocurable monomer component containing the monomers of (a) to (c) described above is used, a volume ratio of the monomer component when the total volume of the inkjet ink is 100 % by volume is preferably 44% by volume or more, more preferably 45% by volume or more, even more preferably 50% by volume or more, and particularly preferably 55% by volume or more. Therefore, the property of fixing to a surface of a printing target and the flexibility after fixing can be achieved to a higher level. Furthermore, from the viewpoint of ensuring sufficiently a content of the inorganic solid part and forming an image (decorative part) excellent in brightness and color development performance, the volume ratio of the monomer component is preferably 85% by volume or less, more preferably 80% by volume or less, even more preferably 75% by volume or less and, in particular, preferably 70% by volume or less.
    [0157] (d) Other monomers
    [0159] Note that, as described above, as the photocurable monomer component in the inkjet ink disclosed herein, a monomer component that can be used for a general photocurable inkjet ink can be used without any particular limitation. , and the photocurable monomer component is not limited to the monomers of (a) to (c) described above.
    [0161] An example of monomers other than (a) to (c) described above is a multifunctional acrylate-based monomer containing at least two acryloyl groups or methacryloyl groups in one molecule. Preferred examples of the multifunctional acrylate-based monomer include 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, tricyclodecane dimethanol diacrylate , hydroxypivalic acid diacrylate neopentyl glycol, triethylene glycol di (meth) acrylate, tetramethylene di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate , neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, di (meth) acrylate 1,4-cyclohexanediol, tetraethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene di (meth) acrylate, adduct diacrylate 3.8 molar bisphenol AEO, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethyloloct tri (meth) acrylate ano, pentaerythritol tri (meth) acrylate, polyethoxytrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol propionic acid tri (meth) acrylate, tris- (2-hydroxyethyl) tri (meth) acrylate , sorbitol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol polypropoxy tetra (meth) acrylate, sorbitol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate Propionic acid, ethoxylated pentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, or the like.
    [0163] Examples of other monomers other than the multifunctional acrylate-based monomer include butylvinyl ether, butylpropenyl ether, butylbutenyl ether, hexylvinyl ether, ethylhexylvinyl ether, phenylvinyl ether, benzylvinyl ether, phenylallyl ether, vinyl acetate, acrylamide, methacrylamide, trimethylolpropane, tri ((meth) acryloxyl ether acryloxypropyl, tri ((meth) (methyl) ether acryloxypropyl bisphenol A acrylic acid diglycidyl ether adduct, or the like.
    [0165] Note that it is not intended to limit the technology disclosed herein, but in the view of achieving an ink in which photocurability and flexibility at a high level have been achieved, it is preferable that the photocurable monomer component does not contain substantially the other monomers described above and the photocurable monomer component containing only the monomers described above from (a) to (c) is used. Note that "the photocurable monomer component does not contain substantially the other monomers" in the foregoing means that the other monomers are not intentionally added to the photocurable monomer component. Therefore, a case where a small amount of a component that can be considered as the other monomers, is inevitably contained because a raw material, a manufacturing process or the like is included in the concept that "the monomeric component The photocurable does not contain substantially the other monomers "in the present specification. For example, in a case where the volume ratio of the other monomers is 1% by volume or less (preferably 0.1% by volume or less, more preferably 0.01% by volume or less, even more preferably 0.001% by volume or less, and particularly preferably 0.0001% by volume or less), "the photocurable monomer component does not contain substantially the other monomers and is constituted solely by the monomers of (a) a (c) described above. "
    [0167] (3) Other components
    [0168] The inkjet ink disclosed herein may further contain a known additive (eg, a dispersant, a photopolymerization initiator, a polymerization inhibitor, a binder, a viscosity modifier, or the like) that can be used for an inkjet ink (typically an inkjet ink for an inorganic base material and a photocurable inkjet ink) as necessary in a range where the effects of the present invention are not affected . Note that the content of the additive can be suitably set according to the purpose of addition and does not characterize the present invention, and therefore the detailed description thereof will be omitted.
    [0169] (a) Dispersant
    [0171] The inkjet ink disclosed herein may contain a dispersant. As a dispersant, for example, a cationic dispersant is used. The cationic dispersant effectively adheres to an inorganic pigment surface due to an acid-base reaction, and therefore, unlike other dispersants, such as a phosphoric acid dispersant or the like, the agglomeration of the inorganic pigment and the Inorganic pigment can be preferably dispersed. An example of a cationic dispersant is an amine-based dispersant. The amine-based dispersant can prevent agglomeration of the inorganic pigment due to a steric barrier and can also stabilize the inorganic pigment. Furthermore, the amine-based dispersant can give the same fillers to the inorganic pigment particles, and therefore, at this point also, it can preferably prevent agglomeration of the inorganic pigment. Therefore, the viscosity of the ink can preferably be lowered to greatly increase the printability. Examples of the amine-based dispersant include a fatty acid amine-based dispersant, a polyester-amine-based dispersant, or the like, and, for example, DISPERBYK-2013 manufactured by BYK Japan KK or the like can be preferably used.
    [0173] (b) Light-curing initiator
    [0175] The inkjet ink disclosed herein may contain a photopolymerization initiator. As the photopolymerization initiator, a conventionally used photopolymerization initiator can be appropriately selected. An example of the photopolymerization initiator is, for example, a radical photopolymerization initiator, such as an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator or the like. As an alkylphenone-based photopolymerization initiator, for example, a photopolymerization initiator based on α-aminoalkylphenone (for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholin) phenyl] -1-butanone or the like) they can be used preferably. As another example of the alkylphenone-based photopolymerization initiator, a photopolymerization initiator based on α-hydroxyalkylphenone (1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, or the like).
    [0176] Among the various photopolymerization initiators described above, the α-aminoalkylphenone-based photopolymerization initiator, such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one or the like can exhibit high reactivity to increase the rate. ink curing property, it has excellent thin film curing property and surface curing property, and therefore can be used particularly.
    [0178] (c) Polymerization inhibitor
    [0180] The inkjet ink disclosed herein may contain a polymerization inhibitor. By adding the polymerization inhibitor, the polymerization and curing of the photocurable monomer component can be suppressed before use, and thus storage of the ink can be facilitated. As a polymerization inhibitor, a polymerization inhibitor conventionally used in the field of photocurable inkjet ink can be used without any particular limitation in a range in which the photocurability of the photocurable monomer component containing the monomers of (a ) to (c) described above is not noticeably affected, and inorganic pigments are not limited to the materials described above. Examples of the polymerization inhibitor include, for example, hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosoamine salt, or the like. Among the compounds included above, the aluminum salt and N-nitrophenyl hydroxylamine has excellent long-term storage stability and is particularly preferable.
    [0182] 2. Preparing the ink for inkjet
    [0183] Next, the preparation (production) methods of the ink jet ink described herein will be described. The inkjet ink disclosed herein can be prepared by cracking and dispersing the inorganic solid part after mixing the raw materials described above in a predetermined ratio. FIG. 1 is a cross-sectional view schematically illustrating a stirred sprayer used to produce an inkjet ink. Note that the following description is not intended to limit the inkjet ink disclosed herein.
    [0185] In producing the inkjet ink disclosed herein, first, the raw materials described above are weighed and mixed to prepare a suspension which is a precursor to the ink.
    [0186] Next, using a stirred sprayer 100 illustrated in FIG. 1, the suspension is stirred and the inorganic solid part (the inorganic pigment and the glass) is sprayed. Specifically, after adding beads (eg, zirconia beads with a diameter of 0.5 mm) to pulverize the suspension described above, the suspension is supplied to a stirring vessel 120 through a supply port 110 A shaft 134 having a plurality of stirring blades 132 is housed in stirring vessel 120. One end of shaft 134 is attached to a motor (not shown), the motor is driven to cause shaft 134 to rotate and thereby Therefore, the suspension is stirred by the plurality of stirring blades 132 while the suspension is sent to a downstream side of a liquid feed direction A. While the suspension is stirred, the inorganic solid part is pulverized by the beads to its pulverization added to the suspension and the atomized inorganic solid part is dispersed in the suspension.
    [0188] Then, the suspension sent to the downstream side in the liquid feed direction A passes through a filter 140. Therefore, the beads for spraying and a part of the inorganic solid part that has not been atomized are collected by the filter. 140 and the ink for inkjet in which the atomized inorganic solid part is sufficiently dispersed is discharged from an exhaust port 150. By setting an orifice diameter of the filter 140 at this time, a maximum particle diameter of the filter can be controlled. inorganic solid part in inkjet ink.
    [0190] 3. Application of inkjet ink
    [0191] Next, the application of the ink jet ink described herein will be described. As described above, the inkjet ink disclosed herein is used for an inorganic base material to be baked. In the present specification, "used for an inorganic base material" is a concept that includes not only a mode in which ink is deposited directly onto a surface of an inorganic base material, but also a mode in which that the ink is indirectly deposited on the surface of the inorganic base material by means of transfer paper or the like. That is, the inkjet ink disclosed herein can be used for printing on transfer paper for an inorganic base material (producing transfer paper) or printing on a surface of an inorganic base material (producing the material inorganic base).
    [0193] (1) Production of transfer paper
    [0194] Using the inkjet ink disclosed herein, a method for producing transfer paper for an inorganic base material (a printing method for drawing an image on a transfer paper surface) will be described. FIG. 2 is a full view schematically illustrating an example of an ink jet device. FIG. 3 is a cross-sectional view schematically illustrating an ink jet head of the ink jet device of FIG. 2.
    [0196] The ink jet ink disclosed herein is stored in an ink jet head 10 of an ink jet device 1 illustrated in FIG. 2. The inkjet device 1 includes four inkjet heads 10 and inks of four different colors, that is, black (K), cyan (C), yellow (Y) and magenta (M), are stored in the ink jet heads 10, respectively. The ink jet heads 10 are housed in a print cartridge 40. The print cartridge 40 is inserted into a guide axis 20 and is configured to alternate along an axial direction X of the guide axis 20. Although not illustrated, the ink jet device 1 includes a movable device that moves the guide axis 20 in a Y direction perpendicular to the guide axis 20. Therefore, ink can be discharged from the ink jet heads 10 to a predetermined position on a transfer paper holder W.
    [0198] A piezoelectric type inkjet head illustrated in FIG. 3 is used for the inkjet heads 10 illustrated in FIG. 2. Each of the piezoelectric type inkjet heads 10 is provided with a storage section 13 which stores the ink in a housing 12, and the storage section 13 communicates with a discharge section 16 through a liquid feed path 15. In the discharge section 16, a discharge port 17 open to the outside of the housing 12 is provided and a piezoelectric element 18 is arranged so that it is opposite the discharge port 17. In the ink jet head 10, the vibrating the piezoelectric element 18, the ink in the discharge section 16 is discharged to the holder W (see FIG. 2) from the discharge port 17.
    [0200] A UV irradiation device 30 is attached to the guide shaft 20 of the ink jet device 1 illustrated in FIG. 2. The UV irradiation device 30 is arranged next to the print cartridge 40, moves according to the reciprocating movement of the print cartridge 40, and irradiates the support W with the ink deposited on it with an ultraviolet ray. Therefore, the ink cures immediately after the ink is deposited in a surface of the W holder, and therefore ink with a sufficient thickness can be fixed on the surface of the transfer paper (W holder).
    [0202] As described above, in the inkjet ink disclosed herein, a volume of the inorganic solid part to the total volume of the inkjet ink is set to 30% by volume or less. Therefore, the viscosity of the ink can be kept low, and therefore the ink can be discharged from the discharge port 17 with high precision to allow an accurate image to be drawn on a surface of a printing target (transfer paper in this case).
    [0204] It is preferable to use the photocurable monomer component containing the monomers of (a) to (c) described above to produce the transfer paper described above. Therefore, an image (cured ink) can be drawn having sufficient flexibility, and therefore, preferably, generation of a crack in the image can be prevented when the transfer paper is curled.
    [0206] (2) Inorganic product production method
    [0207] Next, using the inkjet ink disclosed herein, a method of producing an inorganic product. The production method includes depositing the inkjet ink disclosed herein on a surface of an inorganic base material and baking the inorganic base material.
    [0209] There is no particular limitation on a raw material of the inorganic base material used in the production method of an inorganic product, a raw material that can be used as a general raw material for an inorganic base material can be used without any particular limitation. As an example of the inorganic base material, an inorganic base material, such as a ceramic base material, that is, for example, a ceramic, a ceramic tile or the like, a glass base material, a metal base material. or similar, to be baked.
    [0211] In the production method disclosed herein, first, the ink jet ink is deposited on a surface of an inorganic base material. There is no particular limitation on a device used to deposit the ink on the inorganic base material. The ink can be deposited directly on the surface of the inorganic base material using an ink jet device and the ink can be indirectly deposited on the surface of the inorganic base material by means of the transfer paper described above. Note that in the case where the ink is directly deposited by the inkjet device, it is preferable to discharge the ink to the surface of the inorganic base material according to the same procedures as those of "transfer paper production" previously described.
    [0213] In the production method disclosed herein, below, the inorganic base material with the ink deposited thereon is baked in a condition where the highest baking temperature is set in a range from 500 ° C to 1200 ° C (preferably 500 ° C to 1000 ° C, more preferably 600 ° C to 900 ° C). Thus, a resin component in which the monomers have been cured is burned, and the glass of the inorganic solid part is melted. Then, by cooling the inorganic base material after firing, the molten glass solidifies and the inorganic pigment is fixed to the surface of the base material. At this time, in the inkjet ink disclosed herein, the volume of the glass to the total volume of the inorganic solid part is adjusted to be 78% by volume or more, and therefore the pigment inorganic is coated with a sufficient amount of glass. Therefore, a nice shine can be made to appear on the decorative part (picture) after baking.
    [0215] [Test examples]
    [0217] Test examples related to the present invention will be described below, but it is not intended to limit the present invention to test examples.
    [0219] <Inkjet ink>
    [0220] Twenty-four inkjet inks (Example 1 to 24) were prepared containing the inorganic solid part and the photocurable monomer. Specifically, suspensions were prepared by mixing raw materials in the volume ratios indicated in Tables 1 to 3 and cracking and dispersion processing was performed using the beads (zirconia beads having a diameter of 0.5 mm) for the spraying, thus obtaining the inks of Examples 1 to 25. Note that the volume ratios in the tables are values in a case where the total volume of each of the inks is 100% by volume, unless otherwise indicated. opposite in the tables. In the test examples, in addition to the inorganic solid part and the photocurable monomer, a dispersant (DISPERBYK-2013 manufactured by BYK Japan KK), a photopolymerization initiator (Omnirad 819 manufactured by IGM RESINS) and an inhibitor of the polymerization (Q-1301 (N-nitroso-N-phenylhydroxylamine aluminum) manufactured by FUJIFILM Wako Puré Chemical Corporation). The volume ratios of dispersant, initiator, and inhibitor are also listed in Tables 1 to 3.
    [0222] Note that, for the inorganic solid portion used in the test examples, "yellow" in Tables 1 to 3 is a zirconium (praseodymiozirconium) based inorganic yellow pigment. "Cyan" is a zirconium (vanadium-zirconium) based inorganic cyan pigment. "Black" is a spinel-based black inorganic pigment (spinel black). The "glass" is borosilicate glass whose softening point is 550 ° C.
    [0224] The "light cure component" in Tables 1 to 3 is a component obtained by mixing isobornyl acrylate-based monofunctional monomer (manufactured by Osaka Organic Chemical Industry LTD.), Benzyl acrylate (manufactured by Osaka Organic Chemical Industry LTD. .), phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry LTD.), cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry LTD.); the N-vinyl compound monofunctional monomer of N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.); the multifunctional monomer based on triethylene glycol divinyl ether (manufactured by Nippon Carbide Industries Co., Inc.), diethylene glycol divinyl ether (manufactured by Nippon Carbide Industries Co., Inc.), triethylene glycol divinyl ether and 1,4-cyclohexane dimethanol (manufactured by Nippon Carbide Industries Co., Inc.); and the 1,9-nonanediol acrylate acrylate-based multifunctional monomer (manufactured by Osaka Organic Chemical Industry LTD.) in a predetermined volume ratio.
    [0226] <Assessment test>
    [0228] (1) Evaluation of ink viscosity
    [0229] The ink viscosity of each of the prepared examples was measured using a type B viscometer. Note that the ink temperature in the measurement was set at 25 ° C and the rotational speed of a spindle was set at 5 rpm. . A reference viscosity with which the ink could preferably be discharged from the inkjet device was set to be less than 70 mPa-s, samples that met the reference viscosity were evaluated as "pass" and samples that did not. met the reference viscosity were evaluated as "not passed". The results of the evaluation are indicated in Tables 1 to 3.
    [0231] (2) Gloss evaluation
    [0232] The ink from each of the samples described above was irradiated with a UV beam while being discharged to the surface of a support (manufactured by Marushige Shiko Co., Ltd.) using the inkjet device (MATERIAL PRINTER (DMP-2831 ) manufactured by FUJIFILM Corporation), thus producing transfer paper for an inorganic base material on which a coating film (image) having a thickness of 50 to 100 pm was formed. The transfer paper for an inorganic base material was adhered to a surface of a ceramic article containing, as a main component, bone ash, kaolin, feldspar, or the like, and was baked at 850 ° C, thus producing pieces of ceramics (inorganic product) that have a decorative part.
    [0234] Next, a gloss value of 8 ° of the decorative part (ink after firing) of the ceramic was measured after firing using a spectral colorimeter (Konica Minolta, Inc., Model: CM-600). In case the measured gloss value was 75 or more, the gloss value was evaluated as "good", in case the measured gloss value was 60 or more and less than 75, the gloss value was evaluated as "good". evaluated as "pass", and in a case where the measured gloss value was less than 60, the gloss value was evaluated as "not pass". The results of the evaluation are indicated in Tables 1 to 3.
    [0236] [Table 1]
    [0238]
    [0239]
    [0240] [Table 2]
    [0241]
    [0243] [Table 3]
    [0244]
    [0247] As illustrated in Tables 1-3, Examples 1-16 and Examples 21-23 were rated "pass" or better for both ink viscosity before cure and post-bake gloss. Based on this, it was confirmed that both the ink viscosity and the gloss after baking can be achieved at a high level by making the volume of the inorganic solid part to the total volume of the ink to be 30% by volume or less and the volume of the glass to the total volume of the inorganic solid part of 78% by volume or more.
    [0249] Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the scope of the claims includes various modifications and changes to the specific examples described above.
    [0251] List of reference signs
    [0252] 1 Inkjet device
    [0253] 10 Inkjet head
    [0254] 12 Housing
    [0255] 13 Storage section
    [0256] 15 Fluid feeding path
    [0257] 16 Discharge section
    [0258] 17 Download port
    [0259] 18 Piezoelectric element
    [0260] 20 Guide shaft
    [0261] 30 UV irradiation device
    [0262] 40 Print cartridge
    [0263] 100 Sprayer with shaking
    [0264] 110 Supply port
    [0265] 120 Vasodeagitation
    [0266] 132 Shaking
    [0267] 134 Axle
    [0268] 140 Filter
    [0269] 150 Puertodeescape
    [0270] A Liquid feed direction X Axial direction of guide shaft
    [0271] Y Vertical direction of guide shaft
    权利要求:
    Claims (7)
    [1]
    1. An inkjet ink used for an inorganic base material to be baked, the inkjet ink comprises:
    an inorganic solid part that includes an inorganic pigment and glass; and
    a monomeric component that has light curability, where
    a volume of the inorganic solid part when the total volume of the inkjet ink is 100% by volume is 30% by volume or less, and
    a volume of the glass when the total volume of the inorganic solid part is 100% by volume is 78% by volume or more.
    [2]
    2. The inkjet ink for an inorganic base material according to claim 1, wherein the volume of the inorganic solid part when the total volume of the inkjet ink is 100% by volume is 5% in volume or more.
    [3]
    3. The inkjet ink for an inorganic base material according to claim 1 or 2, wherein the volume of the glass when the total volume of the inorganic solid part is 100% by volume is 91% by volume or less .
    [4]
    The inkjet ink for an inorganic base material according to any of claims 1 to 3, wherein the monomer component includes at least one monofunctional acrylate monomer containing an acryloyl group or a methacryloyl group in a molecule, a monofunctional N-vinyl compound monomer in which a vinyl group is attached to a nitrogen atom (N) of a nitrogen-containing compound, and a polyfunctional vinyl ether-based monomer that contains at least two vinyl ether groups in one molecule .
    [5]
    The inkjet ink for an organic based material according to claim 4, wherein a volume ratio of the monomer component when the total volume of the inkjet ink is 100% by volume is 44% in volume or more and 85% by volume or less.
    [6]
    6. A transfer paper production method for an inorganic base material used for an inorganic base material to be baked, the method comprising:
    depositing the inkjet ink of claim 4 or claim 5 into a surface of a support by means of an ink jet device; and
    irradiating the surface of the support with an ultraviolet ray to cure the inkjet ink deposited on the surface of the support.
    [7]
    7. A method of producing an inorganic product that has a decorative part, the method comprising:
    depositing the inkjet ink of any one of claims 1 to 5 onto a surface of an organic based material; and
    baking the inorganic base material in a condition where a higher baking temperature is set within a range of 500 ° C to 1200 ° C.
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    同族专利:
    公开号 | 公开日
    WO2020174870A1|2020-09-03|
    US20220017761A1|2022-01-20|
    JPWO2020174870A1|2020-09-03|
    CN113490598A|2021-10-08|
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    法律状态:
    2021-09-30| BA2A| Patent application published|Ref document number: 2858529 Country of ref document: ES Kind code of ref document: A2 Effective date: 20210930 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2019034700|2019-02-27|
    PCT/JP2019/051398|WO2020174870A1|2019-02-27|2019-12-27|Inkjet ink|
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