JP5989031B2 - Printed tablet and method for producing the same - Google Patents

Description

  The present invention relates to a tablet with a print on which the surface of the tablet is printed.

In the case of tablets, it is required for users and formulators to display the names and symbols of the tablets on the surface of the tablets so that the tablets can be clearly identified.
There are two types of tablets: uncoated tablets in which drugs and vaginal forms are molded by tableting, and coated tablets whose surfaces are coated with sucrose or water-soluble polymers.

With coated tablets, tablets could be printed, but with uncoated tablets, printing was difficult and the stamping method was used exclusively.
In the past, stamps and the like have been used in uncoated tablets because the uncoated tablets themselves have a property of easily disintegrating, so that the tablets themselves after molding cannot withstand the printing pressure in normal printing. This is because there is a problem in that it is broken or the printability is not stable due to an unstable surface (powder).
In other words, because tablets are fragile, because of poor yield due to disintegration during printing, poor printing due to poor printability of the surface, and lack of adhesion due to peeling of the tablet surface, It was said that general printing using was impossible.

  However, tablets that have not been printed cannot identify a drug, which may cause a medical error. In addition, the method by engraving also has a problem that it is difficult to identify in an actual preparation, and a tablet on which easy-to-identify printing is applied is preferable in the preparation work.

As a printing method that avoids the printing pressure on the tablet, an ink-jet method that is performed without contact has been attempted.
For example, Patent Document 1 discloses a technique for an ink jet printer for writing or marking a medicine molded product.
Examples of the object include tablets, coated tablets, capsules, suppositories and the like.
In addition, as dye solutions to be used, solvent components such as alcohol, water, low aliphatic alcohol, glycol and glycerol, and adhesive components such as methylcellulose, hydroxypropylmethylcellulose, and hydroxypropylmethylcellulose phthalate are also described.
However, as a specific example, a coated tablet is targeted, and only an aqueous solution of a dye, an isopropanol solution, and a glycol dispersion of iron oxide are described.

  Further, Patent Document 2 describes printing on tablets using a continuous ink jet printer, but there is no detailed description about tablets and ink.

  Patent Document 3 discloses prescriptions of continuous ink jet inks using titanium oxide and food dyes using an aluminum lake. However, it is mainly used for foods, and has not yet reached its suitability for easily disintegrating tablets.

Patent Document 4 describes laser marking and inkjet printing as markings on easily disintegrating dosage forms.
Examples of easily disintegrating dosage forms include those that disintegrate in the mouth within 1 or 2 seconds. And it is said that it has become possible to expand what has been limited to impervious markings to porous individual dosage forms.
As the ink, there is a description that a mixture system of water and alcohol can be used. However, there is no specific description about the ink-jet ink and no description about the marked tablet, and it is mainly based on the easily disintegrating technology.

Patent Document 5 describes an ink-jet ink that uses oils or waxes and is also used for marking on tablets.
However, this does not take into consideration the suitability for easily disintegrating tablets, and there is a problem of adhesion on the surface of the tablets with easy disintegration and transfer of ink due to friction between the tablets.

  Patent Document 6 describes a technique intended for coating by an ink jet method, and is described as a method for increasing strength, which is different from the technical content of marking on easily disintegratable tablets.

Patent Document 7 describes printing using an inkjet method on a tablet, and describes a device that can be suitably used as a target tablet even with a bare tablet, particularly an orally disintegrating tablet.
For this reason, it is described that the suitability for the porosity of the tablet is 5 to 40%, and further 5 to 30% is preferable. Multi-color printing is also intended, with a drop-on-demand printer using piezo elements.
Mold locks, wet tablets, pressure tablets and the like are specifically described as objects.
However, no specific ink was described.

Japanese Patent Laid-Open No. 57-1768 Japanese Patent Laid-Open No. 7-81050 Special Table 2000-507820 Special Table 2000-512303 JP-T-2005-531330 gazette JP 2008-48924 International Publication No. 2009/025371

The present invention can also be applied to easily disintegrating tablets that are generally difficult to print, and can be composed only of materials that are allowed to be added to food or recorded on tablets. It is an object of the present invention to provide a tablet with print and a method for producing the same.

  As a result of intensive research to solve the above-mentioned problems, the present inventors have decided to use an ink jet method, and on the premise of an ink containing ethanol in order to improve drying properties, all are food additives. Or the ink was adjusted with the material approved by the Pharmaceutical Affairs Law, and the tablet which invented the printing to the easily disintegrating tablet in the characteristic adjustment with a tablet surface material and surface property was invented.

That is, the printed tablet according to the present invention is a printed tablet in which printing is performed on the surface of the tablet, the tablet comprising magnesium oxide as a main component, the surface being alkaline, and the printing being a tar dye. Composed of at least one dye selected from the following: a printing dot comprising a dry coating film of an ink-jet ink comprising, as essential components, a hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000, and a solvent containing ethanol and water, and Each print dot has a concave shape.

The method for producing a tablet with print according to the present invention is a method for producing a tablet with a print on the surface of the tablet, wherein the tablet comprises magnesium oxide as a main component, the surface is alkaline, and the tablet By printing on the surface with an inkjet ink having at least one pigment selected from tar pigments, hydroxypropylcellulose having a molecular weight of 10,000 to 150,000, and a solvent containing ethanol and water as essential components, inkjet It is characterized in that a printing dot made of a dried ink coating film and having a concave shape is formed on the surface of the tablet.

  Since the printed tablet of the present invention has a concave printed dot, it is prevented that the printed dot is rubbed by contact between tablets or other members, and the printed part is peeled off or transferred. Hateful. Further, the concave shape can be formed along with printing on the tablet, and in this case, no additional process is required to form the concave shape. The printing is composed of printing dots made of a dried coating film of inkjet ink, and since there is little printing pressure on the tablet during printing, it is also intended for easily disintegrating tablets that are generally difficult to print. can do. In addition, the ink-jet ink applied to the printed tablet of the present invention can be composed only of materials that are allowed to be added to food or recorded on tablets.

It is a microscope picture (3D) of the printing dot of the tablet with a printing of Example 2. FIG. It is a microscope picture (3D) of the printing dot of the tablet with a printing of Example 6 (it is a reference example ). It is a microscope picture (3D) of the printing dot of the tablet with a printing of the comparative example 2. It is a microscope picture (3D) of the printing dot of the tablet with a printing of the comparative example 11.

  Hereinafter, the printed tablet according to the present invention will be described in detail. However, the scope of the present invention is not limited to these explanations, and modifications other than the following examples are made as appropriate without departing from the spirit of the present invention. Can do.

〔tablet〕
The tablet with print of the present invention is one in which printing is performed on the surface of the tablet.
The tablet itself may be produced by a conventional method.
Examples of the tablet include those used as foods, pharmaceuticals, quasi drugs, feeds, or additives thereof.

In general, as drugs and excipients to be blended in tablets, those that can be administered orally are selected, and this point is the same in the present invention.
Specifically, the following various components can be mentioned, for example.

  Examples of drugs that can be incorporated into the tablets include gastrointestinal drugs, constipation drugs, vitamins, antipyretic analgesics, antihypnotics, anti-anxiety drugs, cardiotonics, antispasmodic drugs, antitussive expectorants, antiallergic drugs, antihistamines, antihistamines Examples include asthma drugs, antihypertensive drugs, antipruritic drugs, antiarrhythmic drugs, antibiotics, hyperlipidemia drugs, central nervous stimulants, hormone drugs, and crude drugs.

  Additives that can be incorporated into tablets include, for example, excipients, disintegrants, stabilizers, sweeteners, flavoring agents, antioxidants, cooling agents, flavoring agents / fragrances, pH adjusters, fragrances, antiseptics Agents, preservatives and the like.

  The excipients include lactose, mannitol, glucose, sucrose, xylose, maltose, maltitol, sorbitol, fructose, trehalose, erythritol, a combination of organic acid and carbonate, starch, modified starch, polyethylene glycol, liquid paraffin, (fine ) Crystalline cellulose, CMC, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, magnesium stearate, titanium oxide, talc and the like can be exemplified.

  Examples of the disintegrant include crospovidone, sodium carboxymethyl starch, carmellose calcium, croscarmellose sodium, pregelatinized starch and the like.

  Examples of the stabilizer include ascorbic acid, sodium ascorbate, adipic acid, aspartic acid, sodium aspartate, sodium sulfite, arginine, sodium benzoate, inositol, sodium edetate, erythorbic acid, sodium ersorbate, sodium citrate Glycine, glycerin, glycerin fatty acid ester, light anhydrous silicic acid, tocopherol acetate, gelatin, soybean oil unsaponifiable matter, polyoxyethylene polyoxypropylene glycol, anhydrous sodium citrate, glyceryl monostearate, sodium hydrogen phosphate, etc. be able to.

  Sweeteners include, for example, fructose, fructose glucose solution, aspartame, amateur, licorice, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, high fructose liquid sugar, glucose, water candy, lactose, sucrose, purified sucrose, honey, saccharin, Examples include saccharin sodium, stevia, acesulfame potassium, sucralose, erythritol, xylitol, sorbitol, maltitol, maltose, mannitol, and simple syrup.

  As a corrigent, alanine, ascorbic acid, aspartic acid, disodium 5'-inosinate, fennel, sodium chloride, orange oil, cacao powder, glycine, glycerin, glutamic acid, saffron, tartaric acid, ginger, sorbitol, mint, adipine Examples include acids, fumaric acid, peppermint, borneol, menthol, agate, green tea powder, apple juice, apple vinegar, lemon oil, rose oil, royal jelly, and the like.

  Examples of the antioxidant include ascorbic acid, tocopherol acetate, sodium sulfite, erythorbic acid, cysteine hydrochloride, soybean lecithin, butylhydroxyanisole, propyl gallate and the like.

  Examples of the refreshing agent include mint water, mint oil, menthol, geraniol, borneol, mint, peppermint oil and the like.

  As flavorings and fragrances, fennel, menthol, ethyl maltol, orange, ethyl vanillin, camphor, keihi, sugar flavor, cinnamaldehyde, cherry flavor, spruce tincture, peppermint, vanilla flavor, vanillin, bitter essence, fruit flavor, flavor GI , Vermouth flavor, mixed flavor, mint flavor, eucalyptus oil, agate, lemon powder, lemon oil, rosin, rose oil and the like.

  pH adjusters include sodium citrate, acetic acid, dilute hydrochloric acid, glycine, succinic acid, tartaric acid, sodium hydroxide, sodium bicarbonate, sodium carbonate, monosodium fumarate, phosphoric acid, trisodium phosphate, sodium hydrogen phosphate, Examples thereof include dipotassium phosphate and sodium dihydrogen phosphate.

  Examples of the preservative include benzoic acid, aminoethylsulfonic acid, sodium benzoate, ethanol, sodium edetate, agar, sodium citrate, sodium salicylate, sorbic acid, isopropyl paraoxybenzoate, ethyl paraoxybenzoate and the like.

  Examples of preservatives include sodium benzoate, ethanol, propylene glycol, glycerin, sodium edetate, salicylic acid, sorbitol, sorbic acid, isobutyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, methyl paraoxybenzoate and the like. .

As a tablet applied to the present invention, a tablet that exhibits a remarkable effect is a non-planar tablet that is difficult to print by a normal printing machine, or a tablet that is easily disintegratable. Further, it is a surface-formed tablet that is easily wetted and shrinks in volume by water and alcohol.
Furthermore, as an orally disintegrating tablet (OD tablet), for example, a tablet having an alkaline surface mainly composed of magnesium oxide has a significant advantage.
More specifically, for example, 60 to 95% by weight of granular magnesium oxide having a particle diameter of 70 to 500 μm is contained, and as an additive, lactose, crystalline cellulose, starch, powdered cellulose, mannitol, phosphoric acid Calcium hydrogen, anhydrous calcium hydrogen phosphate, low-substituted hydroxypropyl cellulose, low-substituted carboxymethyl starch, crystalline cellulose, carmellose, carmellose calcium, carmellose sodium, croscarmellose sodium, corn starch, calcium stearate, etc. Can be mentioned.

  Moreover, it is preferable that pH of the tablet surface shows the alkalinity of 9-13. The pH of the tablet surface can be confirmed using a universal indicator test paper moistened with distilled water.

[Inkjet ink]
The tablet with printing of the present invention is one in which printing is performed on the surface of the tablet as described above, and the printing is composed of printing dots made of a dry coating film of inkjet ink described in detail below.
That is, the ink-jet ink contains a pigment, a hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000, and a solvent containing ethanol and water as essential components.
In addition to these essential components, shellac resin and other additives may be contained.

<Dye>
The pigment is required to be edible as long as it is applied to tablets.
As such a dye, for example, a tar dye can be preferably used. Specifically, food blue No. 1, food blue No. 2, food yellow No. 4, food yellow No. 5, food red No. 2, food red No. 2, food red No. 3, food red No. 40, and aluminum lakes thereof. Etc. can be exemplified. In addition, iron oxide, titanium oxide, vegetable charcoal powder, and the like can also be used.
These may be used alone or in combination of two or more.

<Hydroxypropyl cellulose>
The inkjet ink applied to the present invention contains hydroxypropyl cellulose (hereinafter sometimes abbreviated as “HPC”).
This HPC also dissolves in water and alcohol, and contributes to the adjustment of the viscosity of the ink, the adhesion between the ink and the tablet, the dispersion stability of the pigment in the inkjet ink, and the like. Furthermore, it penetrates well into the tablet surface, contributing to the formation of a concave shape.

The HPC has a molecular weight of 10,000 to 150,000.
If it is this range, it will be easy to obtain the appropriate viscosity as an inkjet ink. Moreover, a pigment | dye can be disperse | distributed stably.
Conversely, when HPC having a molecular weight of less than 10,000 is used, it is difficult to stably disperse the pigment and prepare a stable inkjet ink.
On the other hand, if an HPC having a molecular weight exceeding 150,000 is used, the viscosity of the HPC itself is too high, so that the viscosity of the inkjet ink becomes excessively high, making it difficult to discharge with an inkjet printer and causing stringing. In addition, since the dispersion has a high viscosity, a dispersion load is excessive when performing the dispersion treatment (because it needs to be used in a disperser for a long time), resulting in a decrease in work efficiency.
Incidentally, the HPC of the above molecular weight distribution has a viscosity of 2 to 10 mPa. Corresponding to s (20 ° C.).
In addition, the molecular weight as used in the field of this invention is computed from intrinsic viscosity (measured value) using the following formula (1) of Mark-Houwink-Sakurada (Mark Fwinck, Sakurada).

                    [Η] = KMα (1)

  In formula (1), [η] is the intrinsic viscosity, M is the molecular weight, K is a constant specific to the substance to be measured, and α is a constant specific to the substance to be measured. The constant K and the constant α are known in advance for each substance to be measured. The intrinsic viscosity [η] is obtained by measuring the viscosity of a plurality of solutions having different concentrations of the solvent and the concentration of the substance to be measured, and extrapolating from the plurality of measured viscosity values.

<Solvent>
In the inkjet ink applied to the present invention, the solvent contains ethanol and water.
As the solvent contains ethanol, the affinity with the material on the tablet surface is increased, and the surface penetration and drying properties of ethanol make it difficult to prevent bleeding immediately after printing and cause transfer problems due to drying properties. Yes.
In the continuous ink jet printer, it is preferable to mainly use ethanol, which improves the drying property as compared with the water-based ink-jet ink containing 50% by weight or more of the entire ink-jet ink. Further, a recording portion having good drying properties can be formed even with a permeable material, and depending on the recording system, high-speed variable information can be printed.
Specifically, in a continuous inkjet ink, the amount of water relative to ethanol is preferably 40% by weight or less of the total solvent component. If it exceeds 40% by weight, the solubility of the resin used may be lowered or the drying property may be lowered.
In a drop-on-demand type (DOD type) ink jet printer, it is preferable to make an adjustment to use more water than ethanol.
As the ethanol, fermented ethanol for food or denatured ethanol is known and can be suitably used in the present invention.
In the range which does not impair the effect of this invention, you may further contain solvents other than ethanol and water.

<Shellac resin>
In the present invention, shellac resin can be used together with hydroxypropylcellulose. The shellac resin used is an edible resin obtained by refining a resinous substance derived from the silkworm, which is a mixture of many types of resin acids and their esterified products, waxes, pigments, etc. Are particularly preferably used. In the inkjet ink, among the shellac resins, it is preferable to use a purified shellac resin from which wax and pigments have been removed in advance. Further, bleached white shellac resin is also preferably used. This shellac resin contributes to the dispersion of the dye used in the present invention and fixing having water resistance, and also has a function of increasing the viscosity of the ink by dissolving in ethanol. The shellac resin is also soluble in a water / ethanol mixed solvent. Thus, it contributes as a preferable binder also in the point which can be used for the solvent which mixed water partially.
In the present invention, the ethanol-soluble shellac resin can be used as it is, but in order to obtain a more stable ink, the following adjustment of the acid value is also an advantageous method. .

"Adjustment of acid value of shellac resin ethanol solution"
In general, shellac resin often has an acid value of about 89 when an ethanol solution is used. In many cases, the pH of the ethanol solution is around 3.6. However, when an ink-jet ink is prepared with such a shellac resin solution having an acid value, the phenomenon of ink flight bending or ink droplet landing position abnormality (dot drop) is likely to occur during long-term continuous ejection. Then, when the acid value was examined, it was confirmed that these problems were remarkably reduced by using a shellac resin ethanol solution having an acid value of 80 to 85 and a pH of 0.5 to 3.0.
That is, in the present invention, it is preferable to use a shellac resin ethanol solution having an acid value of 80 to 85 and a pH of 0.5 to 3.0. The adjustment of the acid value of the ethanol solution can be performed by adding an acid, the elapsed time after adjusting the ethanol solution, or the processing temperature. It is hard to adopt. Therefore, a method of treating a shellac resin ethanol solution by mixing with a solid acid catalyst is preferable. The solid acid catalyst is preferably an H ⁺ type cation exchange resin because it can be performed in a relatively short time. Examples of the acid catalyst used here include XN-1004, XN-1005, Amberlist 15DRY, Amberlist 15WET, Amberlist 15JWET, Amberlist 31WET and the like, which are commercially available from Organo Corporation. In particular, a strongly acidic type is preferable.

Such adjustment of the acid value and pH of the shellac resin is carried out by adjusting a resin solution of 25 to 50% by weight of ethanol from powdered shellac resin and then a solid acid catalyst (for example, H ⁺ type cation exchange resin) 20 to 40% by weight is added, stirred, and contact-treated for about 3 to 10 hours. The treatment temperature can be 20 to 30 ° C. Thereafter, the acid catalyst is removed by filtration. Further, a contact treatment in which an acid catalyst is packed in a column and an ethanol solution of shellac resin is allowed to pass through the column is also applicable.
The acid value is titrated by a conventional method, the acid value is 80 to 85, and the pH is measured with a pH meter to confirm that the pH is 0.5 to 3.0. To do.
In addition, as a change in the characteristics of the shellac resin solution accompanying the adjustment of the acid value, the solid content decreases by about 10%. Further, the viscosity is reduced to about half. Re-solubility is greatly improved. Moreover, the improvement of the wiping speed of about 2 times can also be confirmed in the case of wiping the surface of the film formed by drying the ethanol solution with ethanol.

When the shellac resin is partially mixed with water, the pH of the ink should be adjusted to the alkali side of 7.5 to 10.5 with a pH adjuster in order to maintain stable solubility. Can do. When the pH of the ink is lower than 7.5, a part of the shellac resin is easily precipitated. On the other hand, when the pH of the ink exceeds 10.5, the odor in the printer or during printing becomes a problem.
The pH adjuster for adjusting the pH of the ink within the above range is preferably a food additive and a component that volatilizes after printing from the viewpoint of water resistance. For example, ammonium hydroxide, ammonium carbonate, ammonium chloride Etc. Especially, it is preferable to adjust pH using ammonium hydroxide or ammonium carbonate from a viewpoint from which a residue does not become a problem.

<Other additives>
The inkjet ink applied to the present invention may contain other additives such as a wetting agent, an emulsifier, and a conductive agent as long as the effects of the present invention are not impaired.

(Wetting agent)
Examples of the wetting agent include propylene glycol and glycerin.
The wetting agent serves to adjust the drying property of the inkjet ink and the viscosity of the inkjet ink. Further, depending on the background of the recording material, the effect of adjusting the permeability is also suitable for the purpose of use.
The wetting agent may be used as part of the solvent described above.

(emulsifier)
Examples of the emulsifier include sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester, and lecithin. These emulsifiers are edible and excellent in aqueous stability, and contribute to the dispersion stability of pigments in inkjet inks.

(Conductive agent)
The ink-jet ink applied to the present invention can be used for both continuous ink-jet printers and drop-on-demand ink-jet printers.
Here, the continuous ink jet printer continuously ejects ink droplets from the nozzles at regular time intervals, and adjusts the amount of charge charged to the ink droplets, thereby bending the flight direction of the ink droplets necessary for printing. Ink droplets that are unnecessary for printing are made to fly straight and are received and collected by a gutter. That is, in such a continuous ink jet printer, ink containing a conductive agent is used.
Note that the drop-on-demand ink jet printer operates ink ejecting means only at a timing necessary for printing to eject ink droplets from nozzles. Ink droplets are not ejected at a timing unnecessary for printing, and once ejected ink droplets are not collected. As the ink ejecting means of such a drop-on-demand ink jet printer, a piezo method or a thermal method is typical.
In the case of inkjet ink used in a continuous inkjet printer, the conductivity is adjusted according to the printer used. The conductive agent is used for adjusting the conductivity.
Examples of the conductive agent include sodium lactate, sodium acetate, ammonium carbonate, sodium dehydroacetate, and sodium pantothenate. All of these can be taken orally. In particular, sodium acetate dissolves well in alcohol-containing solvents, and can achieve the role of maintaining the conductivity of inkjet ink droplets in printers in a small amount. It is also effective in suppressing the decrease in stability as much as possible.
In addition, in tableted products where the print object has hygroscopicity, ink peeling and transfer are likely to occur, but sodium acetate has the characteristic that these symptoms are less likely to occur than other conductive agents. doing.
Also, the dispersion stability of the dye exhibits more stability than the addition of other conductive agents. The combination of the dye and sodium acetate is good not only for the stability immediately after the addition but also for the stability over time after the addition.

<Inkjet ink formulation>
As an inkjet ink applied to the present invention, when the total amount of inkjet ink is 100% by weight, it is preferable that each component in the inkjet ink has, for example, the following content ratio.
That is, the content ratio of the dye is preferably 0.3 to 20% by weight.
The HPC content is preferably 0.1 to 10% by weight.
The content of ethanol is preferably 5 to 90% by weight, and more preferably 15 to 90% by weight. In particular, in a continuous ink jet printer, it is preferably 40 to 90% by weight.
The water content is preferably 3 to 80% by weight. In particular, in a continuous ink jet printer, it is preferably 3 to 20% by weight.
In particular, in a continuous ink jet printer, the content ratio of the conductive agent is preferably 0.1 to 2% by weight. By using within this range, the electrical conductivity of the ink-jet ink can be appropriately set to about 0.5 to 5 mS / cm. Adjustment within a small amount is preferable even within the above range. When the addition amount of the conductive agent exceeds 2.0 parts by weight, there is a possibility of causing aggregation of the dye.
When the shellac resin is blended, the content ratio of the shellac resin is preferably 1 to 20% by weight.

  Moreover, it is preferable that it is 0.5-50 weight part of resin components with respect to 1 weight part of pigment | dyes, and it is more preferable that it is 2.5-35 weight part. In such a range, the adhesiveness of the ink with the tablet is excellent, and it is advantageous in forming the concave portion, and it is difficult to cause transfer to other carriers and the occurrence of stains in a transporting machine in the print transporting process.

[Production of inkjet ink]
The inkjet ink applied to the present invention can be prepared by arbitrarily mixing the above essential components and other optional components, and the production method thereof is not particularly limited.
However, in order to obtain a pigment with excellent dispersion stability, a production method including the following first step and the following second step is preferable.
In particular, the conductive agent tends to reduce the dispersion stability of the dye, but the following production method can effectively suppress the decrease in the dispersion stability of the dye due to the conductive agent. This is presumably because the stable dispersion was first prepared and then mixed with the solution containing the conductive agent.

<First step>
In the first step, a pigment is dispersed in a first resin solution in which HPC is dissolved in a first solvent essentially containing water and / or ethanol to obtain a dispersion.
HPC dissolves well in water and ethanol and stabilizes the dispersibility of the dye.

First, preparation of the first resin solution will be described.
The composition of the first solvent may be appropriately determined in consideration of the composition of the ink to be finally obtained in relation to the composition of the second solvent described later and the mixing ratio with the second solvent. Specifically, either water or ethanol may be used, but a mixed solvent of water and ethanol is preferable. In such a mixed solvent, the mutual ratio of water and ethanol is, for example, 90: 0 on a weight basis. ~ 30: 50 is preferred.
The content of HPC in the first resin solution may be appropriately determined in consideration of the composition of the ink to be finally obtained, the amount of HPC used in the second step described later, and the solubility of HPC. For example, it is preferable to select so that it may become 1-20 weight% of HPC with respect to the dispersion whole quantity mentioned later. If the HPC is less than 1% by weight, there is a possibility that a dye having a sufficient concentration cannot be dispersed. On the other hand, if the HPC exceeds 20% by weight, the viscosity of the first resin solution becomes excessive, which may cause clogging of the pipes of the disperser, making it impossible to perform sufficient dispersion treatment.

Next, description will be made on the point of obtaining a dispersion by dispersing the pigment in the first resin solution.
The amount of the dye added is preferably in the range of 5 to 30% by weight with respect to the total amount of the dispersion. If the dye is less than 5% by weight, it is necessary to add a large amount of dispersion in the ink preparation process in order to obtain an ink having a sufficient dye concentration. However, this makes the ink excessively viscous and suitable for an inkjet printer. There is a possibility that the adjustment to the viscosity is limited, or in some cases, clogging of the nozzle hole is caused. On the other hand, if it exceeds 30% by weight, the viscosity of the dispersion becomes excessive, which may cause clogging of the pipes of the disperser, the circulation during dispersion is insufficient, and sufficient dispersion treatment may not be performed.
Further, in relation to HPC in the first resin solution, for example, when 2 to 6 parts by weight of HPC is used with respect to 10 parts by weight of the dye, excellent dispersibility can be obtained. If the content of the HPC is less than 2 parts by weight, it may be difficult to sufficiently disperse the dye. On the other hand, when the content of HPC with respect to the pigment exceeds 6 parts by weight, there is a possibility that the viscosity at the time of dispersion becomes too high and the dispersion efficiency is lowered.
When dispersing in the first resin solution, a method of dispersing the dye and the first resin solution with a high-speed agitator mill, a method of applying an impact with the ball mill between the dye and the first resin solution with a reduced solvent content, etc. are appropriately selected. Can be used. However, from the aspect of mixing with the first resin solution in dispersion, dispersion using a horizontal sand mill using zirconia beads or the like as a dispersion medium is preferable. A medialess disperser that does not use a dispersive medium is also an effective method for producing a dispersoid with less contamination (contamination or contamination). As such a medialess disperser, Nanomizer (Nanomizer), Starburst (Sugino Machine Co., Ltd.), Microfluidizer (Paurec Co., Ltd.), etc. can be used.

<Second step>
In the second step, a second resin solution obtained by dissolving shellac resin or both a shellac resin and a conductive agent in a second solvent containing 50% by weight or more of ethanol as a whole and the dispersion obtained in the first step are prepared. Mix or mix the second resin solution in which HPC or both HPC and conductive agent are dissolved in the second solvent containing 50% by weight or more of ethanol with the dispersion obtained in the first step. To do.
The composition of the second solvent only needs to contain 50% by weight or more of ethanol, and the composition of the ink to be finally obtained, the composition of the first solvent and the mixing ratio with the first solvent described above. It may be determined appropriately in consideration of the above. As the remainder of the solvent, water is preferable, and other solvents such as propylene glycol may be used.
The content of shellac resin, HPC and conductive agent in the second resin solution is also the composition of the ink to be finally obtained, the amount of HPC used in the first step, the solubility of HPC and conductive agent, etc. May be appropriately determined in consideration of the above.
For example, when a second resin solution in which both shellac resin or shellac resin and a conductive agent are used is used, the ratio of shellac resin is preferably 0 to 20% by weight with respect to the total amount of the second resin solution.
When using the 2nd resin solution which dissolved both HPC or HPC and a electrically conductive agent, HPC has a preferable ratio of 1-10 weight% with respect to the 2nd resin solution whole quantity.
The conductive agent is preferably in a proportion of 0.2 to 2% by weight with respect to the total amount of the second resin solution. If the weight is less than 0.2%, sufficient conductivity cannot be imparted. In particular, ink droplets are insufficiently charged in a continuous ink jet printer, and ink droplets cannot be deflected, which may cause printing defects. is there. If it exceeds 2% by weight, the ion concentration of the whole ink becomes excessive. When the ion concentration is excessive, the repulsive force between the dispersed particles is weakened, which may cause aggregation of the dye.
The mixing ratio of the second resin solution and the dispersion is, for example, preferably from 95: 5 to 70:30 on a weight basis.

[Print dots]
The printing in the tablet with printing of the present invention is constituted by printing dots made of the dried ink-jet ink coating film described in detail above.
The formation of the printing dots on the tablet surface can be performed as follows, for example.
When used in an ink jet printer, the ink jet ink may be diluted with a diluting solvent containing ethanol, water and a conductive agent.
By using an inkjet printer while appropriately diluting the inkjet ink with a diluting solvent, even when severe continuous printing is performed with the inkjet printer, it is possible to prevent the concentration of the inkjet ink in the printer and to provide an appropriate conductivity. Can hold. Accordingly, long-term continuous printing performance can be stably continued without lowering the conductivity of the inkjet ink.

  The ink-jet ink applied to the present invention contains ethanol as a solvent and thus has excellent drying properties. Further, even a non-permeable material can form a recording portion having good water resistance, and depending on the recording system, high-speed variable information can be printed.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples. Hereinafter, for convenience, “parts by weight” will be expressed as “parts” and “% by weight” will be expressed as “%”.
In addition, Examples 3, 6, 9, 12, 15, 18, and 21 using the tablets of Prototype Example 3 are not the object of the present invention but are reference examples.

[Tablet prototype 1]
Mix 240 parts of magnesium oxide, 12 parts of croscarmellose sodium, 45.6 parts of crystalline cellulose, 3.6 parts of calcium stearate, add 150 parts of ethanol, disperse and knead, dry, granulate and granulate for tableting And it was compression-molded with a tableting machine to produce an uncoated tablet.
The tablet produced in Prototype Example 1 showed an alkaline surface by universal test paper moistened with purified water.

[Tablet prototype 2]
Add 480 parts of magnesium oxide, 24 parts of croscarmellose sodium, 91.2 parts of crystalline cellulose, 24 parts of corn starch, 4.8 parts of calcium stearate, add 360 parts of ethanol, knead, dry, and sizing Granules for tableting were obtained. The granules for tableting were compression molded with a tableting machine to produce uncoated tablets.
The tablet produced in Prototype Example 2 showed an alkaline surface by universal test paper moistened with purified water.

[Tablet prototype 3]
The powder made of crospovidone was pressed with a small manual tableting press to prepare tablets.
The tablet produced in Prototype Example 3 showed a neutral surface by universal test paper moistened with purified water.

[Tablet prototype 4]
Tablets were prepared by pressing the powder made of granular corn starch with a small manual tableting press.
The tablet produced in Prototype Example 4 showed a neutral surface by universal test paper moistened with purified water.

[Preparation Example 1 of Inkjet Ink]
<Preparation of Dispersion 1>
An HPC aqueous solution (first resin solution) was obtained by dissolving 10 parts of HPC (molecular weight 40,000) in 90 parts of water (first solvent).
A mill base was prepared by mixing 42 parts of an HPC aqueous solution and 3 parts of blue No. 1 aluminum lake, and then dispersed in a horizontal sand mill containing zirconia beads for 2 hours. The average particle size of blue No. 1 aluminum lake was 0.00. Dispersion 1 having a thickness of 38 μm was obtained (first step, see Table 1 described later).
<Preparation of inkjet ink>
Shellac resin (acid value 85) was added to 99 ° fermented ethanol (second solvent) and stirred to obtain an ethanol solution of shellac resin (25% shellac resin solution).
To 20 parts of the above dispersion 1, 12 parts of 25% shellac resin solution, 1 part of ammonium carbonate, 1 part of 50% aqueous sodium lactate solution and 66 parts of ethanol are added, and blue No. 1 in dispersion 1 is added using a horizontal mill. The aluminum lake was further dispersed (second step, see Table 2 below).
The resulting dispersion was designated as No. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Inkjet ink preparation example 2]
Add 2 parts of Blue No. 1, 26 parts of an aqueous solution of 10% HPC (molecular weight 40,000), 1 part of ammonium carbonate, 1 part of 50% aqueous sodium lactate, 10 parts of purified water, and 60 parts of ethanol, and use a stirrer with a blade. Was dissolved well to obtain a blue No. 1 solution.
The obtained lysate was designated as No.1. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Inkjet ink preparation example 3]
<Preparation of Dispersion 2>
An HPC aqueous solution (first resin solution) was obtained by dissolving 10 parts of HPC (molecular weight 40,000) in 90 parts of water (first solvent).
42 parts of the above HPC aqueous solution and 3 parts of yellow No. 5 aluminum lake were mixed to prepare a mill base, and then dispersed in a horizontal sand mill containing zirconia beads for 2 hours. Dispersion 2 having a size of 0.39 μm was obtained (first step, see Table 1 described later).
<Preparation of inkjet ink>
Shellac resin (acid value 83) was added to 99 ° fermented ethanol (second solvent) and stirred to obtain an ethanol solution of shellac resin (25% shellac resin solution).
To 20 parts of the above dispersion 2, 12 parts of 25% shellac resin solution, 1 part of ammonium carbonate, 1 part of 50% aqueous sodium lactate solution and 66 parts of ethanol are added, and yellow No. 5 in dispersion 2 is added using a horizontal mill. The aluminum lake was further dispersed (second step, see Table 2 below).
The resulting dispersion was designated as No. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Inkjet ink preparation example 4]
3 parts of blue No. 1, 1 part of red No. 102, 24 parts of 10% HPC (molecular weight 40,000) aqueous solution, 1 part of ammonium carbonate, 1 part of 50% aqueous sodium lactate solution, 10 parts of purified water and 60 parts of ethanol were added. Then, the mixture was thoroughly dissolved using a bladed stirrer to obtain a black solution.
The obtained lysate was designated as No.1. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Preparation Example 5 of Inkjet Ink]
<Preparation of Dispersion 1 and Dispersion 2>
Dispersion 1 and Dispersion 2 were prepared in the same manner as in Preparation of Dispersion 1 in Preparation Example 1 for Inkjet Ink and Preparation of Dispersion 2 in Preparation Example 2 for Inkjet Ink.
<Preparation of inkjet ink>
In the same manner as in Preparation Example 3, an ethanol solution (25% shellac resin solution) of shellac resin (acid value 83) was obtained.
To 10 parts of dispersion 1 and 6 parts of dispersion 2, add 12 parts of the 25% shellac resin solution, 1 part ammonium carbonate, 1 part 50% aqueous sodium lactate, 10 parts purified water, and 60 parts ethanol. The blue No. 1 aluminum lake and the yellow No. 5 aluminum lake in the dispersion were further dispersed using a horizontal mill (second step, see Table 2 described later).
The resulting dispersion was designated as No. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Inkjet ink preparation example 6]
Blue No. 1 2.4 parts, Red No. 102 1.6 parts, 10% HPC (molecular weight 40,000) aqueous solution 21.1 parts, glycerin 0.8 parts, propylene glycol 19.5 parts, purified water 43.2 And 11.4 parts of ethanol were added and dissolved well using a stirrer with a blade to obtain a black solution.
The obtained lysate was designated as No. Filtered through 63 filters. Subsequently, it filtered with the 0.8 micrometer glass filter, and obtained the inkjet ink.

[Inkjet ink adjustment example 7]
<Preparation of Dispersion 3>
3 parts of HPC (molecular weight 100,000) was dissolved in 39 parts of purified water, and 3 parts of blue No. 1 aluminum lake was added thereto and stirred to prepare a premix of blue No. 1 aluminum lake.
This premix was subjected to a dispersion treatment in a bead mill for 2 hours to prepare a 6.7% dispersion (dispersion 3) of Blue No. 1 aluminum lake.
<Preparation of inkjet ink>
An HPC solution was prepared by dissolving 10 parts of HPC (molecular weight 40,000) in 90 parts of ethanol.
While stirring 18 parts of the dispersion 3, 20 parts of the HPC solution was added thereto, and the dispersion 3 and the HPC solution were sufficiently mixed and dispersed. To this mixed dispersion, 1 part of sodium lactate was added to prepare an inkjet ink. This preparation solution was filtered through a filter having a pore diameter of 1 μm to obtain a blue inkjet ink.

[Inkjet ink preparation example 8]
<Preparation of Dispersion 4>
3 parts of HPC (molecular weight 40,000) was dissolved in 87 parts of purified water, and 10 parts of iron sesquioxide was added thereto and stirred to prepare a premix of iron sesquioxide.
This premix was subjected to a dispersion treatment with a bead mill for 2 hours to prepare a 10% dispersion of iron sesquioxide (dispersion 4).
<Preparation of inkjet ink>
An HPC solution was prepared by dissolving 2 parts of HPC (molecular weight 40,000) with 77 parts of ethanol.
While stirring 20 parts of the dispersion 4, the HPC solution was added thereto to sufficiently mix and disperse the dispersion 4 and the HPC solution. To this mixed dispersion, 1 part of sodium lactate was added to prepare an inkjet ink. This preparation solution was filtered through a filter having a pore size of 1 μm to obtain a reddish brown inkjet ink.

[Physical properties of inkjet ink]
About each inkjet ink obtained by the said preparation examples 1-8, the physical property was measured and evaluated.
Tables 1 and 2 summarize the formulations of dispersions 1 to 4 and each inkjet ink used in each inkjet ink, and Table 2 also lists the physical properties of each inkjet ink.

The measurement / evaluation of each physical property in Table 2 is as follows.
<Average particle diameter of pigment>
The average particle diameter of the pigment in the inkjet ink was measured by the median diameter (d50) using a particle size distribution meter (UPA type) manufactured by Nikkiso Co., Ltd.

<Viscosity of inkjet ink>
The viscosity (20 ° C., mPa · s) of the inkjet ink was measured using a viscometer (EH corn type RE-80L) manufactured by Toki Sangyo Co., Ltd.

<Conductivity of inkjet ink>
The conductivity (mS / cm) was measured using a conductivity meter (ES-51) manufactured by Horiba.

<Visibility>
It printed similarly to evaluation of the following adhesiveness, confirmed whether it was legible by visual observation, and evaluated by the following references | standards.
A: There is no change immediately after printing.
◯: Printing is slightly missing but legible.
X: Unreadable.

<Adhesion (peeling)>
Printing is performed on a processed product compressed by a tableting machine using a continuous inkjet printer (model KGK JET CCS-3000 manufactured by Kishu Giken Kogyo Co., Ltd.) and a drop-on-demand printer (1001 manufactured by XAAR) in a share mode. When 2 seconds passed, it was rubbed with tissue paper, and the presence or absence of peeling of the printed coating film was evaluated according to the following criteria.
A: No peeling at all.
○: Slightly peeled off, but can be read.
X: The print is completely peeled off and cannot be read.

<Printing performance in high temperature environment>
The state of the printing result when a printing test was performed with an ink jet printer in an environmental room maintained at 45 ° C. was evaluated according to the following criteria.
○: The printing state is good. There are no problems with inkjet printers.
X: Ink changes and aggregates at high temperature, causing ejection to become unstable.

<Printing performance in low temperature environment>
The state of the printing result when a printing test was performed with an ink jet printer in an environmental room maintained at 5 ° C. was evaluated according to the following criteria.
○: The printing state is good. There are no problems with inkjet printers.
X: The fluidity of the ink is increased and the piping and nozzles are clogged by lowering the temperature.

<Continuous discharge property>
The ink-jet ink prepared as described above was loaded into a continuous ink-jet printer (model KGK JET CCS-3000 manufactured by Kishu Giken Kogyo Co., Ltd.), and troubles (nozzle clogging, printing failure, The following criteria were used to determine whether or not there was an ink droplet landing position abnormality or ejection pressure abnormality. The DOD ink was confirmed by printing using a share mode drop-on-demand printer (1001 manufactured by XAAR).
○: Each printing dot has landed correctly.
X: Dot lacks or does not land at a predetermined position.

[Examples 1-3]
The inkjet ink obtained in Preparation Example 1 was put into an inkjet printer “CCS3000” (40 μm nozzle) manufactured by Kishu Giken Kogyo Co., Ltd., and printing was performed on each of the tablets according to Prototype Examples 1-3. Each printed tablet of Examples 1 to 3 was obtained.

[Examples 4 to 6]
The ink-jet ink obtained in Preparation Example 2 is put in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 3, whereby each printed tablet of Examples 4 to 6 is printed. Got.

[Examples 7 to 9]
The ink-jet ink obtained in Preparation Example 3 is placed in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 3, whereby each printed tablet of Examples 7 to 9 is printed. Got.

[Examples 10 to 12]
The ink-jet ink obtained in Preparation Example 4 is placed in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 3, whereby each printed tablet of Examples 10 to 12 is printed. Got.

[Examples 13 to 15]
The ink-jet ink obtained in Preparation Example 5 is put in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 3, whereby each of the printed tablets of Examples 13 to 15 is performed. Got.

[Examples 16 to 18]
The inkjet ink obtained in Preparation Example 6 was put into a share mode type drop-on-demand inkjet printer “XAAR Printer 1001”, and printing was carried out on each of the tablets according to Prototype Examples 1-3. Each printed tablet of Examples 16-18 was obtained.

[Examples 19 to 21]
The ink-jet ink obtained in Preparation Example 7 is put in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 3, whereby each printed tablet of Examples 19 to 21 is printed. Got.

[Comparative Examples 1-7]
In Examples 1, 4, 7, 10, 13, 16, and 19, each of the printed tablets of Comparative Examples 1 to 7 is the same except that the tablet according to Prototype Example 1 is changed to the tablet according to Prototype Example 4. Got.

[Comparative Examples 8 to 11]
The ink-jet ink obtained in Preparation Example 8 is placed in the ink-jet printer “CCS3000”, and printing is performed on each of the tablets according to Prototype Examples 1 to 4, whereby each printed tablet of Comparative Examples 8 to 11 is printed. Got.

[Evaluation of printed tablets]
The surface of each printed tablet of Examples 1-21 and Comparative Examples 1-11 was observed using a microscope.
As a result, it was confirmed that each of the printed tablets of Examples 1 to 21 had a concave printed dot. For reference, micrographs (3D) of printed dots are shown in FIGS. 1 and 2 for the printed tablets of Example 2 and Example 6, respectively.
On the other hand, no concave shape was observed in the tablets of Comparative Examples 1-7. For reference, a micrograph (3D) of the printed dots of the printed tablet of Comparative Example 2 is shown in FIG.
In addition, it was confirmed that each of the printed tablets of Comparative Examples 8 to 11 was a flat or convex dot. For reference, a micrograph (3D) of the printed dots of the printed tablet of Comparative Example 11 is shown in FIG.
Furthermore, when the dots after printing were rubbed with a finger, in each of the printed tablets of Comparative Examples 8 to 11, the transfer adhesion from the printing dots or the printing dots were easily removed. In each printed tablet, transfer adhesion and printed dots could not be removed.

[Consideration of results]
<Consideration based on results of Examples>
It was understood that the printed dots on the surface of the tablets were concave, which reduced the resistance to rubbing between the tablets and increased resistance to rubbing.

<Discussion based on results of comparative example>
In particular, from the results of Comparative Examples 8 to 11, it was suggested that the printed dots on the surface of the tablet protruded, thereby increasing the resistance to rubbing due to contact between the tablets. Depending on the adhesiveness to the tablet surface, it is thought that it is easier to peel off from the interface.

  The tablet with print according to the present invention is, for example, easy to discriminate the type of medicine and can be firmly recorded on the tablet, so that the tablet is difficult to peel off or transfer to the tablet. It can utilize suitably for a use.

Claims (12)

A tablet with a print on the surface of the tablet,
The tablet contains magnesium oxide as a main component, and the surface is alkaline.
Printing dots comprising a dry coating film of an ink-jet ink, wherein the printing includes at least one kind of dye selected from tar dyes , hydroxypropylcellulose having a molecular weight of 10,000 to 150,000, and a solvent containing ethanol and water as essential components A printed tablet in which each printing dot has a concave shape. The printed tablet according to claim 1 , wherein the tar pigment is an aluminum lake. The tablet with printing of Claim 1 or 2 in which the said tablet also contains a crystalline cellulose, croscarmellose sodium, and a calcium stearate as an additive. The printed tablet according to claim 3 , wherein the tablet also contains corn starch as an additive. The printed tablet according to any one of claims 1 to 4 , wherein the magnesium oxide has a particle size of 70 to 500 µm. The printed tablet according to any one of claims 1 to 5 , wherein the inkjet ink also contains a conductive agent. The printed tablet according to claim 6 , wherein the conductive agent is at least one selected from sodium acetate, ammonium carbonate, and sodium lactate. In the inkjet ink, the pigment content is 0.3 to 20% by weight, the hydroxypropyl cellulose content is 0.1 to 10% by weight, the ethanol content is 15 to 90% by weight, the water The tablet with printing of Claim 6 or 7 which is an inkjet ink whose content rate is 3 to 80 weight% and whose content rate of the said electrically conductive agent is 0.1 to 2 weight%. A method for producing a printed tablet, wherein the surface of the tablet is printed,
The tablet contains magnesium oxide as a main component, and the surface is alkaline.
By printing on the surface of the tablet with an inkjet ink having at least one dye selected from tar dyes, hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000, and a solvent containing ethanol and water as essential components The printing dots are formed on the surface of the tablet, each consisting of a dry coating film of inkjet ink, and each having a concave shape.
A method for producing printed tablets. The inkjet ink is
A first step of obtaining a dispersion by dispersing a dye in a first resin solution in which hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000 is dissolved in a first solvent essentially containing water and / or ethanol;
A second resin solution obtained by dissolving shellac resin or both a shellac resin and a conductive agent in a second solvent containing 50% by weight or more of ethanol as a whole, and the dispersion obtained in the first step are mixed. The manufacturing method of the tablet with a print of Claim 9 which is an inkjet ink manufactured by the manufacturing method provided with 2 processes. The inkjet ink is
A first step of obtaining a dispersion by dispersing a dye in a first resin solution in which hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000 is dissolved in a first solvent essentially containing water and / or ethanol;
A second resin solution in which hydroxypropyl cellulose having a molecular weight of 10,000 to 150,000 or both of the hydroxypropyl cellulose and a conductive agent is dissolved in a second solvent containing 50% by weight or more of ethanol as a whole; and in the first step, The manufacturing method of the tablet with a print of Claim 9 which is an inkjet ink manufactured by a manufacturing method provided with the 2nd process of mixing the obtained dispersion. The production of a tablet with print according to claim 11 , wherein the inkjet ink is an inkjet ink produced using 2 to 15 parts by weight of the hydroxypropylcellulose with respect to 10 parts by weight of the dye in the first step. Way .