JP2015218268A - Inkjet printing ink and tablets - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet printing ink formulation having improved various resistance properties such as light fastness and moisture resistance of inkjet printed images provided on tablet surfaces, even when a dye-based coloring agent is used when printing a solid formulation (tablets) by using an inkjet method, and to provide tablets provided with printing using the inkjet ink.SOLUTION: Inkjet printing is performed on tablets by using an inkjet printing ink which uses, as a coloring agent, a mixture of chlorophyllin dyes and erythrosine, where a compounding ratio of chlorophyllin dyes and erythrosine is 8 pts.mass or more and 100 pts.mass of chlorophyllin dyes relative to 1 pt.mass of erythrosine. Erythrosine which is a dye having low light fastness is prevented from receiving an effect of light by virtue of chlorophyllin dyes which are dyes having higher light fastness. As a result, light fastness of the inkjet printed image is improved.

Description

  The present invention relates to an ink for inkjet printing for improving various resistances such as light resistance and moisture resistance of an inkjet printed image applied to the surface of a medical tablet or the like, and a tablet subjected to inkjet printing.

There are many types of solid medical tablets such as tablets and capsules that have similar sizes, colors, and shapes. For identification, product names, component contents, etc. are encoded and directly recorded on individual tablets. Signs are often used.
As the marking means, a plate printing method and a plateless printing method are put into practical use.
However, the plate printing method represented by the gravure printing method and the gravure offset printing method is applicable to soft medical tablets, including uncoated tablets such as orally disintegrating tablets and other film-coated tablets, and ramune confectionery-like solid preparations. On the other hand, when the printing is performed, the plate comes into contact and stress is applied, so that the tablet or the solid preparation is broken and cannot be printed. In the case of the plateless printing method by the laser engraving method, there is a problem that the medicinal component of the tablet is thermally denatured by the laser.

  Therefore, printing by an inkjet method has been proposed as a printing method without contacting a tablet and without modifying a medicinal component (for example, see Patent Document 1). However, when printing on solid preparations such as tablets and capsules, it is necessary to use certified materials that can be taken orally as pharmaceutical additives for the pigments used in the ink, so the types of pigments that can be used are limited. ing. In particular, when a dye-based pigment is used, there is a problem that various resistances such as light resistance and moisture resistance are poor.

For applications that do not require long-term storage such as several months or more, such as printing the expiration date of fresh food such as chicken eggs or the date of manufacture directly on the surface of the food, iron chlorophyllin sodium, one of the dye-based pigments In addition, printing using an inkjet printing ink containing copper chlorophyllin sodium is performed (for example, see Patent Document 2 and Patent Document 3). As described above, since the ink used for these applications has poor light resistance and moisture resistance, there is a problem that it cannot be applied as it is to printing on a medical tablet that is premised on storage for 3 years or more. .
In addition, the management of safety against pigments has become stricter worldwide. For example, yellow tar pigments (food yellow No. 4, tartrazine) are legal legal pigments in Japan, but their effects on the human body have been reported. Cannot be used mainly in Europe. In addition, various dyes such as brilliant blue FCF (edible blue No. 1), which is a blue dye, have been restricted or prohibited for reasons such as induction of allergies and carcinogenicity.

Under such circumstances, iron chlorophyllin sodium is a highly safe pigment used as an internal medicine with a deodorizing effect, and copper chlorophyllin sodium is used as a gastrointestinal drug, and a very small amount of pigment containing erythrosine is used. It is very important as a so-called three-pharmaceutical dye in the European Pharmacopeia, the US Pharmacopeia, and the Japanese Pharmacopeia.
On the other hand, there are pigment-based dyes that are excellent in light resistance and moisture resistance, but there are very few pigments that are approved as pharmaceutical additives or food additives, such as red iron oxide and yellow iron oxide. Since the material having an excellent dispersion effect used in the application cannot be used as a pharmaceutical additive, it is extremely difficult to realize an ink in which a pigment is stably dispersed.

JP-A-9-302294 Japanese Patent Laid-Open No. 53-127010 Japanese Patent No. 3873519

With respect to the above problems, it is highly safe and can be used in various countries around the world. Furthermore, even when dye-based pigments are used when printing on solid preparations using the inkjet method, light resistance and moisture resistance There is a demand for an ink formulation that can improve various resistances such as the above.
The present invention has been made in view of such a situation, and the problem is to improve various resistances such as light resistance and moisture resistance of an ink jet printed image applied to the surface of a tablet for medical use. The composition of the ink for inkjet printing for making it and the tablet which performed the printing using the said ink for inkjet printing is provided.

One embodiment of the present invention is an inkjet printing ink used for inkjet printing on a tablet, wherein a pigment is a mixture of a chlorophyrin pigment composed of at least one of iron chlorophyllin sodium, copper chlorophyllin sodium and chlorophyllin sodium, and erythrosine. The blending ratio of the chlorophyllin pigment to the erythrosine in the pigment contained in the ink is 8 parts by mass or more and 100 parts by mass or less with respect to 1 part by mass of the erythrosine. Ink for inkjet printing, characterized by being.
The ratio of the mixture of the chlorophyllin pigment and the erythrosine to the entire ink may be 1 mass percent or more and 10 mass percent or less.

Another aspect of the present invention is a tablet characterized in that ink jet printing is performed using the ink for ink jet printing described in any of the above aspects.
It may be a film-coated tablet having a surface coated with a film coat layer.
The solvent system of the ink for inkjet printing may be a water-soluble solvent, and the film coat layer may include one or a mixed system of hydroxypropylcellulose and hydroxypropylmethylcellulose, and may contain titanium oxide.
It may be a medical tablet.

A mixture of at least one chlorophyllin pigment selected from iron chlorophyllin sodium, copper chlorophyllin sodium and chlorophyllin sodium and erythrosine (edible red No. 3) is used. The amount of the chlorophyllin pigment added to 1 part by mass is 8 parts by mass or more and 100 parts by mass or less of the ink jet printing ink. Red ink 102), Brilliant Blue FCF (Food Blue No. 1), Tartrazine (Food Yellow No. 4), Fast Green FCF (Food Green No. 3), etc. Compared to subjecting tablets, high durability against the effects of light and humidity from the outside, it is possible to suppress the discoloration of the printed image.
In addition, the inkjet of the present invention is also compared with a tablet that is printed with an inkjet ink that contains a chlorophyllin pigment or erythrosine, which is a pigment contained in the inkjet printing ink of the present invention, as a pigment independently without being mixed. The printing ink is confirmed to have excellent durability, and the durability of the printed image on the tablet can be further improved by mixing the chlorophyllin pigment and erythrosine at a specific ratio.

It is a schematic sectional drawing which shows an example of the medical tablet (plain tablet) to which this invention is applied. It is a schematic sectional drawing which shows an example of the medical tablet (film coating tablet) to which this invention is applied. It is an example of the printed image of a medical tablet (plain tablet). It is an example of the printed image of a medical tablet (film coating tablet). It is a graph which shows the light resistance test result of printed goods.

Hereinafter, the contents of the present invention will be described in detail.
The present invention relates to an ink for ink-jet printing that can improve the durability of a printed image applied to the surface of a medical tablet by an ink-jet printing method. In addition to (bare tablets), sugar-coated tablets, enteric-coated tablets, orally disintegrating tablets, and the like, film-coated tablets in which a water-soluble surface layer is formed on the outermost surface of the tablets can be mentioned.

  FIG. 1 is a schematic cross-sectional view showing an example of a medical tablet (plain tablet) that has been printed (printed), and a printed image 3 such as letters is printed on the upper surface of the solid preparation substrate 1 in a cross-sectional view, The uncoated tablet print 5 is formed. FIG. 2 is a schematic cross-sectional view showing an example of a medical tablet (film-coated tablet) on which printing (printing) has been performed, and an upper surface of the solid preparation substrate 1 having a film coat layer 7 formed on the surface in a cross-sectional view. A printed image 3 such as characters is printed on the film to form a film-coated tablet print 9. As shown in FIG. 3, a solid image ψ4 may be printed as the uncoated tablet print image 11, and a two-dimensional barcode is printed as the film coat print image 13 as shown in FIG. Also good.

  The active ingredient contained in the medical tablet is not particularly limited. For example, substances effective for the prevention and treatment of various diseases (eg sleep-inducing action, tranquilizer activity, antibacterial activity, antihypertensive action, anti-angina activity, analgesic action, anti-inflammatory activity, tranquilizing action, diabetes therapeutic activity, diuretic action , Anticholinergic activity, antigastric hyperactivity, antiepileptic activity, ACE inhibitory activity, β-receptor antagonist or agonist activity, anesthetic activity, appetite suppressive activity, antiarrhythmic activity, antidepressant activity, anticoagulant activity, antidiarrheal activity , Antihistaminic activity, antimalarial activity, antitumor activity, immunosuppressive activity, antiparkinsonism activity, antipsychotic activity, antiplatelet activity, antihyperlipidemic activity, etc.) Including, but not limited to, substances having a deodorizing action.

  The solid preparation in the present invention can be blended with an active ingredient together with an active ingredient as necessary. For example, in the case of a pharmaceutical preparation, a pharmaceutically acceptable carrier can be blended. As the pharmaceutically acceptable carrier, various organic or inorganic carrier substances commonly used as pharmaceutical materials are used. For example, excipients, lubricants, binders, disintegrants, thickeners and the like are appropriately mixed in appropriate amounts. . If necessary, additives such as preservatives, antioxidants, colorants, sweeteners and the like can be used.

The coloring matter contained in the ink for ink jet printing in the present invention is a chlorophyllin coloring matter composed of at least one selected from iron chlorophyllin sodium, copper chlorophyllin sodium or chlorophyllin sodium (hereinafter, three types may be collectively indicated as described above). And a mixture of erythrosin. Furthermore, the blending ratio of the chlorophyrin pigment to erythrosine is 8 to 100 parts by mass with respect to 1 part by mass of erythrosin. Iron chlorophyllin sodium, copper chlorophyllin sodium or chlorophyllin sodium are all water-soluble pigment powders, all of which are dark green in the form of a powder, and when dissolved in water, a blue-green to green-black aqueous solution is obtained. Erythrosin is also called Edible Red No. 3, which is a dark red water-soluble pigment powder, and when dissolved in water, it becomes a bright red aqueous solution.
Furthermore, copper chlorophyllin sodium is a pigment that can be used safely and widely in Japan as well as overseas as a pharmaceutical additive. Erythrosine is also a safe dye that can be used.

  As shown so far, both chlorophyllin dyes and erythrosine are used as ink printing ink dyes, but these dyes were used alone as ink printing ink dyes for medical tablets. In this case, the light resistance of the printed image was necessary and sufficient for the ink using the chlorophyllin coloring matter as compared with the application. Specifically, for example, in a sunlight exposure test of 1.2 million lux, the discoloration color ΔE of the solid printed image was 14 or less. On the other hand, both the light resistance was insufficient with the ink using only erythrosine. Specifically, for example, in the same sunlight exposure test of 1.2 million lux, the change color ΔE of the solid print image is 50 or more, and this is a situation in which almost all characters are lost if printed characters.

  In the present invention, the light resistance necessary and sufficient for the formation of a printed image on a medical tablet means that the discoloration color before and after exposure of a solid printed image is 15 or less in a 1,200,000 lux sunlight exposure test. I consider it. This was derived as a result of an opinion test conducted by the inventors with each medical staff. When the discoloration color exceeds 15, the tablet itself begins to be recognized as being altered. In addition, although it is a number larger than 3-6 which is a standard of the discoloration color ΔE in general commercial printed matter, there is no comparison between tablets before and after exposure, and it is assumed that the color fades naturally. Therefore, I was able to get this number. Here, the color change means the degree of color change due to the action of light.

  The reason why the blending ratio of the chlorophyrin pigment to erythrosine in the present invention is limited to a range of 8 parts by mass or more with respect to 1 part by mass of erythrosin is that when the ratio exceeds that range (for example, erythrosine) When the ratio of the chlorophyllin pigment is 4 parts by mass with respect to 1 part by mass), the effect of the discoloration color of erythrosin having low resistance is large, and the discoloration color ΔE exceeds 15 when a light resistance test is performed on a solid printed image. It is. As the blending amount of the chlorophyllin pigment is increased, the discoloration ΔE gradually decreases, and when the blending ratio of the chlorophyllin pigment is larger than the ratio of erythrosin: chlorophyrin pigment = 1: 7, the discoloration color ΔE is generally 14 and has light resistance superior to that of a green ink jet printing ink using a chlorophyllin pigment alone. In consideration of variations in the results of the light resistance test, the blending ratio of the chlorophyllin pigment to erythrosine in the present invention was set to erythrosine: chlorophyllin pigment = 1: 8 or more.

  In addition, the reason why the blending ratio of the chlorophyllin pigment to erythrosine in the present invention is limited to a range of 100 parts by mass or less with respect to 1 part by mass of erythrosin is when the range is exceeded (for example, When the ratio of the chlorophyllin pigment is 120 parts by mass with respect to 1 part by mass of erythrosin), the ink color tone and resistance to change are not affected even if the chlorophyllin pigment is iron chlorophyllin sodium, copper chlorophyllin sodium or chlorophyllin sodium This is because the fading property is no longer equivalent to that of ink containing no erythrosine.

  The reason why the effect of the present invention is manifested is that when light is irradiated, light is absorbed by a chlorophyllin pigment having high light resistance, and as a result, erythrosine having low light resistance is suppressed from being affected by light. It is estimated that. Compared to the case of using chlorophyllin pigments alone, the discoloration when mixed is reduced because chlorophyllin pigments, which are greenish, and red erythrosine are mixed. It is presumed that because the ink has a low color (red brown to black to dark green), the influence of the change in saturation is suppressed and the discoloration color is less noticeable.

  The ink for inkjet printing according to the present invention is characterized in that the blending ratio of the chlorophyllin pigment to erythrosine is 8 to 100 parts by mass with respect to 1 part by mass of erythrosin. If the blending amount of the pigment is 8 parts by mass or more and 100 parts by mass or less, it has light resistance equivalent to or superior to that of a green ink jet printing ink using a chlorophyllin pigment alone. Since the color tone changes, the mixing ratio is determined in accordance with the required ink color tone. Table 1 shows changes in the color tone when copper chlorophyllin sodium and erythrosine are mixed as a standard of the color tone developed for each mixing ratio. However, the color tone varies depending on the mixing ratio of the pigment and the ink solvent. As shown in Table 1, when copper chlorophyllin sodium and erythrosine are mixed, when the blending amount of copper chlorophyllin sodium is 8 parts by mass or more with respect to 1 part by mass of erythrosin, the ink color tone is reddish brown to black to black It turns out to be green.

In particular, the mixing of the two dyes of the present invention realizes black and gray achromatic inks without using brilliant blue FCF (food blue 1), which is sufficiently soluble in water with legal dyes but has been reported to be toxic. I can do it.
Incidentally, indigo carmine (edible blue No. 2) that can be used in Japan and overseas hardly dissolves in water, so it cannot be used as an ink for ink jet printing on water-soluble tablets, that is, as a dye for water-based ink, because it has no coloring effect.

The ratio of the content of the dye mixture comprising at least one chlorophyllin pigment selected from iron chlorophyllin sodium, copper chlorophyllin sodium or chlorophyllin sodium to erythrosine in the ink is 1 mass percent or more and 10 mass percent or less. It is preferable to be within the range. When the content is less than 1 mass percent, the print density of the printed image is insufficient. On the other hand, when the content exceeds 10 mass percent, the dissolution stability of the pigment is poor and the pigment is precipitated as a solid in the ink. However, it may cause nozzle clogging of the inkjet head during printing.
In particular, since chlorophyllin dyes synthesized from natural products have many impurities, they are often subjected to dye purification for removing ink for ink jet. Stable printing characteristics such as increase in viscosity and adhesion of thickened foreign matter during drying near the inkjet head nozzle cannot be obtained.

  The color material contained in the inkjet printing ink of the present invention necessarily contains erythrosin and a chlorophyllin pigment as described above, but the color material other than these two types is not particularly limited as long as it is edible. It can be appropriately selected and added from conventionally known synthetic food colors and natural food colors. Examples of the synthetic food dye include tar dyes, natural dye derivatives, natural synthetic dyes, and the like. As the tar dye, food red No. 2, food red No. 40, food red No. 102, food red No. 104, and the like are listed. Edible red No. 105, edible red No. 106, edible yellow No. 4, edible yellow No. 5, edible blue No. 1, edible blue No. 2, edible red No. 2 aluminum lake, edible red No. 3 aluminum lake, edible red No. 40 aluminum Rake, edible yellow No. 4 aluminum lake, edible No. 5 aluminum rake, edible blue No. 1 aluminum rake, edible blue No. 2 aluminum rake, etc., natural pigment derivatives such as norbixin potassium, etc. -Carotene, riboflavin and the like. Examples of natural edible pigments include anthocyanin pigments, carotenoid pigments, quinone pigments, flavonoid pigments, betaine pigments, monascus pigments, and other pigments originating from natural products. Anthocyanin pigments include red radish pigment, red cabbage pigment, red rice pigment, elderberry pigment, cowberry pigment, gooseberry pigment, cranberry pigment, salmonberry pigment, perilla pigment, Sim Blueberry pigment, strawberry pigment, and dark sweet cherry pigment. , Cherry pigment, hibiscus pigment, hakulberry pigment, grape juice pigment, grape skin pigment, black currant pigment, blackberry pigment, blueberry pigment, plum pigment, white berry pigment, boysenberry pigment, mulberry pigment, purple potato pigment, murasaki Examples include corn pigment, purple potato pigment, raspberry pigment, red currant pigment, Loganberry pigment, and other anthocyanin pigments. Examples of carotenoid pigments include Anato pigment, gardenia yellow, and other carotenoid pigments. Examples of the quinone dye include a cochineal dye, a sicon dye, a rack dye, and other quinone dyes. Examples of flavonoid pigments include safflower yellow, cuilliant pigments, onion pigments, and other flavonoid pigments. Examples of betaine dyes include beet red dyes. Examples of the Monascus pigment include Benikouji pigment and Benikouji yellow. Other pigments originating from natural products include turmeric pigments, wedge pigments, gardenia red pigments, and spirulina blue pigments.

  Among these, in consideration of the dispersion stability of the water-soluble ink, it is preferable that the color material is composed only of a dye-based food coloring because printing can be continued for a long time by the ink jet apparatus. This is because the problem of clogging ink in the nozzles of the ink jet apparatus is reduced because the dispersion of the coloring material in the ink is stable. Specifically as a dye-based food color, specifically, as a red color, edible red No. 102, edible red No. 106, etc., as a blue color, edible blue No. 1, an extract / purified product of gardenia color, etc. Yellow No. 4, food yellow No. 5 and the like are preferably used, but as described above, there are very few pigments internationally recognized such as Food Red No. 102.

  In the present invention, purified water, ethanol, glycerin, propylene glycol, polyethylene glycol 300 (average molecular weight 300) can be used as an ink solvent used when printing an image by the inkjet printing method, and the target ink is It can be used by appropriately mixing according to the physical properties. The mixing ratio is not particularly limited, but in order to prevent drying with a nozzle with ink, any of glycerin, propylene glycol and polyethylene glycol 300 is contained in the ink in the range of 1 to 30 mass percent. It is more preferable. If the content is less than 1 percent by weight, the ink is liable to dry and cause nozzle clogging. If the content exceeds 30 percent by weight, drying of the printed surface on the medical tablet surface becomes too slow, and the printed tablets are When contacted, it may cause a problem such that the undried ink adheres to the other tablet and becomes dirty.

  Although the medical tablet in this invention does not have a restriction | limiting in particular, The effect is high especially in the film coat tablet which coat | covered the film coat layer on the surface. This is because the pigment component tends to remain on the tablet surface due to the fact that the film-coated tablet has fewer voids than the uncoated tablet on the printed tablet surface, and the dye itself when the printing surface is affected by light or humidity. This is because these effects are stronger in the case of film-coated tablets than in plain tablets, and the durability of the dye itself is the largest factor that determines the color change on the printed surface. In particular, when the film coat layer contains hydroxypropylcellulose or hydroxypropylmethylcellulose, or one or a mixed system, and further contains titanium oxide, it is confirmed that the effect is large because the pigment component tends to remain on the tablet surface. It was done. In the case of an uncoated tablet, there are many voids, and even when the dye continues to penetrate into the tablet over time, the color change of the printed surface occurs, so the influence is relatively small.

  The ink for ink jet printing in the present invention is very useful because it can be applied to a commercially available ink jet apparatus. In the embodiments described below, printing examples in so-called drop-on-demand ink jets using piezo elements (piezoelectric ceramics) as actuators have been shown. However, as other drop-on-demand ink jet systems, minute heating elements are instantaneously used. Thermal ink jet method that discharges with water vapor pressure generated at high temperature (200-300 ° C), electrostatic type by vibrating the actuator electrostatically, ultrasonic method using ultrasonic cavitation phenomenon, etc. can be used It is.

Further, if the charging performance can be imparted to the ink, it is possible to use a continuous ejection type (continuous type).
In the above-described embodiment, the case where the tablet is applied to a medical tablet has been described. However, the present invention is not limited to this. For example, the present invention can also be applied to food such as ramune confectionery, feed, fertilizer, and detergent. is there.
In addition, the scope of the present invention is not limited to the illustrated and described exemplary embodiments, and includes all embodiments that provide the same effects as those intended by the present invention. Further, the scope of the invention is not limited to the combinations of features of the invention defined by the claims, but can be defined by any desired combination of specific features among all the disclosed features.

Examples of the present invention will be described below. In addition, this invention is not limited only to a following example.
<Example 1>
Manufacture of printed film-coated tablets using ink containing erythrosin and copper chlorophyllin sodium, and resistance test (manufacture of ink)
First, a printing ink was prepared. The ink was prepared from each component of a dye, an organic solvent, water, an internal resin, and a leveling agent. In order of preparation, first, water and an organic solvent were mixed to obtain a mixed solvent, then an internal resin and a leveling agent were added to obtain a transparent base solution, and then a color material was added to prepare an ink.

The internal resin is a material that functions as a nonvolatile resin component in the ink.
The leveling agent is a material that adjusts the surface tension of the ink so that the ejection drop from the inkjet head can be satisfactorily formed. Specifically, the surface tension of the ink is in the range of 24 mN / m to 34 mN / m. And preferred. However, in consideration of wettability on the surface layer of the solid preparation and penetration into the inside, it is necessary to select a surface tension value as small as possible, that is, good wettability. In this example, the surface tension is 24 to 28 mN / m. It was adjusted to become.
It should be noted that the smaller the surface tension is, the better it is, and if it is less than 24 mN / m, droplets will not be formed, and mist defects and splash phenomena (cracking of the discharge) will be caused.

The water used for the ink was ion-exchanged water, and polyethylene glycol 300 (meaning polyethylene glycol having an average molecular weight of 300) and ethanol were used as organic solvents. 118 g of ethanol and 147 g of polyethylene glycol 300 were added to 357 g of ion-exchanged water and stirred well to obtain 622 g of a mixed solvent.
21 g of polyethylene glycol 1540 (meaning polyethylene glycol having an average molecular weight of 1540) as an internal resin and sorbitan acid fatty acid ester (product name: “Poem O-80V”) as a leveling agent are added to 622 g of the above mixed solvent. 1 g) was added and stirred for about 1 hour to obtain 644 g of a transparent base solution.

  Divide the above-mentioned transparent base solution 644g into 7 equal parts and divide it into 92g parts, each containing 8g of erythrosine and copper chlorophyllin sodium (ink (1) is erythrosine only, ink (7) is copper chlorophyllin sodium) In addition, 100 g of each of seven types of ink (ink (1) / ink (2) / ink (3) / ink (4) / ink (5) / ink (6) / ink (7)) was obtained. Table 2 shows the composition of each ink.

  The solid foreign substances in the liquid were removed by allowing 100 g of each of the seven types of ink described above to pass through the membrane filter. 99 g of purified ink was obtained by passing once through a membrane filter having a diameter of 5.0 μ (cellulose acetate membrane) and then passing once through a membrane filter having a diameter of 0.8 μ (cellulose acetate membrane).

(printing)
Using the above 7 types of purified ink, test film coated tablets (base: adjusted starch, coating: hydroxypropyl methylcellulose 70%, titanium oxide 30% mixed) on an inkjet printer equipped with a bending mode piezo inkjet head , Diameter: 6.5 mm), a circular solid image (diameter: 4.0 mm) was printed. As a result, a film-coated tablet print printed in each color was obtained.

(Light resistance test)
The film-coated tablet printed matter whose chromaticity and optical color density were measured was irradiated with visible light of cumulative 1.2 million lux using a xenon weather meter (Toyo Seiki Seisakusho Ci4000). Chromaticity and optical color density were measured with a spectrophotometer for the uncoated tablet print irradiated with visible light, and the difference in the amount of change before and after the test of the chromaticity and optical color density due to the mixing ratio of the dyes was compared. The comparison results are shown in Table 2. As a result, it was confirmed that when the blending ratio of copper chlorophyllin sodium to erythrosine is 7 parts by mass or more with respect to 1 part by mass of erythrosin, there is little discoloration. The results are shown in FIG. In FIG. 5, the horizontal axis represents the mass of the chlorophyllin pigment with respect to 1 mass of erythrosine, and the vertical axis represents the exposure change color ΔE by the light resistance test of the film-coated tablet print image.

<Example 2>
Manufacture of film-coated tablet-printed products using ink containing erythrosin and iron chlorophyllin sodium, and resistance test (manufacture of ink)
First, a printing ink was prepared. Ink was prepared in the same manner as in Example 1 from each component of a pigment, an organic solvent, water, an internal resin, and a leveling agent. Similarly in the order of preparation, water and an organic solvent are first mixed to obtain a mixed solvent, then an internal resin and a leveling agent are added to obtain a transparent base liquid, and then a color material is added to prepare an ink. did.
The water used for the ink was ion exchange water, and polyethylene glycol 300 and ethanol were used as the organic solvent. 38.4 g of ethanol and 63 g of polyethylene glycol 300 were added to 165 g of ion-exchanged water, and the mixture was stirred well to obtain 266.4 g of a mixed solvent.

96.4 g of polyethylene glycol 1540 (meaning polyethylene glycol having an average molecular weight of 1540) as an internal resin is added to 266.4 g of the above-mentioned mixed solvent, followed by sorbitan acid fatty acid ester (product name: “Poem O-80V”) as a leveling agent. 0.6 g of Riken Vitamin Co.) was added and stirred for about 1 hour to obtain 276 g of a transparent base solution.
Divide the above-mentioned transparent base solution 276g into 3 equal parts and divide it into 92g parts, and add 8g of erythrosin and iron chlorophyllin sodium in different proportions to obtain 100g of each of three types of ink A / ink B / ink C. It was. Table 3 shows the composition of each ink.

  The solid foreign substances in the liquid were removed by passing 100 g of each of the above-mentioned three types of ink through the membrane filter. 99 g of purified ink was obtained by passing once through a membrane filter having a diameter of 5.0 μ (cellulose acetate membrane) and then passing once through a membrane filter having a diameter of 0.8 μ (cellulose acetate membrane).

(printing)
Using the above three types of purified ink, test film coated tablets (base: adjusted starch, coating: hydroxypropyl methylcellulose 70%, titanium oxide 30% mixed) on an inkjet printer equipped with a bending mode piezo inkjet head , Diameter: 6.5 mm), a circular solid image (4.0 mm in diameter) and a two-dimensional barcode (“QR code (registered trademark)”, 3.5 mm square) were printed. As a result, a film-coated tablet print printed in each color was obtained.

(Light resistance test)
The above-mentioned film-coated tablet printed matter whose chromaticity and optical color density were measured was irradiated with visible light of a cumulative 1.2 million lux using a xenon weather meter (Toyo Seiki Seisakusho Ci4000). Chromaticity and optical color density were measured with a spectrophotometer for the uncoated tablet print irradiated with visible light, and the difference in the amount of change before and after the test of the chromaticity and optical color density due to the mixing ratio of the dyes was compared. The comparison results are shown in Table 3. As a result, it was confirmed that the discoloration color was small when the blending ratio of iron chlorophyllin sodium to erythrosine was 7 parts by weight or more of iron chlorophyllin sodium with respect to 1 part by weight of erythrosine. The results are shown in FIG.

<Example 3>
Production of film-coated tablet products using ink containing erythrosin and sodium chlorophyllin, and resistance test (production of ink)
First, a printing ink was prepared. Inks were prepared in the same manner as in Example 1 and Example 2, which consisted of the following components: pigment, organic solvent, water, internal resin, and leveling agent. Similarly in the order of preparation, water and an organic solvent are first mixed to obtain a mixed solvent, then an internal resin and a leveling agent are added to obtain a transparent base liquid, and then a color material is added to prepare an ink. did.
The water used for the ink was ion exchange water, and polyethylene glycol 300 and ethanol were used as the organic solvent. 38.4 g of ethanol and 63 g of polyethylene glycol 300 were added to 165 g of ion-exchanged water, and the mixture was stirred well to obtain 266.4 g of a mixed solvent.

96.4 g of polyethylene glycol 1540 (meaning polyethylene glycol having an average molecular weight of 1540) as an internal resin is added to 266.4 g of the above-mentioned mixed solvent, followed by sorbitan acid fatty acid ester (product name: “Poem O-80V”) as a leveling agent. 0.6 g of Riken Vitamin Co.) was added and stirred for about 1 hour to obtain 276 g of a transparent base solution.
The transparent base liquid 276g was divided into three equal parts and divided into 92g, and 8g of erythrosine and sodium chlorophyllin were added to each of them in different proportions to obtain 100g of each of three types of ink i / ink ii / ink iii. . Table 4 shows the composition of each ink.

  The solid foreign substances in the liquid were removed by passing 100 g of each of the above-described three types of inks i to iii through a membrane filter. 99 g of purified ink was obtained by passing once through a membrane filter having a diameter of 5.0 μ (cellulose acetate membrane) and then passing once through a membrane filter having a diameter of 0.8 μ (cellulose acetate membrane).

(printing)
Using three types of the above purified inks i to iii, with an inkjet printer equipped with a bending mode piezo-type inkjet head, a film coating tablet for testing (base: adjusted starch, coating: hydroxypropylmethylcellulose 70%, titanium oxide) A 30% mixture, diameter: 6.5 mm) was printed with a circular solid image (diameter 4.0 mm) and a two-dimensional barcode (“QR code (registered trademark)”, 3.5 mm square). As a result, a film-coated tablet print printed in each color was obtained.

(Light resistance test)
The above-mentioned film-coated tablet printed matter whose chromaticity and optical color density were measured was irradiated with visible light of a cumulative 1.2 million lux using a xenon weather meter (Toyo Seiki Seisakusho Ci4000). Chromaticity and optical color density were measured with a spectrophotometer for the uncoated tablet print irradiated with visible light, and the difference in the amount of change before and after the test of the chromaticity and optical color density due to the mixing ratio of the dyes was compared. The comparison results are shown in Table 4. As a result, it was confirmed that when the blending ratio of chlorophyllin sodium to erythrosine is 7 parts by mass or more with respect to 1 part by mass of erythrosin, there is little discoloration. The results are shown in FIG.

1: Solid preparation base material 3: Print image 5: Uncoated tablet print 7: Film coat layer 9: Film coat tablet print 11: Uncoated tablet print image (solid image)
13: Printed film-coated tablet (two-dimensional barcode)

Claims (6)

In an inkjet printing ink used for inkjet printing on tablets,
A mixture of erythrosine and a chlorophyllin pigment composed of at least one of iron chlorophyllin sodium, copper chlorophyllin sodium and chlorophyllin sodium as an ink,
The blending ratio of the chlorophyllin pigment to the erythrosine in the pigment contained in the ink is such that the blending amount of the chlorophyllin pigment is 8 parts by mass or more and 100 parts by mass or less with respect to 1 part by mass of the erythrosin. Ink for inkjet printing.   2. The ink for inkjet printing according to claim 1, wherein a ratio of the mixture of the chlorophyllin coloring matter and the erythrosine to the whole of the ink is 1% by mass or more and 10% by mass or less.   A tablet, wherein ink jet printing is performed using the ink for ink jet printing according to claim 1.   4. The tablet according to claim 3, wherein the tablet is a film-coated tablet having a surface coated with a film coat layer.   The solvent system of the ink for inkjet printing is a water-soluble solvent, the film coat layer includes one or a mixed system of hydroxypropylcellulose and hydroxypropylmethylcellulose, and contains titanium oxide. The tablet according to claim 4.   The tablet according to any one of claims 3 to 5, wherein the tablet is a medical tablet.

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