Pattern-containing liquid and manufacturing method thereof

Abstract

The purpose of the present invention is to provide: a pattern-containing liquid which contains, in a liquid base, a pattern capable of generating a sense such as color, taste, texture, tactile sensation and the like, and which has good stability of the pattern; and a method for producing a pattern-containing liquid which is capable of stably forming the pattern in a liquid base. The present invention relates to a pattern-containing liquid or the like, characterized in that a liquid matrix, which is a pseudoplastic fluid and is accommodated in a container, contains a pattern formed from microparticles and / or pigments.

Description

Technical Field

[0001] The present invention relates to a patterned liquid and a method for manufacturing the same. More specifically, it relates to a patterned liquid containing patterns such as characters and drawings in a liquid matrix and a method for manufacturing the same. Background Art

[0002] Three-dimensional printing technology is a technology for forming a three-dimensional structure by successively laminating materials made into two-dimensional layers based on three-dimensional CAD (Computer-Aided Design) data. Using this technology, three-dimensional structures using various materials such as metal materials, polymer materials, food materials, and cells have been formed.

[0003] So far, as an example of three-dimensional printing technology in a liquid phase, a technology has been proposed in which a platform with an exchangeable liquid phase is used in printing, and a polymer material is laminated while exchanging the liquid phase according to the target conditions to construct a polymer structure (for example, refer to Patent Document 1), or a technology in which a solidifying material is stacked in a high-viscosity gel, and by solidifying it, a suspended three-dimensional object is formed in the gel (for example, refer to Patent Document 2), or a technology in which a second fluid that does not mix with the first fluid is introduced into the first fluid, and a pattern is formed in the first fluid by taking advantage of their non-mixing (for example, refer to Patent Document 3). And a proposal has been made to stabilize the pattern by increasing the viscosity of the liquid.

[0004] In addition, in order to impart viscosity to food and beverages and change the ease of swallowing of food and beverages, a thickener exhibiting pseudoplasticity is added to food and beverages (for example, refer to Patent Document 4).

[0005] Patent Documents Patent Document 1: US Patent Application Publication No. 2020 / 247053 Patent Document 2: US Patent Application Publication No. 2018 / 281295 Patent Document 3: International Publication No. 2018 / 218264 Patent Document 4: Japanese Patent Application Laid-Open No. 2022-530927 Summary of the Invention

[0006] However, for drawing in a liquid, even if ink is ejected into a high-viscosity liquid through a nozzle, the flow caused by the movement of the nozzle will change the pattern formed by the ink, making it impossible to perform the desired drawing.

[0007] In the method of laminating a polymer material on the bottom of a container containing a fluid described in Patent Document 1, although the viscosity or rheological properties of the ejected material are discussed, the properties such as the viscosity of the liquid onto which the material is ejected are not considered. In addition, in the method described in Patent Document 2, the viscosity in the gel used is as high as 20,000 mPa to 50,000 mPa, and its scope of application is limited. In addition, the properties such as the pseudoplasticity of the gel are not considered. Similarly, in the method described in Patent Document 3, although it is mentioned that adding a thickening agent to the liquid phase to increase the viscosity is beneficial to the stability of the pattern, the properties such as the pseudoplasticity of the liquid phase are not considered. In Patent Document 4, the ease of swallowing is improved by controlling the pseudoplasticity by adding a thickening agent to food, but the drawing on the liquid is not considered, and the control of the pseudoplasticity of the food and drink used for drawing is not carried out.

[0008] An object of the present invention is to provide a patterned liquid containing a pattern that can produce sensations such as color, taste, texture, and touch in a liquid matrix, and having good stability of the above-mentioned pattern. In addition, an object of the present invention is to provide a method for manufacturing a patterned liquid capable of stably forming the above-mentioned pattern in a liquid matrix.

[0009] The inventors of the present invention conducted in-depth research to solve the above problems, and as a result, found that when manufacturing a patterned liquid containing a pattern formed by fine particles and / or pigments in a liquid matrix, if the liquid matrix is a pseudoplastic fluid, the pattern can be stably formed in the liquid matrix. The inventors also found that the stability of the above-mentioned pattern formed in the pseudoplastic fluid is good.

[0010] Although the present invention is not limited thereto, it includes the following patterned liquid, method for manufacturing a patterned liquid, etc. [1] A patterned liquid, characterized in that the liquid matrix contains a pattern formed by fine particles and / or pigments, the liquid matrix is a pseudoplastic fluid, and the liquid matrix is contained in a container. [2] The patterned liquid according to the above [1], characterized in that the liquid matrix is a fluid that exhibits pseudoplasticity in at least a certain range between a shear rate of 0.3 and 130 s -1 -1. [3] The patterned liquid according to the above [1] or [2], characterized in that the liquid matrix is a fluid that satisfies the following formula (I) in at least a certain range between a shear rate of 0.3 and 130 s -1 -1, log(η1 / η2) / log(γ1 / γ2) ≦ -0.12 Formula (I) In the above formula (I), η1 represents the viscosity (mPa·s) of the fluid at a shear rate of γ1 (s -1 -1), and η2 represents the viscosity (mPa·s) of the fluid at a shear rate of γ2 (s -1) The viscosity (mPa·s) of the fluid at ( ), where γ1 and γ2 satisfy 0.3 ≦ γ2 < γ1 ≦ 130, and the viscosity is the viscosity at 25°C. [4] The patterned liquid according to any one of the above [1] to [3], characterized in that the viscosity of the liquid matrix obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity is 4 mPa·s or more at a shear rate of 100 s -1 at 25°C. [5] The patterned liquid according to any one of the above [1] to [4], characterized in that the liquid matrix contains water and a water-soluble thickener. [6] The patterned liquid according to the above [5], characterized in that the water-soluble thickener is at least one selected from xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan. [7] The patterned liquid according to any one of the above [1] to [6], characterized in that it is a beverage. [8] A method for manufacturing a patterned liquid, characterized by including ejecting a pattern-forming material in which fine particles and / or pigments are dispersed in a dispersion solvent using a nozzle into a liquid matrix contained in a container, and forming a pattern composed of the fine particles and / or pigments in the liquid matrix, and the liquid matrix is a pseudoplastic fluid. [9] The method for manufacturing a patterned liquid according to the above [8], characterized in that the dispersion solvent is a pseudoplastic fluid.

[10] An application, characterized by using a pseudoplastic fluid as the matrix of a patterned liquid.

[0011] According to the present invention, a patterned liquid can be provided that contains a pattern capable of generating sensations such as color, taste, texture, and touch in a liquid matrix, and the stability of the above pattern is good. In addition, according to the present invention, a method for manufacturing a patterned liquid capable of stably forming the above pattern in a liquid matrix can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is a conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid in which a pattern is formed in a liquid matrix. Figure 2 is a conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid using a gantry-type apparatus. Figure 3 is a conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid using a robotic arm. Figure 4 is a perspective view schematically showing an apparatus for manufacturing a patterned liquid fabricated in Reference Example 1. Figure 5A chart showing the relationship between the viscosity and shear rate of the liquids (CMC-a and CMC-b) used in the drawing in Example 1 (squares: CMC-a, circles (〇): CMC-b). Figure 6 A and Figure 6 B are photos taken from the side of the container of the patterns drawn in the liquid in Example 1 (with the drawing surface as the front). Figure 6 A: CMC-a, Figure 6 B: CMC-b). Figure 7 A chart showing the relationship between the viscosity and shear rate of the specimens T1 to T3 prepared in Example 2 (□: specimen T1, △: specimen T2, ◇: specimen T3). Figure 8 A chart showing the relationship between the viscosity and shear rate of the specimens T4 to T5 prepared in Example 2 (□: specimen T4, △: specimen T5). Figure 9 A chart showing the relationship between the viscosity and shear rate of the specimens T6 to T8 prepared in Example 2 (〇: specimen T6, □: specimen T7, △: specimen T8). Figure 10 A chart showing the relationship between the viscosity and shear rate of the specimen T9 prepared in Example 2 (●: specimen T9). Figure 11 A chart showing the relationship between the viscosity and shear rate of the specimen T10 prepared in Example 2 (〇: specimen T10). Figure 12 A chart showing the relationship between the viscosity and shear rate of the specimens T11 to T14 prepared in Example 2 (〇: specimen T11, □: specimen T12, △: specimen T13, ◇: specimen T14). Figure 13 A and Figure 13 B are schematic diagrams showing the patterns drawn in Example 2. Figure 14 A chart showing the relationship between the slope (Δlogη) / (Δlogγ) of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid used in the drawing in Example 2 and the stability of the pattern in the liquid. Figure 15 For showing the shear rate of 100 s of the liquid used in the drawing in Example 2 -1 at 25°C and the relationship between the viscosity (calculated value) and the stability of the pattern in the liquid. Figure 16A chart showing the relationship between the inclination and viscosity of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid used in the drawing in Example 2, and the stability of the pattern in the liquid. Figure 17 A chart showing the relationship between the viscosity and shear rate of specimens T15 to T18 prepared in Example 3 (black square: specimen T15, ●: specimen T16, □: specimen T17, 〇: specimen T18). Figure 18 A chart showing the relationship between the inclination (Δlogη) / (Δlogγ) of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid used in the drawing in Example 3, and the stability of the pattern in the liquid. Figure 19 To represent the shear rate 100s of the liquid used in the drawing in Example 3 -1 The chart showing the relationship between the viscosity (calculated value) at 25°C at this time and the stability of the pattern in the liquid. Figure 20 A chart showing the relationship between the inclination and viscosity of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid used in the drawing in Example 3, and the stability of the pattern in the liquid. Figure 21 A schematic diagram showing the pattern drawn in Example 4. Figure 22 A and Figure 22 B are charts showing the relationship between the inclination (Δlogη) / (Δlogγ) calculated from the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid used in the drawing in Example 4, and the stability of the pattern in the liquid. Figure 23 A and Figure 23 B are charts showing the relationship between the viscosity (calculated value) at 25°C at the shear rate 100s of the liquid used in the drawing in Example 4 and the stability of the pattern in the liquid. -1 The chart showing the relationship between the viscosity (calculated value) at 25°C at this time and the stability of the pattern in the liquid. Figure 24 A chart showing the relationship between the viscosity and shear rate of an aqueous glycerol solution added with xanthan gum (final concentration of glycerol 20% by weight) (black square: aqueous solution added with 0.02% by weight xanthan gum, 〇: aqueous solution added with 0.03% by weight xanthan gum, ●: aqueous solution added with 0.05% by weight xanthan gum, triangle: aqueous glycerol solution without xanthan gum). Figure 25 A, Figure 25 B and Figure 25 C are photos of the dot patterns drawn in Example 5. Figure 26 A graph showing the change over time in the vertical length of the pattern of the points plotted in Example 5 (**: p < 0.01). Detailed Description

[0013] The patterned liquid of the present invention is a patterned liquid characterized in that a pattern formed of fine particles and / or pigments is contained in a liquid matrix, the liquid matrix is a pseudoplastic fluid, and the liquid matrix is contained in a container.

[0014] In the patterned liquid of the present invention, a pattern formed of fine particles and / or pigments is formed in the liquid matrix. Hereinafter, the pattern formed of fine particles and / or pigments may sometimes be simply referred to as a pattern.

[0015] In the present invention, the liquid matrix is a pseudoplastic fluid. Pseudoplasticity refers to the property that the viscosity decreases as the shear rate increases. A pseudoplastic fluid is a type of non-Newtonian fluid, which is a fluid whose viscosity decreases as the shear rate increases. That is, a fluid having pseudoplasticity is called a pseudoplastic fluid. The liquid matrix being a pseudoplastic fluid can be confirmed by using at least two shear rates of a commercially available B-type viscometer well-known to those skilled in the art and the viscosity at that shear rate.

[0016] In the patterned liquid of the present invention, a pattern is formed of fine particles and / or pigments in the liquid matrix. When the liquid matrix is a pseudoplastic fluid, compared with a fluid that does not exhibit pseudoplasticity, the pattern formed in the liquid matrix is less likely to move (for example, float, settle, or diffuse). Therefore, in the patterned liquid of the present invention, the position and shape of the pattern in the liquid matrix are less likely to change, and the stability of the pattern is good. In the patterned liquid of the present invention, for example, even if the viscosity of the liquid matrix is low, the stability of the above pattern is improved compared with the pattern formed in a liquid that does not exhibit pseudoplasticity.

[0017] In the present invention, the liquid matrix is usually a liquid that exhibits pseudoplasticity (has pseudoplasticity). The liquid matrix is preferably a liquid that exhibits pseudoplasticity at least at one point between temperatures of 1 to 90 °C, and more preferably a liquid that exhibits pseudoplasticity at least at a temperature of 25 °C. The liquid matrix is preferably a liquid (liquid state) at 1 to 90 °C, for example.

[0018] In the present invention, the liquid matrix is preferably a fluid that exhibits pseudoplasticity within at least a certain range between a shear rate of 0.1 to 130 s -1 and more preferably within at least a certain range between a shear rate of 0.3 to 130 s -1 and further preferably within at least a certain range between a shear rate of 1 to 100 s -1A fluid that exhibits pseudoplasticity within at least a certain range. In one embodiment, the liquid matrix is preferably a fluid that exhibits pseudoplasticity, for example, within a range including a shear rate of 10 - 20 s -1 and / or 30 - 50 s -1 A fluid that exhibits pseudoplasticity. The liquid matrix is more preferably a fluid that exhibits pseudoplasticity, for example, within at least one of the ranges of shear rate of 0.3 - 20 s -1 , 3 - 65 s -1 , 10 - 34 s -1 , 10 - 90 s -1 and 26 - 130 s -1 In one embodiment, the liquid matrix is further preferably a fluid that exhibits pseudoplasticity within at least a certain range between a shear rate of 10 - 90 s -1 , and more preferably a fluid that exhibits pseudoplasticity between a shear rate of 10 - 20 s -1 (preferably 10 - 30 s -1 , more preferably 10 - 34 s -1 ), and particularly preferably a fluid that exhibits pseudoplasticity between a shear rate of 10 - 90 s -1 .

[0019] In the present invention, the liquid matrix is preferably a fluid that satisfies the following formula (I) within at least a certain range between a shear rate of 0.3 - 130 s -1 . log(η1 / η2) / log(γ1 / γ2) ≤ -0.12 Formula (I) (In the above formula (I), η1 represents the viscosity (mPa·s) of the fluid at a shear rate γ1 (s -1 ), and η2 represents the viscosity (mPa·s) of the fluid at a shear rate γ2 (s -1 ). γ1 and γ2 satisfy 0.3 ≤ γ2 < γ1 ≤ 130. The viscosity is the viscosity at 25°C.) The viscosity of the liquid matrix is measured by a B-type viscometer (e.g., rotational viscometer ViscoQC 300-L, Antonpaar). The pseudoplastic fluid is preferably a fluid that satisfies the above formula (I) within at least a certain range between a shear rate of 0.3 - 130 s -1 . The left side of the above formula (I) represents the slope (logη1 - logη2) / (logγ1 - logγ2) of the straight line connecting the points (logγ2, logη2) and (logγ1, logη1) in a graph with the logarithm of the shear rate γ (logγ) on the x-axis and the logarithm of the viscosity of the fluid at that shear rate (logη) on the y-axis. Between a shear rate of 0.3 - 130 s -1The so-called satisfying the above formula (I) means that the shear rate is 0.3 to 130s -1 The shear rate γ1(s -1 ) and γ2(s -1 )(0.3≦γ2<γ1≦130),γ1(s -1 ) under the viscosity η1 (mPa·s) and γ2 (s -1 ) satisfies the above formula (I). The liquid matrix is preferably at a shear rate of 0.3 to 130 s -1 At least two points between (γ2(s -1 ) and γ1(s -1 )) between the left side of the above formula (I) is -0.12 or less. In the above formula (I), log(η1 / η2) / log(γ1 / γ2) is preferably -2 or more and -0.12 or less (-2≦log(η1 / η2) / log(γ1 / γ2)≦-0.12). In this specification, logarithms refer to common logarithms.

[0020] In the above formula (I), γ1 and γ2 satisfy 0.3≦γ2<γ1≦130. In the above formula (I), the fluid with the left side (log (η1 / η2) / log (γ1 / γ2)) of -0.1 or less at the shear rate γ1 (s -1 ) and above, γ2(s -1 ) or less, it can be said to be pseudoplastic. -1Within at least a certain range, when the value of the left side (log(η1 / η2) / log(γ1 / γ2)) of the above formula (I) is -0.12 or less, the pattern in the liquid matrix is more stable. In one mode, log(η1 / η2) / log(γ1 / γ2) in the above formula (I) is preferably -2 or more, more preferably -1.5 or more, further preferably -1 or more, and in addition, more preferably -0.16 or less, further preferably -0.17 or less, still further preferably less than -0.17, particularly preferably -0.2 or less, and most preferably -0.4 or less. In one mode, log(η1 / η2) / log(γ1 / γ2) in the above formula (I) is preferably -2 or more and -0.16 or less (-2 ≦ log(η1 / η2) / log(γ1 / γ2) ≦ -0.16), more preferably -2 or more and -0.17 or less (-2 ≦ log(η1 / η2) / log(γ1 / γ2) ≦ -0.17), further preferably -2 or more and less than -0.17 (-2 ≦ log(η1 / η2) / log(γ1 / γ2) < -0.17), still further preferably -2 or more and -0.2 or less (-2 ≦ log(η1 / η2) / log(γ1 / γ2) ≦ -0.2), particularly preferably -1.5 or more and -0.4 or less (-1.5 ≦ log(η1 / η2) / log(γ1 / γ2) ≦ -0.4), and most preferably -1 or more and -0.4 or less (-1 ≦ log(η1 / η2) / log(γ1 / γ2) ≦ -0.4).

[0021] In one mode, the difference (γ1 - γ2) (s -1 ) of the above γ1 and γ2 is preferably 10 to 104 (s -1 ), more preferably 20 to 104 (s -1 ), further preferably 20 to 80 (s -1 ), particularly preferably 62 to 80 (s -1 ).

[0022] In one mode, the liquid matrix is preferably a fluid that satisfies the above formula (I) at a shear rate of 10 to 20 s -1 (in the above formula (I), γ1 is 20 (s -1 ) and γ2 is 10 (s -1 )) and / or at a shear rate of 30 to 50 s -1 (in the above formula (I), γ1 is 50 (s -1 ) and γ2 is 30 (s -1 )). The liquid matrix is more preferably a fluid that satisfies the above formula (I) at a shear rate in at least one of the following ranges. Shear rate 0.3 to 20 s -1(In the above formula (I), γ1 is 20 (s -1 ), γ2 is 0.3 (s -1 )) Shear rate 3 - 65 s -1 (In the above formula (I), γ1 is 65 (s -1 ), γ2 is 3 (s -1 )) Shear rate 10 - 34 s -1 (In the above formula (I), γ1 is 34 (s -1 ), γ2 is 10 (s -1 )) Shear rate 10 - 90 s -1 (In the above formula (I), γ1 is 90 (s -1 ), γ2 is 10 (s -1 )) Shear rate 26 - 130 s -1 (In the above formula (I), γ1 is 130 (s -1 ), γ2 is 26 (s -1 )) In one mode, the liquid matrix is preferably a fluid that satisfies the above formula (I) when between the above γ2 (s -1 ) and γ1 (s -1 ).

[0023] In one mode, the liquid matrix is a fluid that satisfies the above formula (I) at a shear rate of 10 - 90 s -1 . At this time, γ1 in the above formula (I) is 90 (s -1 ), and γ2 is 10 (s -1 ).

[0024] As the liquid matrix, a liquid containing water is preferred, and a liquid based on water is more preferred. For example, pseudoplasticity can be imparted by adding a thickening agent to the liquid. In the present invention, a water-soluble thickening agent is preferably used as the thickening agent. In one mode, the liquid matrix preferably contains water and a water-soluble thickening agent, and more preferably an aqueous solution containing a water-soluble thickening agent. Examples of the liquid used as the liquid matrix include liquid foods and beverages such as drinks, liquid oral pharmaceuticals or oral pharmaceutical products for external use (such as liquid preparations, oral liquids), perfumes, cosmetics (skin cosmetics such as lotions, emulsions), liquid non-oral pharmaceuticals or pharmaceutical products for external use (such as eye drops, nasal drops), and water in a water tank. The above liquid matrix can also be a liquid suitable for cell culture or maintenance, such as a culture medium, a buffer solution. The liquid matrix can also be a matrix obtained by adding the above thickening agent to the above liquid. The thickening agent is preferably dissolved or uniformly dispersed in the liquid matrix.

[0025] In one way, the liquid matrix is preferably edible. Here, "edible" means suitable for human ingestion, and does not particularly limit whether it can be digested or absorbed by the human body.

[0026] In one way, as an edible liquid matrix, it is preferred that the beverage contains an edible water-soluble thickener to impart pseudoplasticity. In one way, the liquid matrix is preferably a beverage containing a water-soluble thickener. As beverages, for example, water; tea; coffee; fruit juice beverages, carbonated beverages, functional beverages, sports beverages, energy beverages, non-alcoholic beverages and other soft drink waters; alcoholic beverages; nutritional drinks; milk; soy milk; soup; smoothies; iced smoothies; milkshakes and other beverages can be cited.

[0027] As the water-soluble thickener, xanthan gum, gellan gum, carboxymethyl cellulose, locust bean gum, tara gum, carrageenan, etc. can be cited. The water-soluble thickener can be one kind or a combination of two or more kinds. Among them, as the water-soluble thickener, it is preferably at least one selected from carboxymethyl cellulose, xanthan gum, gellan gum, locust bean gum, tara gum and carrageenan, and more preferably at least one selected from xanthan gum, gellan gum, locust bean gum, tara gum and carrageenan. When the liquid matrix contains at least one selected from xanthan gum, gellan gum, locust bean gum, tara gum and carrageenan, the stability of the pattern is better and thus preferred. As the pseudoplastic fluid in the present invention, a liquid containing water and the above-mentioned water-soluble thickener is preferred.

[0028] Xanthan gum is a polysaccharide and can be produced by fermenting sugars such as starch by the microorganism Xabthomonas campestris. Xanthan gum can use xanthan gum produced by microorganisms according to general methods, or commercially available products. As commercially available products, for example, Sun Ace (Sanrion F.F.I Co., Ltd.), CX930QD (Unitec Foods Co., Ltd.) and the like can be cited.

[0029] Gellan gum is a polysaccharide obtained by fermentation. Gellan gum can be produced by the microorganism Sphingomonas elodea. In the present invention, gellan gum includes HA gellan gum containing high acyl groups and LA gellan gum from which acyl groups are removed. HA gellan gum containing high acyl groups is preferred. Gellan gum can use gellan gum produced according to general methods, or commercially available products. As commercially available products, for example, Kerkogel LT-1000 (Sanrion F.F.I Co., Ltd.), Kerkogel HM (Sanrion F.F.I Co., Ltd.), Kerkogel MOT(D) (Sanrion F.F.I Co., Ltd.) and the like can be used.

[0030] Locust bean gum is a seed mucilage obtained from the cotyledons of the carob tree, a leguminous plant. It is a galactomannan composed of repeating units with a linear main chain of four mannoses and one galactose bonded to the side chain, and is a plant-based water-soluble polymer. As commercial products, for example, Soar Locust (Mitsubishi Chemical Corporation), A-200 or B-175 (Enomoto Sangyo Co., Ltd.) etc. can be cited.

[0031] Tara gum is a neutral polysaccharide obtained from the endosperm of the seeds of the tara tree, a leguminous plant. It is a galactomannan composed of repeating units with a linear main chain of three mannoses and one galactose bonded to the side chain, and is a plant-based water-soluble polymer. As commercial products, for example, tara gum (Mitsubishi Chemical Corporation), tara gum (Ina Food Industry Co., Ltd.) etc. can be cited.

[0032] Carrageenan is a polysaccharide extracted from red algae and has a structure in which a sulfate group is attached to a galactose group. As commercial products, for example, Soagina (Mitsubishi Chemical Corporation), refined carrageenan (Margo Corporation) etc. can be cited.

[0033] The concentration (content) of the water-soluble thickener in the liquid matrix only needs to be a concentration at which the liquid matrix exhibits pseudoplasticity, and can be appropriately set according to the type of the water-soluble thickener etc. Preferably, the concentration of the water-soluble thickener etc. is adjusted so as to exhibit pseudoplasticity at a temperature of 25°C. In one mode, when the liquid matrix contains at least one water-soluble thickener selected from xanthan gum, gellan gum, locust bean gum, tara gum and carrageenan, the total concentration of the water-soluble thickener is preferably 0.01 to 2% by weight, more preferably 0.02 to 1% by weight. In one mode, when the liquid matrix contains xanthan gum, the concentration of xanthan gum is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight. When the liquid matrix contains gellan gum, the concentration of gellan gum is preferably 0.01 to 1% by weight, more preferably 0.02 to 0.5% by weight, further preferably 0.02 to 0.4% by weight. When the liquid matrix contains locust bean gum, the concentration of locust bean gum is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, further preferably 0.1 to 1% by weight. When the liquid matrix contains tara gum, the concentration of tara gum is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, further preferably 0.1 to 1% by weight. When the liquid matrix contains carrageenan, the concentration of carrageenan is preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, further preferably 0.1 to 1% by weight.

[0034] From the viewpoint of being able to visually recognize the pattern based on the microparticles and / or pigments from the outside of the liquid matrix, it is preferable that the liquid matrix has a transparency at which the pattern can be visually recognized.

[0035] In one embodiment of the present invention, the viscosity of the liquid matrix at 25°C when the shear rate is, for example, obtained from the linear approximation of the logarithm of the shear rate and the logarithm of the viscosity, is preferably 4 mPa·s or more when the shear rate is 100 s -1 . This is because when the viscosity at 25°C when the above shear rate is 100 s -1 is 4 mPa·s or more, the pattern formed in the liquid matrix is more stable. In addition, when the viscosity at 25°C when the above shear rate is 100 s -1 is 4 mPa·s or more, when forming a pattern in the liquid matrix using the pattern forming material described below, the pattern can be formed more stably. The viscosity of the liquid matrix at 25°C when the above shear rate is 100 s -1 is more preferably 7 mPa·s or more, further preferably 10 mPa·s or more, particularly preferably 15 mPa·s or more. In addition, it is preferably 6000 mPa·s or less, more preferably 1000 mPa·s or less, further preferably 150 mPa·s or less, particularly preferably 100 mPa·s or less. In one embodiment, the viscosity of the liquid matrix at 25°C when the above shear rate is 100 s -1 is preferably 4 to 6000 mPa·s, more preferably 7 to 1000 mPa·s, further preferably 10 to 1000 mPa·s, still more preferably 15 to 1000 mPa·s, particularly preferably 15 to 150 mPa·s, and most preferably 15 to 100 mPa·s.

[0036] In the present invention, the above "viscosity at 25°C when the shear rate obtained from the linear approximation of the logarithm of the shear rate and the logarithm of the viscosity is 100 s -1 " means that, in order to measure the viscosity of the liquid matrix, the logarithm of the measured shear rate and the logarithm of the viscosity at that shear rate are calculated, and the viscosity at 25°C when the shear rate obtained from the linear approximation obtained by performing linear regression analysis on the obtained calculated values is 100 s -1 . Specifically, it refers to the value (calculated value) of the viscosity at 25°C when the shear rate obtained by the following method is 100 s -1 . (1) Measure the viscosity (η) at 25°C within the range where the shear rate (γ) is from 0.3 s -1 to 130 s -1 at three or more points. (2) Calculate the logarithm of the shear rate (logγ) and the logarithm of the viscosity (logη) measured in (1) respectively, and perform linear regression analysis on these values to obtain the linear approximation of logγ and logη. (3) Calculate the shear rate of 100 s from the linear approximation obtained in (2)-1 The viscosity at 25°C. In the above (1), the difference (γmax-γmin) between the maximum value (γmax) and the minimum value (γmin) of the shear rate (γ) for measuring the viscosity is preferably 10s -1 More than 20s, more preferably -1 More than 60s, more preferably -1 More than, in addition, preferably 104s -1 Below, preferably 80s -1 In one embodiment, the difference (γmax-γmin) can be, for example, 10 to 104 s. -1 10~80s -1 20~80s -1 or 60-80s -1 In one embodiment, it is preferred to include a shear rate of 10 to 20 s -1 Within the range of , measure the viscosity at 25℃ at more than 3 points, and find the shear rate in 100s -1 The viscosity at 25°C.

[0037] In one embodiment, the liquid matrix is subjected to a shear rate of 10 s -1 The viscosity at 25°C is preferably 10 mPa·s or more, more preferably 10 to 7000 mPa·s, and even more preferably 10 to 500 mPa·s. The shear rate is 10s -1 The viscosity at 25°C can be measured using a B-type viscometer (e.g., rotational viscometer ViscoQC 300-L, Antonpaar) at a shear rate of 10s at 25°C. -1 The shear rate is 10s -1 When the viscosity at 25°C is within the above range, the stability of the pattern in the liquid matrix is better. In the present invention, even if the viscosity of the liquid matrix is low, the stability of the above pattern is good. In the present invention, for example, even if the liquid matrix is a shear rate of 10s -1 The stability of the pattern is also good when the viscosity of the liquid matrix is 10 to 500 mPa·s at 25° C. Furthermore, the stability of the pattern is further improved when the viscosity of the liquid matrix is high.

[0038] The viscosity can be adjusted by adjusting the content of the thickener. In one embodiment, the liquid matrix is preferably subjected to the above-mentioned shear rate of 100s -1 The viscosity at 25°C is within the above range, and the liquid matrix contains the water-soluble thickener. In one embodiment, the shear rate is 10s -1 The liquid base contains the water-soluble thickener so that the viscosity at 25° C. when the liquid base is in the above range.

[0039] The density of the liquid matrix is preferably 0.9 to 1.1 g / mL, more preferably 1 to 1.1 g / mL. The so-called "density" refers to the weight per unit volume. In this specification, the density refers to the density at 25°C when not otherwise specified. The density of liquids such as the liquid matrix can be measured by a densitometer (for example, DMA4500M, manufactured by Anton Paar).

[0040] In the patterned liquid of the present invention, a pattern is formed in the liquid matrix by fine particles and / or pigments. The fine particles and pigments that form the pattern in the liquid matrix are sometimes also referred to as first fine particles and first pigments, respectively. Any of the above patterns can be a one-dimensional pattern (line), a two-dimensional pattern (plane), or a three-dimensional pattern (solid). The type of the pattern is not particularly limited, and examples thereof include patterns that generate colors such as marks such as letters, lines, and drawings; patterns that generate tastes, aromas, textures, tactile sensations, etc.; and patterns that generate these sensations in combination. The pattern in the liquid matrix may be in contact with the inner side of the container that holds the liquid matrix, or may not be in contact with the inner side of the container. The pattern may also float in the liquid matrix.

[0041] The above pattern is formed by fine particles and / or pigments. The pigment is not particularly limited, and examples thereof include red pigments, yellow pigments, blue pigments, green pigments, black pigments, white pigments, etc., and may be one kind or a combination of two or more kinds.

[0042] Examples of the pigment include natural pigments such as capsanthin, gardenia pigment, monascus pigment, chlorophyll, β-carotene, astaxanthin, sepia ink pigment, caramel pigment, tomato pigment, red pepper pigment, safflower pigment, and green algae pigment; azo pigments, pigments, etc. Examples of the pigment include titanium dioxide, silicon oxide, carbon fine particles, etc. Examples of the azo pigment include Red No. 2, Red No. 3, Red No. 40, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, etc. The pigment is preferably an edible pigment.

[0043] The so-called fine particles are particles of a micro size. The particle structure of the fine particles is not particularly limited, and examples thereof include a uniform type, a core-shell type, a double-sided type, etc. The fine particles are preferably particles that are insoluble or hardly soluble in the liquid matrix. Thus, the pattern formed by the fine particles can be maintained in the liquid matrix for a long time.

[0044] Preferably, the microparticles constituting the pattern are not chemically bonded to each other with a crosslinking agent. This is because the pattern formed by the microparticles will agglomerate. Thus, for example, when the liquid containing the pattern is a beverage, the pattern can be more easily consumed simultaneously with the liquid matrix.

[0045] The diameter of the microparticles can be, for example, 0.13 μm or more, preferably 0.2 μm or more and 1000 μm or less. This is because when the diameter of the microparticles is, for example, 0.13 μm or more, preferably 0.2 μm or more, the pattern formed by the microparticles becomes more stable in the liquid matrix. When the diameter is 1000 μm or less, a roughness can be not felt at the time of microparticle intake (for example, refer to the Bulletin of the Faculty of Engineering, Hachinohe National College of Technology, 2007, Vol. 26, p. 9-13). From this viewpoint, the diameter of the microparticles is more preferably 100 μm or less. The diameter of the microparticles is more preferably 0.3 μm or more, further preferably 0.5 μm or more, and in addition, further preferably 50 μm or less. In one embodiment, the diameter of the microparticles is preferably 0.13 to 1000 μm, more preferably 0.2 to 1000 μm, further preferably 0.3 to 100 μm, and particularly preferably 0.5 to 50 μm. Here, the "diameter of the microparticles" is the mode diameter of the particle size distribution of the microparticles measured by the dynamic light scattering method (DLS).

[0046] The ratio of the density of the microparticles to the density of the above liquid matrix (density of the microparticles / density of the liquid matrix) is preferably 0.9 or more and 1.1 or less. When the above density ratio is 0.9 or more and 1.1 or less, the pattern formed by the microparticles floating or settling in the liquid matrix can be more suppressed. From this viewpoint, the above density ratio (density of the microparticles / density of the liquid matrix) is more preferably 0.92 or more and 1.08 or less, and further preferably 0.95 or more and 1.05 or less.

[0047] Here, the "density of the microparticles" is the density equivalent to the minimum density in the density of the solution in which microparticles (which may be the material in which microparticles are dispersed described later) are dropped into solutions with various concentrations (for example, glycerol aqueous solution) and centrifuged under specific conditions (for example, 18,500×g for 1 minute) and no sedimentation of the microparticles is observed.

[0048] The above microparticles are preferably microparticles containing an organic substance. In the present invention, the microparticles are preferably organic microparticles. The so-called organic microparticles refer to particles containing an organic substance as the main component of the shape of the particles forming the particles. The organic substance is preferably an edible organic substance. In the present invention, the microparticles are more preferably edible organic microparticles.

[0049] The above-mentioned microparticles preferably contain at least one component selected from pigments, flavor components, nutrients, and aroma components. By incorporating these additives into the microparticles, various spatial sensory designs can be achieved through the patterns formed by the microparticles. For example, when containing pigments, a spatial color design based on the pattern formed by the microparticles can be achieved; when containing flavor components, a spatial taste design based on the pattern formed by the microparticles can be achieved; when containing nutrients, a spatial nutrition design based on the pattern formed by the microparticles can be achieved; when containing aroma components, a spatial aroma design based on the pattern formed by the microparticles can be achieved. Examples of pigments include the above-mentioned pigments. Examples of flavor components include sucrose, fructose, table salt, glucose, amino acids, nucleic acids, acetic acid, malic acid, citric acid, caffeine, tannins, capsaicin, glycerin, food extracts, etc. Examples of nutrients include vitamins, minerals, lipids, fatty acids, polypeptides, saccharides, health material molecules, food extracts, etc. Examples of aroma components include food flavor compounds containing vanillin, eugenol, geraniol, citral, etc. specified in the First Schedule of the Enforcement Regulations of the Japanese Food Sanitation Law, and food extracts. In addition, the microparticles can be microparticles containing a variety of particles with or without pigments and different types of pigments (e.g., different colors). The same applies to flavor components, nutrients, and aroma components respectively. The microparticles can contain a variety of particles with or without these additives or different types of additives.

[0050] In one embodiment, the above-mentioned microparticles preferably contain at least one of silicon oxide (silica) and titanium oxide (titanium dioxide). By incorporating these additives into the microparticles, good white performance or the development of other colors can be achieved.

[0051] The above-mentioned microparticles can contain hydrophobic substances or hydrophilic substances to maintain additives such as the above-mentioned pigments and silica within the microparticles. In addition, the microparticles can have, for example, the following structure: a structure in which layers containing hydrophobic substances and layers containing hydrophilic substances are alternately arranged from the center to the outside in a three-layer structure such as hydrophilic substance / hydrophobic substance / hydrophilic substance or hydrophobic substance / hydrophilic substance / hydrophobic substance.

[0052] When the above-mentioned microparticles contain an edible organic substance, the edible organic substance preferably functions as the main component in forming the shape of the particles of the microparticles. The molecular weight of the edible organic substance is not particularly limited, and the edible organic substance is preferably a high-molecular-weight substance.

[0053] The above-mentioned edible organic compound is preferably an edible organic substance selected from at least one of polysaccharides, polypeptides, higher alcohols, natural resins, lipids, higher fatty acid esters, polyphenols, polyvinyl alcohol, polyethylene glycol, and nucleic acids (DNA). In addition, the so-called "polysaccharide" here refers to a sugar formed by bonding of multiple (two or more molecules) monosaccharides. Furthermore, "polypeptide" refers to a compound in which multiple amino acids are connected by peptide bonds, including proteins here.

[0054] As preferred specific examples of the above-mentioned polysaccharides, dextrin, pectin, agar, agarose, glucomannan, polydextrose, maltodextrin, alginic acid (sodium alginate, calcium alginate, etc.), cellulose, hemicellulose, chitin, chitosan, starch (Starch, etc.), dextran, agarose, sucrose, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, etc. can be cited. The polysaccharides can be used alone or in combination of two or more.

[0055] As preferred specific examples of the above-mentioned polypeptides, gelatin, protein hydrolysate, collagen, albumin, etc. can be cited. The polypeptides can be used alone or in combination of two or more.

[0056] As preferred specific examples of the above-mentioned higher alcohols, dodecanol, hexadecanol, etc. can be cited. The higher alcohols can be used alone or in combination of two or more.

[0057] As preferred specific examples of the above-mentioned natural resins, gum arabic, shellac, wax, lignin, polylactic acid, etc. can be cited. The natural resins can be used alone or in combination of two or more.

[0058] As preferred specific examples of the above-mentioned lipids, lecithin, etc. can be cited. The lipids can be used alone or in combination of two or more.

[0059] In addition, two or more combinations can also be adopted for the above-mentioned preferred specific examples belonging to different classifications such as polysaccharides and polypeptides.

[0060] In addition, although the specific examples of the edible organic substance contain substances common to the specific examples of the above-mentioned flavor components or nutrients and other additives, these common examples are edible organic substances that can function as flavor components or nutrients and other components. In addition, in this specification, the "edible organic substance" is not limited to so-called foods and food additives, etc., and can be pharmaceuticals, quasi-drugs, etc., and refers to organic substances that can be orally ingested.

[0061] The above-mentioned microparticles can be cells such as human cells, animal cells, plant cells, microbial cells, protoplasts, etc.; organoids. When the microparticles are these cells, the patterns formed by the microparticles can endow various physiological functions. In addition, these cells contain edible organic compounds.

[0062] The above-mentioned microparticles aggregate with each other through non-covalent bond aggregability and can be microparticles that generate taste or touch. Thus, spatial taste or touch design based on the pattern formed by the microparticles can be achieved. In addition, the method of aggregating microparticles with each other through non-covalent bond aggregability is not particularly limited. For example, they can be aggregated by charging the surface of the microparticles.

[0063] In the present invention, the pattern can be formed by a pigment. When the pattern is formed by a pigment, spatial color design based on the pattern formed by the pigment can be achieved. The pattern formed by the pigment is preferably visually recognizable from the outside of the container that holds the liquid matrix. Generally, the molecular weight of a pigment molecule is smaller than that of a microparticle. Therefore, the pattern formed by microparticles tends to be more stable. In one mode, the pattern is preferably formed by microparticles. In the present invention, the pattern can be formed in the liquid matrix by the method described later, for example.

[0064] The patterned liquid of the present invention is contained in a container. The liquid matrix containing the above-mentioned pattern is contained in a solvent. The container is not particularly limited and can be appropriately selected. For example, when the patterned liquid is a beverage, a container that can hold the beverage can be used. In one mode, from the viewpoint of the pattern being visually recognizable from the outside, as the container, a transparent container is preferred. As a transparent container that can hold a beverage, for example, transparent glass, a cup made of transparent glass; a transparent drinking cup made of plastic, etc. can be cited.

[0065] The patterned liquid of the present invention can be a beverage, a cosmetic, a pharmaceutical product, a quasi-drug, a cell culture solution, a chemical reaction solution, etc. In one mode, the patterned liquid is preferably used as a beverage. The patterned liquid is preferably a beverage. When the patterned liquid is a beverage, the beverage is a beverage that contains an edible pattern formed by microparticles and / or a pigment in an edible liquid matrix. The patterned liquid of the present invention is preferably a patterned beverage.

[0066] In the patterned liquid of the present invention, within the range that does not impair the effects of the present invention, in addition to the first microparticles and / or the first pigment that form the pattern, microparticles and / or pigments can also be dispersed in the liquid matrix. The above-mentioned microparticles and pigments dispersed in the liquid matrix are respectively called second microparticles and second pigments. The liquid matrix may also not contain the second microparticles and / or the second pigment. As the second microparticles and second pigments, the same substances as the above-mentioned first microparticles and first pigment can be cited. In the patterned liquid of the present invention, as shown later, the dispersion solvent used in the production of the liquid may also be contained. The pattern in the liquid matrix can also be formed by a dispersion liquid obtained by dispersing the first microparticles and / or the first pigment in the dispersion solvent.

[0067] The patterned liquid of the present invention can be produced, for example, by the following method. A method for manufacturing a liquid containing a pattern, characterized in that it includes using a nozzle to eject a pattern-forming material in which fine particles and / or pigments are dispersed in a dispersion solvent into a liquid substrate contained in a container, forming a pattern composed of the fine particles and / or pigments in the liquid substrate, and the liquid substrate is a pseudoplastic fluid. The above method for manufacturing a liquid containing a pattern is also included in the present invention.

[0068] According to the method for manufacturing a liquid containing a pattern of the present invention, a pattern-forming material in which fine particles and / or pigments are dispersed in a dispersion solvent is ejected using a nozzle into a liquid substrate contained in a container to form a pattern composed of the fine particles and / or pigments. The fine particles and / or pigments contained in the pattern-forming material form a pattern in the liquid substrate. The fine particles and pigments contained in the pattern-forming material are the same as the first fine particles and the first pigments described in the above liquid containing a pattern. In the present invention, the liquid substrate during pattern formation is a pseudoplastic fluid. Thus, patterns such as characters and drawings composed of fine particles and / or pigments can be stably formed in the liquid substrate. When the liquid substrate is a pseudoplastic fluid, compared with using a liquid that does not exhibit pseudoplasticity, a pattern of a desired shape can be formed without destroying the already formed pattern. Therefore, a liquid containing a pattern with a high degree of freedom in patterns such as color, taste, aroma, texture, and touch can be provided. For example: by making the fine particles contain pigments, flavoring substances, aroma components, etc., a spatial design of color, taste, and aroma can be achieved in the liquid substrate. In addition, by controlling the aggregability of the fine particles, a spatial design of texture or touch in the liquid substrate can also be implemented. In addition, as described above, since the liquid substrate is a pseudoplastic fluid, for example, even when the viscosity of the liquid substrate is low, the pattern formed in the liquid substrate is not easily moved and the stability of the pattern is good. In addition, when the viscosity of the liquid substrate is high, a pattern can be formed more stably in the liquid substrate, and in addition, the stability of the formed pattern becomes better.

[0069] In the manufacturing method of the present invention, the liquid substrate and its preferred embodiments are the same as those of the liquid substrate in the above liquid containing a pattern of the present invention. The liquid substrate is preferably a fluid that satisfies the above formula (I) within at least a certain range between a shear rate of 0.3 and 130 s -1 -1. The liquid substrate, for example, the shear rate obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity is 100 s -1The viscosity at 25 °C is preferably 4 mPa·s or more. As described above, the liquid matrix can be prepared, for example, by adding a thickening agent to a liquid such as water. As the thickening agent, a water-soluble thickening agent is preferred. The preferred form of the water-soluble thickening agent, the preferred concentration in the liquid matrix, etc. are the same as those of the patterned liquid of the present invention described above. In the manufacturing method of the present invention, the fine particles, pigments, and their preferred forms are also the same as those of the patterned liquid of the present invention described above.

[0070] The pattern-forming material is a liquid material for pattern formation obtained by dispersing fine particles and / or pigments in a dispersion solvent. The pattern-forming material can be regarded as a dispersion of fine particles and / or pigments. The pattern-forming material can be prepared by dispersing fine particles and / or pigments in a dispersion solvent. A liquid is used as the dispersion solvent. The dispersion solvent can be a pseudoplastic fluid or a liquid that does not exhibit pseudoplasticity, and a pseudoplastic fluid is preferred. As the dispersion solvent used in the pattern-forming material, liquids such as water, beverages, lotions, culture media, aqueous solutions, etc. used in the preparation of the above liquid matrix can be used. The dispersion solvent can be the same liquid as that used in the liquid matrix or a different liquid. The dispersion solvent can also contain a surfactant, etc.

[0071] When the above dispersion solvent is a pseudoplastic fluid, it is easier to suppress the diffusion of the dispersion solvent into the liquid matrix, so the shape of the pattern formed by the fine particles and / or pigments can be maintained in the liquid matrix for a long time. For example, by adding a thickening agent to the dispersion solvent, pseudoplasticity can be imparted. As the thickening agent, the above water-soluble thickening agent is preferred. The water-soluble thickening agent and its preferred form are the same as those of the water-soluble thickening agent used in the above liquid matrix. In one mode, the dispersion solvent preferably contains the above water-soluble thickening agent. As the water-soluble thickening agent, at least 1 kind selected from xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan is preferred. The content of the water-soluble thickening agent can be appropriately set in a manner that gives the desired pseudoplasticity to the dispersion solvent. In one mode, when the dispersion solvent contains a water-soluble thickening agent selected from at least 1 kind of xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan, the total concentration of the water-soluble thickening agent is preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.1% by weight. In one mode, the dispersion solvent preferably contains xanthan gum. When the dispersion solvent contains xanthan gum, the content of xanthan gum in the dispersion solvent is preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.1% by weight.

[0072] When the dispersion solvent is a pseudoplastic fluid, it can be confirmed by using at least two shear rates of a commercially available B-type viscometer well-known to those skilled in the art and the viscosities at these shear rates. Unless otherwise specified, the viscosity of the dispersion solvent refers to the viscosity measured by a B-type viscometer (for example, the rotational viscometer ViscoQC 300-L, Antonpaar). The dispersion solvent is preferably a liquid that exhibits pseudoplasticity at least at a temperature of 25 °C. In one embodiment, the dispersion solvent is preferably a fluid that exhibits pseudoplasticity within at least a certain range between shear rates of 10 and 129 s -1 between. In one embodiment, the dispersion solvent is preferably a fluid that exhibits pseudoplasticity within a shear rate range of 10 to 20 s -1 , more preferably within a shear rate range of 10 to 70 s -1 , and further preferably a fluid that exhibits pseudoplasticity between shear rates of 10 and 129 s -1 between.

[0073] When the dispersion solvent is a pseudoplastic fluid, the fluid preferably satisfies the above formula (I) (log(η1 / η2) / log(γ1 / γ2) ≤ -0.12) within at least a certain range between shear rates of 0.3 and 130 s -1 between, and more preferably satisfies the above formula (I) within at least a certain range when the shear rate is between 1 and 130 s -1 (1 ≤ γ2 < γ1 ≤ 130). This is because the stability of the formed pattern is better. In one embodiment, for the dispersion solvent, within the range including a shear rate of 10 to 70 s -1 , the value of the left side (log(η1 / η2) / log(γ1 / γ2)) of the above formula (I) is preferably -2 or more and -0.12 or less (-2 ≤ log(η1 / η2) / log(γ1 / γ2) ≤ -0.12), more preferably -1.5 or more and -0.27 or less (-1.5 ≤ log(η1 / η2) / log(γ1 / γ2) ≤ -0.27), and further preferably -1 or more and -0.3 or less (-1 ≤ log(η1 / η2) / log(γ1 / γ2) ≤ -0.3). In one embodiment, for the pseudoplastic fluid, at a shear rate of 10 to 70 s -1 (γ1 = 129, γ2 = 10) (preferably 10 to 129 s -1 (γ1 = 129, γ2 = 10)), the value of the left side of the above formula (I) is preferably -2 or more and -0.12 or less, more preferably -1.5 or more and -0.27 or less, and further preferably -1 or more and -0.3 or less.

[0074] When the dispersion solvent is a pseudoplastic fluid, the dispersion solvent, for example, the shear rate obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity is 100 s -1The viscosity (calculated value) at 25°C is preferably 3 to 40 mPa·s, more preferably 4 to 12 mPa·s. This is because when the shear rate of the dispersion solvent is 100 s -1 and the viscosity at 25°C is 3 mPa·s or more, the pattern formed in the liquid matrix is more stable. In addition, when a pattern is formed in the liquid matrix using the pattern-forming material, the pattern can be formed more stably. When the shear rate is 100 s -1 and the viscosity at 25°C is 40 mPa·s or less, the ejection from the nozzle is good, which is preferred. The viscosity at 25°C when the shear rate is 100 s -1 can be obtained by the same method as the viscosity of the above liquid matrix.

[0075] When the dispersion solvent is a pseudoplastic fluid, the viscosity of the fluid at 25°C when the shear rate is 10 s -1 is preferably 5 to 110 mPa·s, more preferably 7 to 30 mPa·s, and further preferably 9 to 26 mPa·s. When the shear rate of the dispersion solvent is 10 s -1 and the viscosity at 25°C is within the above range, the stability of the pattern in the liquid matrix becomes better.

[0076] The viscosity of the above dispersion solvent measured by a tuning fork vibration viscometer (e.g., SV-10, manufactured by A&D Company) is preferably 0.8 mPa·s or more and 6 Pa·s or less at 25°C. When the viscosity of the dispersion solvent measured by a tuning fork vibration viscometer is 0.8 mPa·s or more and 6 Pa·s or less at 25°C, it is easier to suppress the diffusion of the dispersion solvent into the liquid matrix, and the shape of the pattern formed by the fine particles and / or pigments can be maintained in the liquid matrix for a longer time. From this viewpoint, the above viscosity of the dispersion solvent at 25°C is more preferably 3 Pa·s or less, and further preferably 1 Pa·s or less. In one mode, the viscosity of the dispersion solvent measured by a tuning fork vibration viscometer is more preferably 0.8 mPa·s or more and 3 Pa·s or less, and further preferably 0.8 mPa·s or more and 1 Pa·s or less at 25°C. In addition, in one mode, the above viscosity of the dispersion solvent is preferably 1 mPa·s or more and 100 mPa·s or less, more preferably 1 mPa·s or more and 50 mPa·s or less at 25°C. In one mode, when the dispersion solvent is a liquid that does not exhibit pseudoplasticity, the viscosity measured by a tuning fork vibration viscometer (25°C) is preferably within the above range.

[0077] In one mode, the ratio of the density of the fine particles to the density of the dispersion solvent used in the pattern-forming material (density of the fine particles / density of the dispersion solvent) is preferably 0.9 or more and 1.1 or less. In addition, the ratio of the density of the dispersion solvent to the density of the liquid matrix (density of the dispersion solvent / density of the liquid matrix) is preferably 0.9 or more and 1.1 or less. When both the ratio of the density of the microparticles to the density of the dispersion solvent and the ratio of the density of the dispersion solvent to the density of the liquid matrix are 0.9 or more and 1.1 or less, floating or precipitation of the pattern formed by the microparticles and / or pigment together with the dispersion solvent in the liquid matrix can be suppressed. From this perspective, the above density ratios are more preferably 0.92 or more and 1.08 or less, and further preferably 0.95 or more and 1.05 or less.

[0078] In one mode, the ratio of the density of the pattern-forming material to the density of the liquid matrix (density of the pattern-forming material / density of the liquid matrix) is preferably 0.9 or more and 1.1 or less, more preferably 0.92 or more and 1.08 or less, and further preferably 0.95 or more and 1.05 or less. When the ratio of the density of the pattern-forming material to the density of the liquid matrix is within the above range, the pattern can be formed more stably.

[0079] Before the above-mentioned microparticles and / or pigment are ejected into the liquid matrix, they are dispersed in the dispersion solvent. The pattern-forming material in which the microparticles and / or pigment are dispersed is ejected into the liquid matrix using a nozzle. In this way, the dispersion solvent can eject the microparticles and / or pigment into the liquid matrix using a nozzle, thereby constituting a liquid material containing the microparticles and / or pigment. When the microparticles contain a pigment component (when coloring) or the pattern-forming material contains a pigment, the pattern-forming material can function as a pattern-forming ink. The method of dispersing the microparticles and / or pigment in the dispersion solvent is not particularly limited and can be implemented by a known method such as stirring.

[0080] When the above-mentioned pattern-forming material contains microparticles, the volume percentage concentration of the microparticles in the material is not particularly limited, preferably 0.05% by volume or more and 50% by volume or less, more preferably 0.1% by volume or more and 40% by volume or less, and further preferably 0.5% by volume or more and 30% by volume or less. When the above-mentioned pattern-forming material contains a pigment, the volume percentage concentration of the pigment in the material is not particularly limited, preferably 0.01% by volume or more and 30% by volume or less, more preferably 0.05% by volume or more and 20% by volume or less, and further preferably 0.1% by volume or more and 10% by volume or less.

[0081] Here, the "volume percentage concentration of the microparticles in the pattern-forming material" can be measured by the Coulter counter method.

[0082] In addition, the material for pattern formation is not particularly limited. One kind of material for pattern formation may be ejected into the liquid substrate, or two or more different materials for pattern formation, such as at least one of fine particles, pigments, and dispersion solvents, may be ejected into the liquid substrate simultaneously or successively.

[0083] From the viewpoint of maintaining the pattern composed of fine particles and / or pigments in the liquid substrate for a long time, the dispersion solvent is preferably a solvent suitable for the liquid substrate, and may be the same liquid as the liquid substrate or a liquid similar to the liquid substrate. The following will explain this in detail.

[0084] The absolute value of the difference in water content between the above-mentioned dispersion solvent and the above-mentioned liquid substrate is preferably 0% or more and 50% or less. By combining liquids with no difference in water content, the flavor or color can be changed without changing the taste or texture. By combining liquids with different water contents, the taste or texture can be changed. The absolute value of the difference between the two is more preferably 25% or less, and even more preferably 15% or less. In addition, usually the water content of the dispersion solvent is lower than the water content of the liquid substrate.

[0085] Herein, the "water content of the liquid" can be measured by the drying loss method. That is, after weighing the weight of the water-containing sample (here the liquid), then the sample is placed in a constant temperature drying oven at a specified temperature to evaporate the water, and the water content can be measured by measuring the change in the weight of the sample.

[0086] In the present invention, in the liquid substrate onto which the material for pattern formation is ejected, the above-mentioned fine particles and / or pigments (second fine particles and / or second pigments) may also be dispersed. The liquid substrate may also not contain the second fine particles and / or second pigments. When the liquid substrate contains the second fine particles, the volume percentage concentration of the fine particles in the liquid substrate can be set to exceed 0% by volume and be 74% by volume or less, preferably 0.1% by volume or more and 70% by volume or less, more preferably 1% by volume or more and 60% by volume or less, and even more preferably 5% by volume or more and 50% by volume or less. In addition, the pattern formation in the liquid substrate is not affected by the concentration of the second fine particles in the liquid, so its concentration can be freely set. When the same particles are arranged in the densest manner in the liquid, its structure is a hexagonal closest packing structure, and the packing rate at this time can be calculated to be about 74% by volume. Therefore, the maximum volume percentage concentration of the second fine particles in the liquid substrate is 74% by volume.

[0087] Using a nozzle, the above-described pattern-forming material is ejected into a liquid substrate accommodated in a container, and a pattern composed of the above-described fine particles and / or pigments (first fine particles and / or first pigments) is formed in the liquid substrate. The formation of the pattern is usually carried out at a temperature at which the liquid substrate exhibits pseudoplasticity. The nozzle is preferably a nozzle whose position can be controlled. The nozzle whose position can be controlled is preferably a nozzle whose three-dimensional position and / or the ejection flow rate of the pattern-forming material to be ejected can be controlled by, for example, a control device described later.

[0088] The above-described nozzle is a cylindrical body with a hollow inside and openings at both ends. The pattern-forming material is introduced from the base end of the nozzle, flows through the hollow inside the nozzle, and is ejected from the front end of the nozzle. The nozzle is preferably controlled in its three-dimensional position and the ejection flow rate of the pattern-forming material ejected from the front end of the nozzle by a control device of a manufacturing device for a liquid containing a pattern described later. In addition, the number of nozzles used is not particularly limited and may be one or more.

[0089] The above-described nozzle is preferably movable freely on multiple axes (for example, 3 or more axes and 8 or less axes). Thereby, as a pattern composed of the pattern-forming material, a three-dimensional pattern can be easily formed. In addition, not only can the nozzle be moved, but also the container accommodating the liquid can be moved.

[0090] The opening shape of the front end of the above-described nozzle is not particularly limited, and is preferably circular, elliptical, triangular, rectangular, square, rhombic, V-shaped, U-shaped, or C-shaped.

[0091] The diameter of the above-described nozzle is not particularly limited, and is preferably 0.1 mm or more and 5.0 mm or less, more preferably 0.2 mm or more and 3.0 mm or less, and further preferably 0.2 mm or more and 1.0 mm or less.

[0092] Here, the so-called "diameter of the nozzle" refers to the length measured at the longest part of the opening at the front end of the nozzle. For example, when the opening shape at the front end of the nozzle is circular, it represents the diameter; when it is elliptical, it represents the major axis length; when it is square, it represents the length of the longer diagonal. In addition, when the opening shape at the front end of the nozzle is a shape with a concave part such as V-shaped, U-shaped, or C-shaped, it represents the diameter of the smallest circle surrounding the shape.

[0093] The ejection flow rate (ejection speed) of the pattern-forming material ejected from the nozzle is preferably 0.1 μL / s or more and 200 mL / s or less, more preferably 0.2 μL / s or more and 50 mL / s or less, further preferably 0.3 μL / s or more and 20 mL / s or less, still more preferably 0.3 μL / s or more and 10 mL / s or less, particularly preferably 0.4 μL / s or more and 5 μL / s or less, and most preferably 0.5 μL / s or more and 3 μL / s or less. In addition, the ejection flow rate (ejection speed) of the pattern-forming material ejected from the nozzle is sometimes hereinafter simply referred to as "the ejection flow rate of the nozzle".

[0094] The moving speed of the nozzle during drawing is preferably 0.1 mm / s or more and 250 mm / s or less, more preferably 0.1 mm / s or more and 150 mm / s or less, further preferably 0.5 mm / s or more and 130 mm / s or less, particularly preferably 1 mm / s or more and 100 mm / s or less, and most preferably 5 mm / s or more and 60 mm / s or less.

[0095] The moving speed of the nozzle from a certain pattern (line) to the next pattern (line) is preferably 0.1 mm / s or more and 250 mm / s or less, more preferably 0.1 mm / s or more and 150 mm / s or less, further preferably 0.5 mm / s or more and 130 mm / s or less, particularly preferably 1 mm / s or more and 100 mm / s or less, and most preferably 5 mm / s or more and 100 mm / s or less.

[0096] The acceleration of the nozzle during drawing is preferably 0.000001 mm / s 2 or more and 250 mm / s 2 or less, more preferably 0.000001 mm / s 2 or more and 150 mm / s 2 or less, further preferably 0.1 mm / s 2 or more and 130 mm / s 2 or less, particularly preferably 1 mm / s 2 or more and 100 mm / s 2 or less, most preferably 1 mm / s 2 or more and 20 mm / s 2 or less.

[0097] The acceleration of the nozzle from a certain pattern (line) to the next pattern (line) is preferably 0.000001 mm / s 2 or more and 250 mm / s 2 or less, more preferably 0.000001 mm / s 2 or more and 150 mm / s 2 or less, further preferably 0.1 mm / s2 130 mm / s or more 2 and preferably 1 mm / s or less, particularly preferably 1 mm / s 2 100 mm / s or more 2 and preferably 1 mm / s or less, most preferably 1 mm / s 2 50 mm / s or more 2 and preferably 50 mm / s or less.

[0098] The pattern formed from the above-described pattern-forming material may be any one of a one-dimensional pattern (line), a two-dimensional pattern (plane), and a three-dimensional pattern (solid). The type of the pattern is not particularly limited. For example, marks such as characters, lines, drawings, and other visually recognizable patterns can be cited; patterns that generate taste, aroma, texture, touch, etc.; and patterns that generate these sensations in combination. The pattern in the liquid matrix may be in contact with the inner side of the container containing the liquid matrix, or may not be in contact with the inner side of the container. The pattern may also float in the liquid matrix.

[0099] The pattern drawn with the above-described pattern-forming material may also contain a straight line portion and / or a curved line portion, and specifically, marks such as characters or drawings can be cited. In addition, the lines drawn with the above-described pattern-forming material may be straight lines, curved lines, or may contain one or more straight line portions and / or one or more curved line portions.

[0100] The liquid matrix for forming the pattern is contained in a container. The container is not particularly limited and can be appropriately selected according to the liquid matrix. For example, when the obtained liquid containing the pattern is a beverage, a container that can hold the beverage can be used. In one mode, from the viewpoint of visually recognizing the pattern from the outside, a transparent container is preferably used. As a transparent container that can hold a beverage, for example, a transparent glass, a cup made of transparent glass; a transparent drinking cup made of plastic, etc. can be cited.

[0101] The above-described liquid matrix is contained in a container (for example, a glass or a cup), and the length of the above-described nozzle is preferably at least longer than the depth of the above-described liquid matrix contained in the above-described container. Thus, a pattern composed of the pattern-forming material can be formed at any place in the liquid using the nozzle.

[0102] In one mode, the above-described pattern-forming material forms a pattern or a line in the liquid matrix in a fixed or uncured state to form a pattern. In one mode, it is preferable that the pattern formed by the pattern-forming material maintains a fixed or uncured state in the liquid matrix, and more preferably, it exists in a suspended state in the liquid matrix.

[0103] The above-described material for forming a pattern is not particularly limited as long as it is a liquid fluid. As the liquid containing the pattern, it can be appropriately selected according to the target to be manufactured. The material for forming a pattern is preferably a pseudoplastic fluid. Regarding the liquid matrix, it is not particularly limited as long as it is a pseudoplastic fluid, and it can be appropriately selected according to the use of the liquid containing the pattern to be manufactured.

[0104] Hereinafter, as the liquid containing the pattern, the material for forming a pattern and the liquid matrix that are preferable when manufacturing a beverage or cosmetic provided with a pattern, or a liquid containing a pattern of cells will be described, and the method for forming a pattern that is preferable in these cases will be described.

[0105] In addition, the following features can also be appropriately applied in uses other than the above.

[0106] In one mode, as the above-described material for forming a pattern, a nozzle capable of controlling the position is used, and a material for forming a pattern (hereinafter referred to as a microparticle dispersion material) in which microparticles containing an organic substance (preferably an edible organic substance) are dispersed in a dispersion solvent is ejected into a liquid matrix to form a pattern (pattern or line) composed of the above microparticles.

[0107] The formation of a pattern in a liquid matrix can be carried out, for example, by using a microparticle dispersion material as the material for forming a pattern and using the manufacturing apparatus for a liquid containing a pattern described below. In the present invention, the manufacturing apparatus for a liquid containing a pattern that can be used (hereinafter, sometimes simply referred to as a manufacturing apparatus) will be described.

[0108] The above-described manufacturing apparatus is a manufacturing apparatus for a liquid containing a pattern that forms a pattern in a liquid matrix. As the above-described manufacturing apparatus, it preferably includes: a tank that accommodates a material for forming a pattern in which microparticles and / or pigments are dispersed in a dispersion solvent, a nozzle that ejects the material for forming a pattern, a pump that feeds the material for forming a pattern to the nozzle, and a control device that controls the position of the nozzle and the ejection flow rate of the material for forming a pattern ejected from the nozzle. With such a manufacturing apparatus, the material for forming a pattern can be supplied from the tank to the nozzle by a pump, and the material for forming a pattern can be ejected from the nozzle to an arbitrary place of the target liquid (liquid matrix) while controlling the position of the nozzle and the ejection flow rate of the material for forming a pattern by the control device. In addition, the ejection flow rate of the material for forming a pattern can be controlled by a change in the pump pressure or a change in the pressure inside the nozzle caused by applying a voltage to a piezoelectric element such as a piezoelectric element provided in the nozzle portion. Thus, a pattern is designed using software such as CAD, and the nozzle is controlled based on this design, whereby a pattern can be automatically formed in the liquid. Therefore, by using the above-described manufacturing apparatus, a liquid containing a pattern can be automatically manufactured. That is, a liquid containing a pattern with a high degree of freedom in design in which a pattern that can produce sensations such as color, taste, aroma, texture, and touch is formed in the liquid can be manufactured.

[0109] The pattern-forming material contained in the above-described tank can also be supplied to the nozzle through a liquid supply pipe. The tank only needs to be a container that can hold the pattern-forming material, and there is no particular limitation. The tank can be separately provided from the pump and the nozzle, or can be integrated with the pump and the nozzle. In addition, multiple tanks can be provided according to the type of the pattern-forming material.

[0110] The above-described nozzle is as described above. In addition, the nozzle can also be connected to a piezoelectric element such as a piezoelectric (piezoelectric) element, and the pressure inside the nozzle can be changed by applying a voltage to the piezoelectric element, so as to control the ejection flow rate of the pattern-forming material from the nozzle.

[0111] The above-described pump only needs to be able to feed the pattern-forming material to the nozzle, and there is no particular limitation. For example, an injection pump, a peristaltic pump, etc. can be used.

[0112] The above-described control device can also be provided with a multi-axis mechanism (for example, a mechanism with 3 or more axes and 8 or less axes) that is connected to the nozzle and moves its position. Thereby, the nozzle can be controlled in multiple axes, so the nozzle can be moved three-dimensionally. That is, a three-dimensional pattern can be easily formed. As the multi-axis mechanism, for example, a gantry system (for example, 3 axes) or a robotic arm (for example, 8 axes) can be used.

[0113] In addition, in order to control the ejection flow rate of the pattern-forming material, the above-described control device can also control the pump pressure and can also control the voltage applied to the piezoelectric element provided in the nozzle portion.

[0114] Furthermore, the above-described control device can also be provided with a control processing device that performs control processing on the nozzle, the pump, the multi-axis mechanism, etc. The control processing device is composed of, for example, a software program for implementing various processes such as control processing, a CPU (Central Processing Unit) that executes the software program, and various hardware (such as a storage device) controlled by the CPU. The software program (for example, a control program using 3D-CAD data) or data required for the operation of the control processing device is stored in the storage device. In addition, the control processing device can be arranged together with the multi-axis mechanism at the place where the liquid containing the pattern is manufactured (for example, in the same store), and the devices related to at least a part of the functions of the control processing device can also be dispersedly arranged at a place different from the place where the liquid containing the pattern is manufactured (for example, in the cloud).

[0115] The above-described manufacturing device can also be further provided with a stage (Stage) on which a container for accommodating the liquid substrate can be set. The stage can also be configured to be movable, and the control device can move not only the nozzle but also the stage, that is, while moving the liquid substrate accommodated in the container, eject the pattern-forming material from the nozzle into the liquid substrate.

[0116] Figure 1Conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid that forms a pattern in a liquid substrate. Figure 1 The shown manufacturing apparatus 100 for a patterned liquid includes: a plurality of tanks 110 that accommodate a pattern-forming material 10 (for example, a microparticle dispersion material obtained by dispersing microparticles 11 in a dispersion solvent 12), a nozzle 120 that ejects the pattern-forming material 10, a pump 130 that feeds the pattern-forming material 10 to the nozzle 120, a control device 140 having an angle adjustment mechanism 153 that changes the angle (posture) of the nozzle 120, a stage 150 on which a container 40 that accommodates a liquid substrate 20 is provided, a liquid feed pipe 151 that connects the tank 110 and the pump 130, and a liquid feed pipe 152 that connects the pump 130 and the nozzle 120. The control device 140 controls the position and angle of the nozzle 120 and the ejection flow rate of the pattern-forming material 10 ejected from the nozzle 120. The angle adjustment mechanism 153 includes at least a spherical member that can rotate in the vertical and horizontal directions, and can freely change the inclination of the nozzle 120 under the control of the control device 140. According to the manufacturing apparatus 100, a pattern 30 composed of the pattern-forming material 10 (for example, microparticles 11) can be automatically formed in the liquid substrate 20. A plurality of different pattern-forming materials 10 can be accommodated in the plurality of tanks 110, and a plurality of pattern-forming materials 10 can be ejected from the nozzle 120 simultaneously or sequentially. In addition, the manufacturing apparatus 100 can include a plurality of nozzles 120, and a plurality of pattern-forming materials 10 can be ejected from the plurality of nozzles 120 simultaneously or sequentially.

[0117] Figure 2 Conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid that uses a gantry-type device. Figure 2The manufacturing apparatus 200 for the patterned liquid shown includes: a tank 210 that houses a material for forming a pattern (not shown, for example, a microparticle dispersion material in which microparticles are dispersed in a dispersion solvent), a nozzle 220 that ejects the material for forming a pattern, a stage 250 that sets a container 40 housing the liquid substrate 20, a gantry system 260 that is a multi-axis mechanism as a control device (not shown), and an angle adjustment mechanism 253 that is a control device for changing the angle (posture) of the nozzle 220. The angle adjustment mechanism 253 includes a spherical member that can rotate at least in the vertical and horizontal directions, and can freely change the inclination of the nozzle 220 under the control of the control device. In addition, a pump (not shown) for feeding the material for forming a pattern to the nozzle 220 and an x-axis drive motor (not shown) of the gantry system 260 are integrally provided on the tank 210. The gantry system 260 is a three-axis drive mechanism, and includes an x-axis rail 261 that supports the tank 210 so as to be movable in the x-axis direction, a z-axis rail 262 that supports the x-axis rail 261 so as to be movable in the z-axis direction, a z-axis drive motor 263 that drives the x-axis rail 261 supported by the z-axis rail 262 in the z-axis direction, a y-axis rail 264 that supports the z-axis rail 262 so as to be movable in the y-axis direction, and a y-axis drive motor 265 that drives the z-axis rail 262 supported by the y-axis rail 264 in the y-axis direction. Under the control of the control device, the nozzle 220 can be freely moved in three axes. The control device can control the position of the nozzle 220 through the gantry system 260, control the angle of the nozzle 220 through the angle adjustment mechanism 253, and further control the ejection flow rate of the material for forming a pattern ejected from the nozzle 220. Through the manufacturing apparatus 200, a pattern 30 composed of the material for forming a pattern (for example, microparticles) can also be automatically formed in the liquid substrate 20.

[0118] Figure 3 It is a conceptual diagram showing an example of a manufacturing apparatus for a patterned liquid using a robotic arm. Figure 3The manufacturing apparatus 300 for the patterned liquid shown includes: a tank 310 that accommodates a material for forming a pattern (not shown, for example, a microparticle dispersion material in which microparticles are dispersed in a dispersion solvent), a nozzle 320 that ejects the material for forming a pattern, a robotic arm 360 that is a multi-axis mechanism as a control device (not shown), and an angle adjustment mechanism 353 of the control device that changes the angle (posture) of the nozzle 320. The angle adjustment mechanism 353 includes a spherical member that can rotate at least in the vertical and horizontal directions, and can freely change the inclination of the nozzle 320 under the control of the control device. In addition, a pump (not shown) for feeding the material for forming a pattern to the nozzle 320 is integrally provided in the tank 310. The robotic arm 360 is, for example, an 8-axis drive mechanism, and under the control of the control device, the nozzle 320 can freely move on 8 axes. The control device controls the position of the nozzle 320 through the robotic arm 360, and at the same time controls the angle of the nozzle 320 through the angle adjustment mechanism 353, and further controls the ejection flow rate of the material for forming a pattern ejected from the nozzle 320. Through the manufacturing apparatus 300, a pattern 30 formed of a material for forming a pattern (for example, microparticles) can also be automatically formed in the liquid matrix 20.

[0119] The above example of using a manufacturing apparatus to form a pattern in a liquid matrix is described, but the method of forming a pattern composed of the above microparticles and / or pigments (first microparticles and / or first pigments) in a liquid matrix is not limited to this. By the method of the present invention, a patterned liquid in which a pattern composed of microparticles and / or pigments is formed in a liquid matrix can be obtained. In a preferred embodiment, a beverage is used as the liquid matrix and an edible material for forming a pattern is used, and a beverage containing a pattern can be obtained.

[0120] As described above, by using a pseudoplastic fluid as the matrix of the patterned liquid, a pattern can be stably formed in the matrix by microparticles and / or pigments. In addition, a patterned liquid with good pattern stability can be obtained. The present invention also includes the application of a pseudoplastic fluid as the matrix of the patterned liquid. The pseudoplastic fluid and its preferred embodiments are the same as those of the liquid matrix in the above-mentioned patterned liquid of the present invention.

[0121] In this specification, a numerical range represented by a lower limit value and an upper limit value, that is, "lower limit value to upper limit value" includes these lower limit values and upper limit values. For example, the range represented by "1 to 2" means 1 or more and 2 or less and includes 1 and 2. In this specification, the upper limit and the lower limit can be ranges based on any combination.

[0122] In addition, the academic documents and patent documents described in this specification are incorporated into this specification as references.

[0123] This specification also discloses the following patterned liquid and its manufacturing method. <1>A liquid with a pattern, characterized in that the liquid matrix contains a pattern formed by fine particles and / or pigments, the liquid matrix is a liquid containing at least one water-soluble thickener selected from xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan, and the liquid matrix is contained in a container. <2>The liquid with a pattern according to <1> above, characterized in that the total concentration of the water-soluble thickener in the liquid matrix is 0.01 to 2% by weight, preferably 0.02 to 1% by weight. <3>The liquid with a pattern according to <1> or <2> above, characterized in that it is a beverage. <4>A method for manufacturing a liquid with a pattern, characterized in that it includes spraying a pattern-forming material in which fine particles and / or pigments are dispersed in a dispersion solvent using a nozzle into a liquid matrix contained in a container to form a pattern composed of the fine particles and / or pigments in the liquid matrix, and the liquid matrix is a liquid containing at least one water-soluble thickener selected from xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan. <5>The manufacturing method according to <4> above, characterized in that the total concentration of the water-soluble thickener in the liquid matrix is 0.01 to 2% by weight, preferably 0.02 to 1% by weight. In the liquid with a pattern and the method for manufacturing a liquid with a pattern of the present disclosure, the preferred forms of the liquid matrix and the water-soluble thickener are the same as their preferred forms in the liquid with a pattern and the method for manufacturing a liquid with a pattern of the present invention above. For example, as the liquid matrix, a liquid containing water is preferred, and a liquid based on water is more preferred. The preferred forms of the fine particles, pigments, and them are the same as those of the liquid with a pattern and the method for manufacturing a liquid with a pattern of the present invention above. In the present disclosure, the dispersion solvent, the pattern-forming material, the method for forming the pattern, or their preferred forms, etc. are the same as those of the method for manufacturing a liquid with a pattern of the present invention above. For example, the dispersion solvent preferably contains the water-soluble thickener. Examples

[0124] Hereinafter, the present invention will be described in more detail based on examples. In addition, the present invention is not limited to these examples.

[0125] In the examples, the density of the liquid was measured by a densitometer DMA4500M (manufactured by Antonpaar). In the examples, when not otherwise specified, the operations were carried out at 25°C.

[0126] <Reference Example 1> In order to manufacture a liquid with a pattern, the following device was trial-produced. Figure 4Schematic perspective view showing a device fabricated in Reference Example 1 for manufacturing a patterned liquid.

[0127] As Figure 4 shown, at the front end of the arm of a collaborative robot 460 (COBOTTA, a collaborative robot manufactured by DENSOWAVE Co., Ltd.), a syringe extrusion device 470 composed of a stepping motor and a lead screw is equipped. The syringe extrusion device 470 is designed to be extruded at various speeds according to an external input. On the syringe extrusion device 470, syringes of various sizes can be equipped. In the following examples, as the syringe 480, a syringe with an N727 pst-3 (inner diameter: 0.21 mm) installed as the nozzle 420 on a plunger 1010TLL (capacity: 10 mL, Hamilton, USA) is used. The maximum ejection flow rate (maximum ejection speed) at this time is 0 mL / s to 200 mL / s. Also, the maximum speed of the nozzle movement speed is 150 mm / s, and the minimum speed is 0.15 mm / s. In addition, when the nozzle movement speed is α mm / s, the acceleration of the nozzle movement has an upper limit: α mm / s 2 , lower limit: 0.000001 mm / s 2 . The device fabricated in Reference Example 1 can eject a liquid pattern-forming material such as ink from the nozzle 420.

[0128] <Preparation Example 1> Prepare a carboxymethyl cellulose (CMC) dispersion having pseudoplasticity. Since the degree of etherification is as low as 0.20 (mol / C6) to 0.30 (mol / C6), its solubility in water is low, and this carboxymethyl cellulose (Japanese: Sunrose (registered trademark) SLD-F1, manufactured by Nippon Paper Industries Co., Ltd.) is suspended in 1000 g of water so that the final concentration (content) reaches 2% by weight. The resulting dispersion is turbid. Using an ultra-high pressure wet atomization device, the Starburst system (HJP-25001, manufactured by Sugino Machine Co., Ltd.), the suspension is mechanically and uniformly dispersed by causing it to collide obliquely at high speed. The carboxymethyl cellulose (SLD-F1) dispersion treated three times by the Starburst system is clear, confirming uniform dispersion.

[0129] <Example 1> Using the device shown in Reference Example 1, a liquid containing a meaningful pattern was manufactured by observing from the side of the container. At this time, the influence of different thickeners on the stability of the pattern was studied.

[0130] As the liquid (liquid matrix) to be drawn, CMC-a is prepared. In the preparation of CMC-a, a dispersion of carboxymethyl cellulose (Japanese: Sunrose (registered trademark) SLD-F1, manufactured by Nippon Paper Industries Co., Ltd.) prepared in Preparation Example 1 is used. The dispersion of carboxymethyl cellulose prepared in Preparation Example 1 is suspended in an aqueous glycerol solution such that the final concentration of carboxymethyl cellulose reaches 0.5% by weight. The resulting suspension of carboxymethyl cellulose is used as CMC-a. The final concentration of glycerol in the liquid CMC-a to be drawn is 20% by weight. The density of CMC-a (25 °C) is 1.05 g / mL.

[0131] In addition, outside of CMC-a, the liquid CMC-b to be drawn is separately prepared. In the preparation of CMC-b, carboxymethyl cellulose (Japanese: Sunrose (registered trademark) FJ08HC, manufactured by Nippon Paper Industries Co., Ltd.) is suspended in an aqueous sugar solution such that the final concentration reaches 0.5% by weight. The resulting suspension of carboxymethyl cellulose is used as CMC-b. The final concentration of sugar in the liquid CMC-b to be drawn is 13% by weight. The density of CMC-b (25 °C) is 1.05 g / mL.

[0132] By combining a B viscometer LVDV2T (manufactured by Brookfield Engineering Laboratories, Inc.) and a UL low-viscosity transformer kit, the relationship between the viscosity η and the shear rate γ of CMC-a and CMC-b at 25 °C is measured. In addition, it is measured for 1 minute at the rotational speeds of 1 rpm, 2 rpm, 5 rpm, 10 rpm, or 20 rpm of the rotating shaft, respectively.

[0133] Figure 5 is a graph showing the relationship between the viscosity and the shear rate of CMC-a and CMC-b (square: CMC-a, circle (〇): CMC-b). Figure 5 The graph shown is a double-logarithmic graph of the shear rate and the viscosity represented on a logarithmic scale. Figure 5 and those described later Figures 7 to 12 、 Figure 17 and Figure 24 In the graph shown in, the vertical axis represents the logarithm of the viscosity (mPa·s), and the horizontal axis represents the logarithm of the shear rate (s -1 ). As Figure 5 shown, pseudoplasticity in which the viscosity decreases depending on the shear rate is confirmed in CMC-a. On the other hand, a state of a Newtonian fluid in which the viscosity remains constant regardless of the shear rate is confirmed in CMC-b. The Figure 5 slope of the double-logarithmic graph shown in is obtained by the following calculation formula (I). Slope = log(η1 / η2) / log(γ1 / γ2) Formula (I) The right side of the above calculation formula (I) can also be expressed as (log 10 η1 - log 10 η2) / (log 10 γ1 - log 10 γ2). In the above calculation formula (I), η1 represents the viscosity (mPa·s) of the fluid at the shear rate γ1 (s -1 ), and η2 represents the viscosity (mPa·s) of the fluid at the shear rate γ2 (s -1 ). γ2 < γ1. The viscosity is the viscosity at 25°C. Through the above calculation formula (I), the slope of the straight line connecting the two points (logγ1, logη1) and (logγ2, logη2) can be obtained.

[0134] Regarding the slope obtained from the above calculation formula, it is -0.228 for CMC-a and -0.064 for CMC-b. The above slope of CMC-a is Figure 5 the slope under the shear rates of 1 - 12 s -1 (γ1 = 12 (s -1 ), γ2 = 1 (s -1 )) of the chart shown. The above slope of CMC-b is Figure 5 the slope under the shear rates of 1 - 24 s -1 (γ1 = 24 (s -1 ), γ2 = 1 (s -1 )) of the chart shown. In addition, regarding the viscosity at 25°C at the shear rate of 100 s -1 obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity, it is 30 mP·s for CMC-a and 20 mP·s for CMC-b.

[0135] Next, a pattern is drawn in these liquids to be drawn on. To draw a pattern, an ink in which microparticles are dispersed in a liquid is prepared. The ink is a water suspension of red polystyrene microparticles with a diameter of 1 μm (Polystyrene Red Dyed Microsphere 1.00 μm, density 1.05 g / mL, manufactured by Polysciences) suspended in an aqueous glycerol solution so that the final concentration of the microparticles reaches 1% by weight and the final concentration of glycerol reaches 20% by weight. The viscosity (25°C) of this ink is 2 mP·s, and the density is 1.05 g / mL. The viscosity (25°C) of the ink is measured using a tuning fork vibration viscometer SV-10 (manufactured by A&D). The density of the ink is measured by a densitometer DMA4500M (manufactured by Antonpaar).

[0136] Put CMC-a and CMC-b into a transparent container, and use the device prepared in Reference Example 1 to draw the words "Love" and a heart-shaped pattern in these liquids. The ink is contained in the syringe 480 of the above device, and the ink is ejected through the nozzle 420 for drawing. Specifically, first draw the word "Love", and then draw a heart-shaped pattern around the word. At this time, the moving speed of the nozzle during drawing is 50 mm / s, and the acceleration during drawing is 2 mm / s 2 , and the moving speed until the next line is 90 mm / s, and the acceleration until the next line is 18 mm / s 2 . In addition, the ink ejection flow rate is drawn at 1.7 μL / s.

[0137] Figure 6 A and Figure 6 B are the photos taken from the side of the container in Example 1 of the pattern drawn in the liquid (with the drawing surface as the front). Figure 6 A is the photo of the pattern drawn in CMC-a, Figure 6 B is the photo of the pattern drawn in the liquid CMC-b. Compared with CMC-b, on the side of CMC-a, a stable pattern can be formed in the liquid. Specifically, on the side of CMC-a, the above-mentioned words and heart shape formed by fine particles in the liquid are not affected by the movement of the nozzle for drawing the next line during drawing and are in a stable state. On the side of CMC-a, the pattern made during drawing is not easily disordered, and a clearer heart shape can be formed. In addition, on the side of CMC-a, the formed pattern is not easily changed. This result indicates that among the liquids showing pseudoplasticity, a more stable pattern can be formed compared with the liquids not showing pseudoplasticity.

[0138] <Example 2> Using the above device, by observing from the side of the container, a liquid containing a meaningful pattern is manufactured, and the viscosity physical properties of the liquid that makes the pattern stable are studied. As the liquid (liquid matrix) to be drawn, specimens T1 to T14 are prepared. In the preparation of the specimens, the thickeners gum arabic, carboxymethyl cellulose, xanthan gum, and gellan gum commonly used in foods are used. These are water-soluble thickeners. These thickeners are suspended in water at various concentrations to prepare 14 kinds of liquids with changed viscosity characteristics as specimens T1 to T14. The density of specimens T1 to T14 is 1.05 g / mL. At this time, in some of the liquids, sugar is added so that the density reaches 1.05 g / mL. The thickeners used in the preparation of specimens T1 to T14 are shown in Table 1. The thickener concentrations and sugar concentrations in specimens T1 to T14 are shown in Table 1.

[0139] The thickeners used in the preparation of specimens T1 to T14 are as follows. Sample T1: Gum Arabic (trade name: Instantgum AA, manufactured by Nexira) Sample T2: Gum Arabic (trade name: Instantgum BA, manufactured by Nexira) Sample T3: carboxymethyl cellulose (trade name BiNFi-s TFo-10002, manufactured by Sugino Machine Co., Ltd.) Samples T4 and T5: Xanthan gum (trade name Sun Ace ES, manufactured by Saneigen F·F·I Co., Ltd.) Samples T6 to T9: Xanthan gum (trade name: Xanthan gum granules, manufactured by Unitec Foods Co., Ltd.) Sample T10: carboxymethylcellulose (trade name: Sunrose (registered trademark) F01MC, manufactured by Nippon Paper Industries, Ltd.) Samples T11 and T12: gellan gum (trade name Kelkogel LT100, manufactured by Saneigen F.F.I. Co., Ltd.) Samples T13 and T14: Gum Arabic and xanthan gum (trade name Thixogum S, manufactured by Nexira)

[0140] [Table 1]

[0141] The relationship between viscosity η and shear rate γ at 25°C for these samples was measured using a ViscoQC 300-L (B-type viscometer, Antonpaar) measuring system, either DG26, SC4-18, SC4-21, or SC4-27. The measurement was performed for 1 minute at a spindle speed of 1 rpm, 2 rpm, 4 rpm, 6 rpm, 8 rpm, 10 rpm, 20 rpm, or 30 rpm. The measurement was performed for 30 seconds at a spindle speed of 40 rpm, 50 rpm, 60 rpm, 70 rpm, 80 rpm, 90 rpm, or 100 rpm.

[0142] Figure 7 、 Figure 8 、 Figure 9 、 Figure 10 、 Figure 11 and Figure 12 Two logarithmic graphs showing the relationship between the viscosity (25° C.) and the shear rate of the sample are shown, each showing the shear rate and the viscosity on a logarithmic scale. Figure 7 Graph showing the relationship between the viscosity and shear rate of samples T1 to T3 (□: sample T1, △: sample T2, ◇: sample T3). Figure 8Chart showing the relationship between the viscosity and shear rate of specimens T4 - T5 (□: specimen T4, △: specimen T5). Figure 9 Chart showing the relationship between the viscosity and shear rate of specimens T6 - T8 (〇: specimen T6, □: specimen T7, △: specimen T8). Figure 10 Chart showing the relationship between the viscosity and shear rate of specimen T9 (●: specimen T9). Figure 11 Chart showing the relationship between the viscosity and shear rate of specimen T10 (〇: specimen T10). Figure 12 Chart showing the relationship between the viscosity and shear rate of specimens T11 - T14 (〇: specimen T11, □: specimen T12, △: specimen T13, ◇: specimen T14).

[0143] As Figure 7 , Figure 8 , Figure 9 , Figure 10 , Figure 11 and Figure 12 shown, liquids with high or low viscosity dependence on the shear rate γ can be prepared by the type or concentration of the thickener. Specimens T4 - T9 and T11 - T14 are fluids that exhibit pseudoplasticity at 25°C. Specimens T1 - T3 and T10 are fluids that do not exhibit pseudoplasticity.

[0144] The viscosities (at 25°C) of specimens T4 - T9 and T12 - T14 at a shear rate of 10 s -1 are listed below. Specimen T4: 15 mPa·s, Specimen T5: 28 mPa·s, Specimen T6: 50 mPa·s, Specimen T7: 90 mPa·s, Specimen T8: 471 mPa·s, Specimen T9: 15 mPa·s, Specimen T12: 38 mPa·s, Specimen T13: 25 mPa·s, Specimen T14: 50 mPa·s The viscosities (at 25°C) of specimens T1 - T3 and T10 at a shear rate of 10 s -1 are listed below. Specimen T1: 18 mPa·s, Specimen T2: 13 mPa·s, Specimen T3: 26 mPa·s, Specimen T10: 150 mPa·s

[0145] The above - mentioned shear rate of 10 s -1 The viscosity at 25°C was measured under the following measurement conditions. In the case of the measurement system DG26, it is carried out for 1 minute at a rotational speed of 8 rpm of the rotating shaft (specimens T1 to T5, T9, T10, T12 to T14). In the case of the measurement system SC4-21, it is carried out for 1 minute at a rotational speed of 10 rpm of the rotating shaft (specimens T6, T7). Or in the case of the measurement system SC4-27, it is carried out for 1 minute at a rotational speed of 30 rpm of the rotating shaft (specimen T8).

[0146] Calculate the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of specimens T1 to T14, and find their inclination (Δlogη) / (Δlogγ). Specifically, use Figures 7 to 12 the values of the chart shown, and obtain the inclination (Δlogη) / (Δlogγ) through the above calculation formula (I) in the same manner as in Example 1. For specimens T1 to T14, the inclination (Δlogη) / (Δlogγ) obtained by the above calculation formula is shown in Table 2. Liquids with an inclination shown in Table 2 of -0.1 or less can be said to exhibit pseudoplasticity within the range of the shear rate at which the inclination is obtained.

[0147] [Table 2] Specimen Inclination Specimen Inclination T1 -0.04 T8 -0.88 T2 0.05 T9 -1.06 T3 -0.08 T10 -0.03 T4 -0.38 T11 -0.17 T5 -0.50 T12 -0.47 T6 -0.51 T13 -0.47 T7 -0.49 T14 -0.62

[0148] For specimens T1, T2, T4, T5, T7, T10, and T12 to T14, for the shear rate range of 10 s -1 ~90 s -1 (γ1 = 90, γ2 = 10), obtain the inclination from the above calculation formula (I). For specimens T3 and T11, for the shear rate range of 26 s -1 ~130 s -1 (γ1 = 130, γ2 = 26), obtain the inclination from the above calculation formula (I). For specimen T6, for the shear rate range of 3 s -1 ~65 s -1 (γ1 = 65, γ2 = 3), obtain the inclination from the above calculation formula (I). For specimens T8 and T9, for the shear rate range of 0.3 s -1 ~20 s -1 (γ1 = 20, γ2 = 0.3), obtain the inclination from the above calculation formula (I).

[0149] Furthermore, for Figures 7 to 12The logarithmic values (logη) of the viscosities η of the specimens T1 to T14 shown and the logarithmic values (logγ) of the shear rates γ are subjected to regression analysis. Calculate the logarithmic values (logγ) of the measured shear rates and the logarithmic values (logη) of the viscosities at these shear rates, perform linear regression analysis on these values, and obtain the linear approximation formula for logγ and logη. At this time, in order to calculate the measurement error Sa of the slope, the residual variance Ve of the viscosity η is obtained. The residual variance Ve of the viscosity η is obtained by the sum of the squares of the differences (residual sum of squares ∑(η o and the calculated value η i ) of the viscosities at each shear rate γ. o -η i ) 2 ) divided by the degrees of freedom n - 2. In addition, the average m γ of the shear rate γ is obtained, and the sum of the squares of the deviations ∑(γ - m γ ) 2 of γ is calculated. Then, the residual variance Ve of the viscosity η is divided by the sum of the squares of the deviations of γ, and the square root thereof is taken as the standard error Sa of the slope. In addition, the viscosities of each liquid at 25°C at a shear rate of 100 s -1 are calculated from the regression line (linear approximation formula) of this logη and logγ.

[0150] The viscosities (calculated values) of the specimens T1 - T14 at 25°C at a shear rate of 100 s -1 obtained from the linear approximation formula of the logarithmic values of the above shear rates and the logarithmic values of the viscosities are shown below. Specimen T1: 17 mPa·s, Specimen T2: 16 mPa·s, Specimen T3: 6 mPa·s, Specimen T4: 5 mPa·s, Specimen T5: 8 mPa·s, Specimen T6: 10 mPa·s, Specimen T7: 24 mPa·s, Specimen T8: 65 mPa·s, Specimen T9: 77 mPa·s, Specimen T10: 17 mPa·s, Specimen T11: 5 mPa·s, Specimen T12: 13 mPa·s, Specimen T13: 8 mPa·s, Specimen T14: 15 mPa·s

[0151] Next, the specimens T1 to T14 prepared above were placed in a transparent container, and a pattern was drawn. To draw a pattern with respect to these liquids to be drawn (specimens T1 to T14), an ink in which fine particles were dispersed in the liquid was prepared. The ink was prepared by suspending red polystyrene fine particles with a diameter of 1 μm (Polystyrene Red Dyed Microsphere 1.00 μm, density 1.05 g / mL, manufactured by Polysciences) in an aqueous glycerol solution such that the final concentration of the fine particles reached 1 wt% and the final concentration of glycerol reached 20 wt%. The viscosity (25 °C) of this ink was 2 mPa·s, and the density was 1.05 g / mL. The viscosity (25 °C) of the ink was measured using a tuning fork vibration viscometer SV-10 (manufactured by A&D). In addition, the density of the ink was measured using a densitometer DMA4500M (manufactured by Anton Paar).

[0152] Using the device fabricated in Reference Example 1, the above ink was used to draw a pattern on specimens T1 to T14. The ink was accommodated in syringe 480 of the above device, and the ink was ejected from nozzle 420 to perform the drawing. Figure 13 A and Figure 13 B are schematic views showing the patterns drawn in Example 2. As Figure 13 shown in B, in the liquid to be drawn, for the pattern where "≠" is visible when viewed from the side of the container, the upper line of the pattern where "=" is visible is at a position 20 mm from the liquid surface, and the uppermost part of the pattern where " / " is visible is drawn at a position 10 mm from the liquid surface. That is, when viewed from the side of the container, these patterns were drawn such that the distance (height difference in the liquid) between the upper line of the pattern where "=" is visible and the uppermost part of the pattern where " / " is visible reached 10 mm. The length of each line of the pattern where "=" is visible is 40 mm. As Figure 13 shown in A, the drawing of the pattern where "=" is visible and the drawing of the pattern where " / " is visible were respectively depicted as drawing surfaces 2a and 2b, and the distance between the drawing surfaces (2a, 2b) was 3 mm. The angle formed by the drawing surface and the nozzle was maintained at 30° for the drawing. The drawing sequence was: first, the upper line of the pattern where "=" is visible was drawn, then the lower line was drawn, and finally the pattern where " / " is visible was drawn from top to bottom. Also, the moving speed of the nozzle during drawing was 20 mm / s, and the acceleration during drawing was 2 mm / s 2 , the moving speed to the next line was 90 mm / s, and the acceleration to the next line was 18 mm / s 2 . In addition, the ink ejection flow rate was 0.7 μL / s for the drawing.

[0153] The stability of the pattern after drawing was measured as the distance ( Figure 13 the height difference in liquid B #1) from the upper line of the pattern visible as "=" to the uppermost part of the pattern visible as " / " when viewed from the side, and was evaluated by this distance (mm). The value of the stability score was taken as the above distance (mm) from the upper line of the pattern visible as "=" to the uppermost part of the pattern visible as " / ". That is, when it was most stable (when the distance was 10 mm), the stability score was 10. When the pattern visible as " / " settled 5 mm (when the above distance was 5 mm), the stability score was 5. Or when the pattern visible as " / " floated 5 mm (when the above distance was 5 mm), the stability score was 5. When the above distance was 0 mm or when it separated by more than 10 mm, the stability score was 0. For example, when the stability score was 8, it meant that when viewed from the side, the distance from the upper line of the pattern visible as "=" to the uppermost part of the pattern visible as " / " was 8 mm. This time, it was drawn 5 times in each liquid, and the average value and standard error of the value of the stability score were calculated.

[0154] Figure 14 shows a graph representing the relationship between the inclination (Δlogη) / (Δlogγ) calculated by the calculation formula (I) from the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid (samples T1 to T14) used in the drawing and the stability of the pattern in this liquid. Figure 14 The value of "stability" on the vertical axis of the shown graph was the value of the stability score obtained by the above evaluation. Figure 14 、 Figure 15 and Figure 16 T1 to T14 in represent samples T1 to T14. As Figure 14 shown, it was confirmed that the pattern with a smaller value of the inclination (Δlogη) / (Δlogγ) of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid had a higher tendency of stability. In fact, the correlation coefficient between the two was also -0.92, and a strong negative correlation was confirmed. Compared with the samples that did not exhibit pseudoplasticity (samples T1 to T3 and T10), when the inclination (Δlogη) / (Δlogγ) was -0.1 or less, a pattern with a stability score of 6 or more could be drawn, and it was known that it could be drawn stably.

[0155] For samples T1 to T14, by the regression analysis of the logarithm of the above viscosity η (logη) and the logarithm of the shear rate γ (logγ), the viscosity (25 °C) at a shear rate of 100 s -1 was calculated. The relationship between the calculated value of the viscosity at a shear rate of 100 s -1 and the stability score evaluated above is shown inFigure 15 . Figure 15 To represent the relationship between the viscosity of the liquid used in drawing at 25°C at the above-calculated shear rate of 100 s -1 and the stability of the pattern in the liquid, in a chart. The "viscosity" on the horizontal axis is the viscosity (calculated value) at 25°C at a shear rate of 100 s -1 . The value of "stability" on the vertical axis represents the value of the stability score. As Figure 15 shown, in the specimens with pseudoplasticity, it was also confirmed that for the shear rate of 100 s -1 , the pattern with the higher viscosity (calculated value) has a higher tendency of stability. The correlation coefficient between this viscosity and stability was also confirmed to be a weak correlation of 0.47.

[0156] Figure 16 shows the relationship between the inclination (Δlogη) / (Δlogγ) of specimens T1 to T14 and the viscosity (calculated value) at 25°C at a shear rate of 100 s -1 and the pattern stability in the specimen. Figure 16 The inclination shown is the inclination (Δlogη) / (Δlogγ) obtained from the logarithmic value of viscosity η (logη) and the logarithmic value of shear rate γ (logγ) by calculation formula (I). Figure 16 The horizontal axis of -1 represents the logarithmic value of the viscosity (mP·s) (calculated value) at 25°C at a shear rate of 100 s Figure 16 . In it, the circle (〇) represents the liquid that forms a pattern with a stability score of 9 or more, the square (□) represents the liquid that forms a pattern with 8 ≤ stability score < 9, the triangle (△) represents the liquid that forms a pattern with 6 ≤ stability score < 8, and the cross (×) represents the liquid that forms a pattern with a stability score less than 6. When comparing at the same viscosity, it was confirmed that the side with a smaller value of the above inclination tends to obtain a stable pattern.

[0157] These results show that when the liquid to be drawn is a pseudoplastic fluid, the stability of the pattern in the liquid is improved compared to the liquid that does not exhibit pseudoplasticity. In addition, it is implied that a more stable pattern can be obtained when the viscosity at a shear rate of 100 s -1 of the liquid to be drawn is high.

[0158] <Example 3> Using the apparatus shown in Reference Example 1, by observing from the side of the container, a liquid containing a meaningful pattern was manufactured, and the viscosity physical properties of the liquid that stabilizes the pattern at this time were studied. As the liquid (liquid matrix) to be drawn, specimens T15 to T18 were prepared. In the preparation of the specimens, thickeners commonly used in foods, such as pectin, carrageenan, locust bean gum, and tara gum, were used. These are water-soluble thickeners. These thickeners were suspended in water at various concentrations to prepare four kinds of liquids with changed viscosity characteristics as specimens T15 to T18. The density of specimens T15 to T18 was all 1.05 g / mL. At this time, glycerol was added to a part of the liquid so that the density reached 1.05 g / mL. The thickeners used in the preparation of specimens T15 to T18 are shown in Table 3. The thickener concentrations and glycerol concentrations in specimens T15 to T18 are shown in Table 3. The thickeners used in the preparation of the specimens are as follows. Specimen T15: Pectin (trade name AYD3110SB, manufactured by Unitec Foods Co., Ltd.) Specimen T16: Carrageenan (trade name Sogina MW210, manufactured by Mitsubishi Chemical Corporation) Specimen T17: Locust bean gum (trade name Soar Locust A200, manufactured by Mitsubishi Chemical Corporation) Specimen T18: Tara gum (trade name Tara gum MT120, manufactured by Mitsubishi Chemical Corporation)

[0159] [Table 3]

[0160] The relationship between the viscosity η and the shear rate γ of these specimens at 25°C was measured by the DG26 or SC4-27 measurement system of a rotational viscometer ViscoQC 300-L (B-type viscometer, manufactured by Antonpaar). In addition, it was measured for 1 minute respectively when the rotational speed of the rotating shaft was 1 rpm, 2 rpm, 4 rpm, 6 rpm, 8 rpm, 10 rpm, 20 rpm, or 30 rpm. It was measured for 30 seconds respectively when the rotational speed of the rotating shaft was 40 rpm, 50 rpm, 60 rpm, 70 rpm, 80 rpm, 90 rpm, or 100 rpm.

[0161] Figure 17 The relationship between the viscosity (25°C) of the specimens and the shear rate is shown (black square: specimen T15, ●: specimen T16, □: specimen T17, ○: specimen T18). Figure 17 The shown graph is a double-logarithmic graph representing the shear rate and viscosity on a logarithmic scale. From Figure 17 , liquids with high or low viscosity dependence on the shear rate γ can be prepared by the type or concentration of the thickener. Specimens T16 to T18 are fluids that exhibit pseudoplasticity at 25°C. Specimen T15 is a fluid that does not exhibit pseudoplasticity. The viscosities (at 25°C) of specimens T15, T16, T17, and T18 at a shear rate of 10 s -1 are shown below. Specimen T15: 72 mPa·s, Specimen T16: 100 mPa·s, Specimen T17: 219 mPa·s, Specimen T18: 161 mPa·s The viscosities at 25°C at the above shear rate of 10 s -1 were evaluated for 1 minute at a rotational speed of 30 rpm using the measurement system SC4-27. The logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of specimens T15 to T18 were calculated, and the slope (Δlogη) / (Δlogγ) was obtained. Specifically, in the same manner as in Example 1, the slope (Δlogη) / (Δlogγ) was obtained from the above calculation formula (I). Regarding specimens T15 to T18, the slopes (Δlogη) / (Δlogγ) obtained from the above calculation formula are shown in Table 4. Liquids with a slope of -0.1 or less shown in Table 4 can be said to exhibit pseudoplasticity within the range of the shear rate at which the slope was obtained.

[0162] [Table 4] Specimen Inclination T15 -0.08 T16 -0.16 T17 -0.18 T18 -0.12

[0163] For specimen T15, for the range of shear rate from 13 s -1 to 34 s -1 (γ1 = 34, γ2 = 13), the slope was obtained from the above calculation formula (I). For specimens T16, T17, and T18, for the range of shear rate from 10 s -1 to 34 s -1 (γ1 = 34, γ2 = 10), the slope was obtained from the above calculation formula (I). Furthermore, for Figure 17 the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of specimens T15 to T18 shown, regression analysis was performed. The logarithm of the measured shear rate (logγ) and the logarithm of the viscosity at that shear rate (logη) were calculated, and linear regression analysis was performed on these values to obtain the linear approximation formula of logγ and logη. At this time, in order to calculate the measurement error Sa of the slope, the residual variance Ve of the viscosity η was obtained. The residual variance Ve of the viscosity η was obtained by dividing the sum of the squares of the differences (residual sum of squares Σ(η o - η i ) of the measured value η o and the calculated value η i ) by the degree of freedom n - 2. In addition, the average m of the shear rate γ was obtained 2 )γ , calculate the sum of squared deviations of γ, Σ(γ - m γ ) 2 . Then divide the residual variance Ve of the viscosity η by the sum of squared deviations of γ, and take the square root as the standard error Sa of the inclination. Furthermore, calculate the viscosities of each liquid at 25°C at a shear rate of 100 s -1 from the regression line (linear approximation formula) of logη and logγ.

[0164] For the shear rate of 100 s obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity as described above -1 , the viscosities (calculated values) of specimens T15 to T18 at 25°C are shown below. Specimen T15: 60 mPa·s, Specimen T16: 70 mPa·s, Specimen T17: 149 mPa·s, Specimen T18: 125 mPa·s

[0165] Next, put the specimens T15 to T18 prepared above into a transparent container and draw a pattern. To draw a pattern for these liquids to be drawn (specimens T15 to T18), prepare an ink in which fine particles are dispersed in the liquid. The ink is prepared by suspending red polystyrene fine particles with a diameter of 1 μm (Polystyrene Red Dyed Microsphere 1.00 μm, density 1.05 g / mL, manufactured by Polysciences) in an aqueous glycerol solution so that the final concentration of the fine particles reaches 1 wt% and the final concentration of glycerol reaches 20 wt%. The viscosity (25°C) of this ink is 2 mP·s and the density is 1.05 g / mL.

[0166] Measure the viscosity (25°C) of the ink using a tuning fork vibration type viscometer SV-10 (manufactured by A&D). In addition, measure the density of the ink using a densitometer DMA 4500M (manufactured by Antonpaar).

[0167] Using the device made in Reference Example 1, in the same manner as in Example 2, draw a pattern in specimens T15 to T18 with the above ink under the same conditions, and evaluate the stability. This time, perform drawing 3 times in each liquid, and calculate the average value and standard error of the stability score values.

[0168] Figure 18 Show a graph representing the relationship between the inclination (Δlogη) / (Δlogγ) calculated by the calculation formula (I) from the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ of the liquid (specimens T15 to T18) used in the drawing and the stability of the pattern in this liquid. Figure 18The value of "stability" on the vertical axis of the chart shown is the value of the stability score of the above evaluation. Figure 18 , Figure 19 and Figure 20 In T15 to T18, it represents specimens T15 to T18. As Figure 18 shown, it can be seen that when the slope (Δlogη) / (Δlogγ) of the logarithm of the viscosity η of the liquid (logη) and the logarithm of the shear rate γ (logγ) is -0.12 or less, a pattern with a stability score of 8 or more can be drawn and can be stably drawn.

[0169] For specimens T15 to T18, by the regression analysis of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) as described above, the viscosity (25 °C) at a shear rate of 100 s -1 is calculated. The relationship between the calculated value of the viscosity at a shear rate of 100 s -1 and the stability score of the above evaluation is shown in Figure 19 . Figure 19 It is a chart showing the relationship between the viscosity at 25 °C of the liquid used in drawing at the above calculated shear rate of 100 s -1 and the stability of the pattern in the liquid. The "viscosity" on the horizontal axis is the viscosity (calculated value) at 25 °C at a shear rate of 100 s -1 . The value of "stability" on the vertical axis represents the value of the stability score.

[0170] Figure 20 shows the relationship between the slope (Δlogη) / (Δlogγ) of specimens T15 to T18 and the viscosity (calculated value) at 25 °C at a shear rate of 100 s -1 and the pattern stability in the specimen. Figure 20 The slope shown is the slope (Δlogη) / (Δlogγ) obtained from the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) by calculation formula (I). Figure 20 The horizontal axis of -1 represents the logarithm of the viscosity (mP·s) (calculated value) at 25 °C at a shear rate of 100 s. Similar to Figure 16 , Figure 20 in, a circle (〇) represents a liquid that gives a pattern with a stability score of 9 or more, a square (□) represents a liquid that gives a pattern with 8 ≤ stability score < 9, a triangle (△) represents a liquid that gives a pattern with 6 ≤ stability score < 8, and a cross (×) represents a liquid that gives a pattern with a stability score less than 6.

[0171] These results do not contradict the results of Example 2, showing that when the liquid of the drawn object is a pseudoplastic fluid, the stability of the pattern in the liquid is improved compared to a liquid that does not exhibit pseudoplasticity. In addition, it is shown that in order to form a stable pattern in the liquid, the inclination (Δlogη) / (Δlogγ) calculated by the above formula (I) for the liquid is preferably -0.12 or less.

[0172] <Example 4> The difference in the temporal stability of the drawn pattern based on the type of thickener added to the liquid of the drawn object was evaluated. As the liquid of the drawn object, the specimens T3, T7, T10, T11, T15 to T18 prepared in Examples 2 to 3 were used. The ink used was the same ink as in Example 2 (ink in which fine particles were dispersed in the liquid).

[0173] Using the device manufactured in Reference Example 1, a pattern was drawn with the above ink in the specimens T3, T7, T10, T11, T15 to T18. The ink was accommodated in the syringe 480 of the above device, and the ink was ejected through the nozzle 420 for drawing. In Example 4, drawing was performed under the same conditions as in Example 2 Figure 13 A and Figure 13 the patterns shown in the schematic diagrams of B. Figure 13 The length of each line of the pattern presenting "=" as viewed from the side of the container shown in B was set to 40 mm.

[0174] The drawn pattern was observed from the side of the container (the front of the drawing surface). The stability of the drawn pattern was evaluated for the upper line of the pattern presenting "=" immediately after the drawing of the pattern "≠". That is, the drawn line deforms over time, and the height difference ( Figure 21 of #2) between the position closest to the liquid surface and the position closest to the bottom surface of the deformed line was measured. The value obtained by subtracting this height difference (mm) from 10 was used as the value of the stability score. That is, in the most stable case (when the distance is 0 mm), the stability score is 10. When the line deforms and the height difference between the highest point and the lowest point of the line is 5 mm, the stability score is 5. When the above height difference is 10 mm or more, the stability score is 0. For example, a stability score of 8 means that when observing from the side, when the upper line of the pattern presenting "=" deforms, the height difference between the highest point and the lowest point of the line is 2 mm.

[0175] In Example 4, drawing was performed 3 times in each liquid, and the average value and standard error of the values of the stability scores were calculated. Figure 22 A and Figure 22Graph B shows the relationship between the gradient (Δlogη) / (Δlogγ) calculated by formula (I) and the stability of the pattern in the liquid, where the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquids (specimens T3, T7, T10, T11, T15 - T18) used in the drawing are shown. Figure 22 A: Immediately after drawing, Figure 22 B: 1 minute after drawing). Figure 22 The value of "stability" on the vertical axis of the graph shown in A is the value of the stability score of the above evaluation immediately after drawing. And Figure 22 The value of "stability" on the vertical axis of the graph shown in B is the value of the stability score of the above evaluation 1 minute after drawing. Figure 22 A, Figure 22 B, Figure 23 A and Figure 23 In A and B, T3, T7, T10, T11, T15 - T18 respectively represent specimens T3, T7, T10, T11, T15 - T18.

[0176] As Figure 22 shown in A and Figure 22 B, it can be seen that when the value of the gradient (Δlogη) / (Δlogγ) of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) of the liquid is small, there is a tendency to confirm high pattern stability. In particular, it can be seen that when the gradient (Δlogη) / (Δlogγ) is -0.12 or less, even after 1 minute, the stability score is 2 or more, and compared with specimens that do not exhibit pseudoplasticity, the pattern is maintained and can be stably drawn.

[0177] For specimens T3, T7, T10, T11, T15 - T18, by regression analysis of the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) as described above, the viscosity at a shear rate of 100 s -1 is calculated. The relationship between the calculated value of the viscosity at a shear rate of 100 s -1 and the stability score of the above evaluation is shown in Figure 23 A and Figure 23 B ( Figure 23 A: Immediately after drawing, Figure 24 B: 1 minute after drawing). Figure 23 Graph A shows the relationship between the viscosity at 25°C of the liquid used in the drawing at the above-calculated shear rate of 100 s -1 and the stability of the pattern immediately after drawing. Figure 23 Graph B shows the relationship between the viscosity at 25°C of the liquid used in the drawing at the above-calculated shear rate of 100 s -1Chart showing the relationship between the viscosity at 25°C and the stability of the pattern drawn after 1 minute. The "viscosity" on the horizontal axis is the viscosity (calculated value) at 25°C when the shear rate is 100 s -1 The viscosity (calculated value) at 25°C when the shear rate is. The value of "stability" on the vertical axis represents the value of the stability score. These results show that when the liquid to be drawn is a pseudoplastic fluid, the stability of the pattern in the liquid is improved compared to a liquid that does not exhibit pseudoplasticity. In addition, it is shown that in order to form a stable pattern in the liquid, the inclination (Δlogη) / (Δlogγ) calculated by the above formula (I) for the liquid is preferably -0.12 or less.

[0178] <Example 5> When manufacturing a liquid with a pattern using the device shown in Reference Example 1, the viscosity characteristics of the ink that stabilizes the pattern were studied. The ink was prepared by suspending an aqueous suspension of red polystyrene microparticles with a diameter of 1 μm (Polystyrene Red Dyed Microsphere 1.00 μm, density 1.05 g / mL, manufactured by Polysciences) in an aqueous glycerol solution so that the final concentration of the microparticles reached 0.5% by weight, the final concentration of the thickener reached 0.02% or 0.03% by weight, and the final concentration of glycerol reached 20% by weight. As the thickener, xanthan gum (trade name xanthan gum granules, manufactured by UnitecFoodS Co., Ltd.) was used. The xanthan gum concentrations in the prepared inks (specimens IX-1, IX-2, IX-4) are described below. Specimen IX-4 is an ink without xanthan gum prepared by suspending the above-mentioned polystyrene microparticles (final concentration 0.5% by weight) in a 20% by weight aqueous glycerol solution. Xanthan gum concentration of the ink specimens Specimen IX-1: 0.02% by weight, Specimen IX-2: 0.03% by weight, Specimen IX-4: 0% by weight

[0179] In addition to the above ink samples, glycerol aqueous solutions containing 0.02 wt%, 0.03 wt% or 0.05 wt% of xanthan gum (final glycerol concentration 20 wt%) and a glycerol aqueous solution without xanthan gum (final glycerol concentration 20 wt%) were prepared as samples X-1 to X-4, respectively. Micro-particles made of polystyrene were not added to samples X-1 to X-4. The relationship between the viscosity η and the shear rate γ of these glycerol aqueous solutions containing xanthan gum at 25 °C was measured by the measurement system of DG26 or SC4-27 of a rotational viscometer ViscoQC 300-L (B-type viscometer, Anton Paar). In addition, when the rotational speed of the rotating shaft was 1 rpm, 2 rpm, 4 rpm, 6 rpm, 8 rpm, 10 rpm, 20 rpm or 30 rpm, it was measured for 1 minute respectively. When the rotational speed of the rotating shaft was 40 rpm, 50 rpm, 60 rpm, 70 rpm, 80 rpm, 90 rpm or 100 rpm, it was measured for 30 seconds respectively. Figure 24 The relationship between the viscosity (25 °C) and the shear rate of the glycerol aqueous solution added with xanthan gum (final glycerol concentration 20 wt%) is shown (black square: aqueous solution added with 0.02 wt% xanthan gum (sample X-1), 〇: aqueous solution added with 0.03 wt% xanthan gum (sample X-2), ●: aqueous solution added with 0.05 wt% xanthan gum (sample X-3), triangle: glycerol aqueous solution without xanthan gum (sample X-4)). The aqueous solution added with xanthan gum shows pseudoplasticity. In addition, the relationship between the viscosity (25 °C) and the shear rate of the aqueous solution containing only glycerol with a final concentration of 20 wt% (sample X-4) is that of a Newtonian fluid.

[0180] The shear rates of samples X-1 to X-4 were 10 s -1 The viscosities (25 °C) at this time were 9 mPa·s for the aqueous solution added with 0.02 wt% xanthan gum (X-1), 12 mPa·s for the aqueous solution added with 0.03 wt% xanthan gum (X-2), 26 mPa·s for the aqueous solution added with 0.05 wt% xanthan gum (X-3), and 2 mPa·s for the aqueous solution added with 20 wt% glycerol (X-4). The above shear rate was 10 s -1 The viscosity at 25 °C at this time was evaluated for 1 minute at a rotational speed of 8 rpm of the rotating shaft using the measurement system DG26. The concentrations of xanthan gum and glycerol in samples X-1, X-2 and X-4 were the same as those in the ink samples IX-1, IX-2 and IX-4, respectively. It is generally considered that the above ink samples IX-1, IX-2 and IX-4 added with 0.5 wt% micro-particles made of polystyrene in samples X-1, X-2 and X-4 also show the same degree of viscosity physical properties as this sample. Calculate the logarithm of the viscosity η (logη) and the logarithm of the shear rate γ (logγ) for each sample, and find their slope (Δlogη) / (Δlogγ). Specifically, in the same manner as in Example 1, find the slope (Δlogη) / (Δlogγ) from the above calculation formula (I). For each sample, the slope (Δlogη) / (Δlogγ) obtained from the above calculation formula is shown in Table 5. Liquids with a slope shown in Table 5 of -0.1 or less can be said to exhibit pseudoplasticity within the range of the shear rate at which the slope was obtained.

[0181] [Table 5]

[0182] For sample X-1, for the shear rate range of 10 s -1 ~129 s -1 (γ1 = 129, γ2 = 10), find the slope from the above calculation formula (I). For sample X-2, for the shear rate range of 7 s -1 ~129 s -1 (γ1 = 129, γ2 = 7), find the slope from the above calculation formula (I). For sample X-3, for the shear rate range of 1 s -1 ~72 s -1 (γ1 = 72, γ2 = 1), find the slope from the above calculation formula (I). For sample X-4, for the shear rate range of 60 s -1 ~129 s -1 (γ1 = 129, γ2 = 60), find the slope from the above calculation formula (I).

[0183] Furthermore, for Figure 24 the logarithms of the viscosity η (logη) and the shear rate γ (logγ) of samples X-1 to X-4 shown, perform a regression analysis. Calculate the logarithm of the measured shear rate (logγ) and the logarithm of the viscosity at that shear rate (logη), perform a linear regression analysis on these values, and find the linear approximation formula for logγ and logη. Calculate the viscosity at 25°C of each liquid at a shear rate of 100 s -1 from the regression line (linear approximation formula) of logη and logγ. At the shear rate of 100 s -1 obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity, the viscosities (calculated values) at 25°C of samples X-1 to X-4 are as follows: sample X-1: 4 mPa·s, sample X-2: 6 mPa·s, sample X-3: 12 mPa·s, sample X-4: 2 mPa·s.

[0184] Next, a pseudoplastic liquid (liquid matrix) to be drawn is prepared by suspending it in an aqueous glycerol solution such that xanthan gum (trade name: xanthan gum granules, manufactured by Unitec Foods Co., Ltd.) reaches a final concentration of 0.05% by weight and glycerol reaches a final concentration of 20% by weight. In addition, a liquid of Newtonian fluid to be drawn is prepared by suspending it in water such that glycerol reaches a final concentration of 20% by weight. The density of these liquids is 1.05 g / mL.

[0185] 3 mL of the above-prepared pseudoplastic liquid to be drawn is placed in a transparent container, and samples IX-1 to IX-2 are used as respective inks, and dots are drawn using the device fabricated in Reference Example 1. In addition, sample IX-4 without added xanthan gum is used as the ink to draw the same dots. Furthermore, as a control, 3 mL of an aqueous glycerol solution without added thickener is used as the object to be drawn, and sample IX-4 without added xanthan gum is used as the ink to draw dots. This time, the nozzle is moved to the dotting position at a nozzle speed of 30 mm / s, and the ink is ejected at 1 μL / s for 2 seconds. Then, the nozzle is left in place without movement for 20 seconds, and then the nozzle is withdrawn at a nozzle speed of 100 mm / s. Immediately after withdrawing the nozzle (0 s) and 30 seconds after drawing (30 s), the pattern is photographed, and the length in the vertical direction of the drawn dots is measured using this image. Each sample is tried 10 times (N = 10), the average and dispersion are obtained, and the difference between each value is evaluated by the Tukey method. A p-value < 0.01 indicates a significant difference.

[0186] Figure 25 A, Figure 25 B, Figure 25 C and Figure 26 show the results. Figure 25 A, Figure 25 B and Figure 25 C are photos of the patterns of the dots drawn in the liquid matrix in Example 5. These are photos taken from the side of the container after drawing in the liquid to be drawn placed in the container by the above method. Samples using a pseudoplastic liquid in the liquid matrix are denoted as M(+), and samples using a liquid without pseudoplasticity are denoted as M(-). In addition, samples using an ink with pseudoplasticity are denoted as I(+), and samples using an ink that does not exhibit pseudoplasticity are denoted as I(-). Figure 25 A is the pattern of the dots drawn with sample IX-4 in a liquid that does not exhibit pseudoplasticity. Figure 25 B is the pattern of the dots drawn with sample IX-4 in a pseudoplastic liquid. Figure 25 C is the pattern of the dots drawn with ink sample IX-1 in a pseudoplastic liquid. Figure 25 A, Figure 25 B andFigure 25 In the upper figure of C, it is immediately after drawing (0 s), and in the lower figure, it is 30 seconds after drawing (30 s).

[0187] Figure 26 It is a graph showing the change over time of the length in the vertical direction of the pattern of the points drawn in Example 5 (**:p < 0.01). The results are expressed as mean ± standard error (S.E.) (N = 10). “Glycerol” in the lower part of the horizontal axis indicates a sample using an aqueous glycerol solution without xanthan gum (a liquid without pseudoplasticity) in the liquid to be drawn (liquid matrix). “Xanthan gum 0.05 wt%” indicates a sample using an aqueous glycerol solution containing 0.05 wt% xanthan gum in the liquid to be drawn. “No thickener” in the upper part of the horizontal axis indicates a sample using Specimen IX-4 as the ink for drawing. 0.02% Xan and 0.03% Xan respectively indicate samples using Specimen IX-1 and IX-2 as the ink for drawing. The “dot diameter” on the vertical axis indicates the length in the vertical direction of the pattern of the dots drawn with the ink. The black bars indicate immediately after drawing, and the white bars indicate 30 seconds after drawing.

[0188] The result is that when the liquid to be drawn is a fluid that does not exhibit pseudoplasticity, a tendency for the ink to extend up and down is observed immediately after drawing ( Figure 25 A, upper figure (0 s)). On the other hand, for a drawing object with pseudoplasticity, when drawing with an ink without adding a thickener, it appears as a dot shape immediately after drawing. A tendency for the ink to extend up and down is observed 30 seconds after drawing, but compared with Figure 25 the sample shown in A, the extension of the dot pattern is suppressed ( Figure 25 B, lower figure (30 s)). When drawing with the ink of Specimen IX-1 with pseudoplasticity on a pseudoplastic fluid, the extension of the dot pattern is well suppressed 30 seconds after drawing ( [[ID= C, lower figure (30 s)). When drawing with Specimen IX-2 on a drawing object with pseudoplasticity, similar to the case of Specimen IX-1, the extension of the dot pattern after drawing is well suppressed. From this result, it can be seen that by making the drawing object pseudoplastic, the drawing stability can be improved, but further by also imparting pseudoplasticity to the ink, the pattern after drawing is more stable ( ​ ). Symbol Explanation

[0189] 2a, 2b - drawing surface; 10 - material for pattern formation; 11 - microparticles; 12 - dispersion solvent; 20 - liquid matrix; 30 - pattern; 40 - container; 100, 200, 300 - Manufacturing apparatus for liquid containing patterns; 110, 210, 310 - Tanks; 120, 220, 320, 420 - Nozzles; 130 - Pumps; 140 - Control devices; 150, 250 - Stages; 151, 152 - Liquid supply pipes; 153, 253, 353 - Angle adjustment mechanisms; 260 - Gantry system; 261 - X - axis rails; 262 - Z - axis rails; 263 - Z - axis drive motors; 264 - Y - axis rails; 265 - Y - axis drive motors; 360 - Robotic arms; 460 - Collaborative robots; 470 - Syringe extrusion devices; 480 - Syringes.

Claims

1. A patterned liquid, characterized in that, The liquid matrix contains a pattern formed by microparticles and / or pigments, the liquid matrix is a pseudoplastic fluid, and the liquid matrix is contained in a container.

2. The patterned liquid according to claim 1, wherein The liquid matrix is a fluid that exhibits pseudoplasticity within at least a certain range between a shear rate of 0.3 and 130 s -1 -1.

3. The patterned liquid according to claim 1 or 2, characterized in that, The liquid matrix is a fluid that satisfies the following formula (I) within at least a certain range between a shear rate of 0.3 and 130 s -1 -1 log(η1 / η2) / log(γ1 / γ2) ≦ -0.12 Formula (I) In the above formula (I), η1 represents the viscosity (mPa·s) of the fluid at a shear rate γ1 (s -1 ), η2 represents the viscosity (mPa·s) of the fluid at a shear rate γ2 (s -1 ), γ1 and γ2 satisfy 0.3 ≦ γ2 < γ1 ≦ 130, and the viscosity is the viscosity at 25°C.

4. The patterned liquid according to claim 1 or 2, characterized in that, The viscosity of the liquid matrix at 25 °C when the shear rate is 100 s -1 is 4 mPa·s or more, obtained from the linear approximation formula of the logarithm of the shear rate and the logarithm of the viscosity.

5. The patterned liquid according to claim 1 or 2, characterized in that, The liquid matrix contains water and a water-soluble thickening agent.

6. The patterned liquid according to claim 5, wherein The water-soluble thickening agent is at least one selected from xanthan gum, gellan gum, locust bean gum, tara gum, and carrageenan.

7. The patterned liquid according to claim 1 or 2, characterized in that, It is a beverage.

8. A method for manufacturing a liquid containing a pattern, characterized in that, It includes a pattern-forming material that disperses microparticles and / or pigments in a dispersion solvent using a nozzle, ejects the pattern-forming material into the liquid matrix contained in a container, and forms a pattern composed of the microparticles and / or pigments in the liquid matrix, and the liquid matrix is a pseudoplastic fluid.

9. The method for manufacturing a liquid containing a pattern according to claim 8, characterized in that, The dispersion solvent is a pseudoplastic fluid.

10. An application, characterized in that, A pseudoplastic fluid is used as the matrix of the liquid containing the pattern.

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