WO2019142899A1 - Pigment composition, inkjet water-based ink composition, and solid formulation - Google Patents

Pigment composition, inkjet water-based ink composition, and solid formulation Download PDF

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Publication number
WO2019142899A1
WO2019142899A1 PCT/JP2019/001424 JP2019001424W WO2019142899A1 WO 2019142899 A1 WO2019142899 A1 WO 2019142899A1 JP 2019001424 W JP2019001424 W JP 2019001424W WO 2019142899 A1 WO2019142899 A1 WO 2019142899A1
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Prior art keywords
pigment
lake
pigment composition
mass
content
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PCT/JP2019/001424
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French (fr)
Japanese (ja)
Inventor
悠人 榎本
聡一郎 森川
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
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Priority claimed from JP2019006331A external-priority patent/JP7362252B2/en
Application filed by 株式会社Ｓｃｒｅｅｎホールディングス filed Critical 株式会社Ｓｃｒｅｅｎホールディングス
Publication of WO2019142899A1 publication Critical patent/WO2019142899A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints

Definitions

  • the present invention relates to a pigment composition, an aqueous ink composition for inkjet, and a solid preparation, and more specifically, it is applicable to image printing for solid preparations such as pharmaceuticals and foods, and dispersion stability of lake pigment (storage stability) Pigment composition, an aqueous ink composition for inkjet, and a solid preparation.
  • Ink-jet inks used for printing on solid preparations are classified into a dye ink using a dye and a pigment ink (for example, patent document 1) in which a pigment is dispersed. It is divided roughly.
  • dye inks have the advantage that they have various colors and are excellent in vivid color developability, but they have the disadvantage of being easily discolored and inferior in light resistance.
  • pigment inks have the advantage of being hardly faded compared to dye inks and having excellent light resistance, but have the disadvantage of being inferior in color development to dye inks. Therefore, from the viewpoint of printing an image excellent in light resistance on a solid preparation, it is preferable to use a pigment ink.
  • the pigments are roughly classified into organic pigments and inorganic pigments, and examples of the organic pigments include lake pigments obtained by laked dyes soluble in a solvent. Lake pigments exhibit bright colors like dyes and have the property of being insoluble in water. Therefore, if printing is performed on the surface of a solid preparation with a pigment ink using this lake pigment, it becomes possible to form a printed image having excellent color developability and having light resistance and water resistance.
  • the present invention has been made in view of the above problems, and the object of the present invention is applicable to the printing of an image excellent in color development for solid preparations such as pharmaceuticals and foods, and the dispersion stability of the lake pigment (storage stability Pigment composition, an aqueous ink composition for inkjet, and a solid preparation.
  • the lake pigment storage stability Pigment composition, an aqueous ink composition for inkjet, and a solid preparation.
  • the pigment composition according to the present invention is an edible pigment composition comprising at least one of a lake pigment, a pigment dispersant, and a dispersion stabilizer, in order to solve the problems described above, wherein the dispersion stabilizer is And at least one selected from the group consisting of carboxylic acid, carboxylic acid salt, phosphonic acid, phosphonic acid salt and ethylenediaminetetraacetic acid salt, and the content of the lake pigment is 20% of the total weight of the pigment composition.
  • the content of the dispersion stabilizer is 10% by mass or less based on the total mass of the pigment composition.
  • a lake pigment for example, when a pigment composition dispersed with a desired average dispersed particle size is produced using a paint shaker, the average dispersed particle size increases with the passage of time, and the pigment composition gels.
  • the problem was found. This is considered to be the result of metal ions derived from the lake pigment binding to the pigment dispersant, and in the present invention, the dispersion state of the lake pigment is stabilized in the present invention as described above, against the problem of gelation.
  • at least one selected from the group consisting of carboxylic acid, carboxylic acid salt, phosphonic acid, phosphonic acid salt and ethylenediaminetetraacetic acid salt as a dispersion stabilizer to be maintained in the above.
  • the content of the dispersion stabilizer is 10% by mass or less with respect to the total mass of the pigment composition, thereby suppressing the decrease in the dispersibility of the lake pigment due to the presence of an excess of the dispersion stabilizer. it can. Further, by setting the content of the lake pigment to 20% by mass or less with respect to the total mass of the pigment composition, the ejection stability at the time of ejecting the aqueous ink composition containing the pigment composition from the inkjet nozzle is favorably maintained. can do.
  • the content of the lake pigment is preferably 15% by mass or less based on the total mass of the pigment composition.
  • the lake pigment is a group consisting of Red No. 2, Red No. 3, Red No. 40, Red No. 102, Yellow No. 4, Yellow No. 5, Yellow No. 3, Green No. 3, Blue No. 1 and Blue No. 2. It is preferable that it is what rake-ized any one kind of dye selected more.
  • the pigment dispersant is sodium polyacrylate, polyvinyl pyrrolidone, polysaccharide, gelatin, collagen, polyvinyl alcohol, polyvinyl alcohol derivative, aminoalkyl methacrylate copolymer, methacrylic acid copolymer, ammonio alkyl methacrylate copolymer, acrylic It may be at least one selected from the group consisting of ethyl acid / methyl methacrylate copolymer and vinyl acetate.
  • the aqueous ink composition for inkjet according to the present invention contains a pigment composition and has edible properties in order to solve the above-mentioned problems.
  • the pigment composition contains 10% by mass or less of carboxylic acid or the like with respect to the total mass of the pigment composition as a dispersion stabilizer for stably maintaining the dispersed state of the lake pigment.
  • the aqueous ink composition for inkjet according to the present invention comprises such a pigment composition, whereby the average dispersed particle size of the lake pigment in the present invention increases with the passage of time. It is possible to provide an aqueous ink composition for ink jet that suppresses the gelation of the pigment composition and suppresses the gelation of the pigment composition. In addition, since the content of the lake pigment is 20% by mass or less based on the total mass of the pigment composition, it is possible to provide an aqueous ink composition for inkjet having good ejection stability from the inkjet nozzle.
  • the solid preparation according to the present invention is a solid preparation having a dry film of an aqueous ink for ink jet on the surface to solve the above-mentioned problems, wherein the aqueous ink for ink jet is the aqueous ink composition for ink jet Is included.
  • the dried film of the inkjet ink contains at least one type of lake pigment, so the printed image formed by the dried film is excellent in color development while maintaining good light resistance. ing.
  • the aqueous ink composition contains a dispersion stabilizer that stably maintains the dispersed state of the lake pigment, when the aqueous ink composition is ejected onto the surface of the solid preparation by the inkjet method, the ejection failure is suppressed. can do. As a result, a dry film can be formed on the surface of the solid preparation without discharge failure, and an image with excellent visibility can be formed.
  • a solid preparation capable of preventing dispensing errors, accidental ingestion, and the like.
  • a dispersion stabilizer consisting of at least one selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphonic acids, phosphonic acid salts and ethylenediaminetetraacetic acid salts is used in an amount of 10% relative to the total mass of the pigment composition.
  • the dispersion stability (storage stability) of the lake pigment can be improved by containing a dispersion stabilizer such as a carboxylic acid.
  • the lake pigment is contained at 20% by mass or less based on the total mass of the pigment composition, direct printing can be favorably performed on solid preparations such as pharmaceuticals and foods by the inkjet method without impairing the ejection stability. . Furthermore, by using a lake pigment as a coloring agent, it is possible to make the light resistance and color development of the printed image excellent.
  • the pigment composition according to the present embodiment is a composition of a pigment dispersion containing at least one lake pigment as a colorant, a pigment dispersant, and a dispersion stabilizer.
  • the pigment composition of the present embodiment can be made edible by using a material conforming to the pharmaceutical additive defined by the Pharmaceutical Affairs Law, the Japanese Pharmacopoeia, or the standard of food additives. Thus, it can be suitably used for recording an image or the like by an inkjet method on a solid preparation such as a medicine or food.
  • the term "edible” as used herein means a substance approved for oral administration as a pharmaceutical product or pharmaceutical additive, and / or a substance recognized as a food or food additive.
  • the "ink jet system” means a system in which an aqueous ink composition is discharged as droplets from a fine ink jet head, and the droplets are fixed on a solid preparation to form an image. The details of the solid preparation will be described later.
  • the lake pigment is present in the pigment composition in a dispersed state.
  • the lake pigment is not particularly limited as long as it is edible.
  • “lake pigment” means a pigment obtained by lake forming a dye soluble in a main solvent, and more specifically, the dye is adsorbed to the precipitant by adding a precipitant such as a metal salt, It is a precipitate precipitated as an insoluble salt (insoluble fine particles).
  • the dye that is soluble in the main solvent is not particularly limited, but preferably red 2, red 3, red 40, red 102, yellow 4, yellow 5, yellow 5, green 3, blue 1, and blue. It is at least one selected from the group consisting of No. 2.
  • lake pigment More specific examples of the lake pigment include red No. 2 aluminum lake, red No. 3 aluminum lake, red No. 4 aluminum lake, red No. 40 aluminum lake, red No. 102 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4 Barium lake, yellow No. 4 zirconium lake, yellow No. 5 aluminum lake, yellow No. 5 barium lake, yellow No. 5 zirconium lake, green No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 1 barium lake, blue No. 1 zirconium lake , Blue No. 2 aluminum lake, and the like. These lake pigments can be used alone or in combination of two or more.
  • the content of the lake pigment is 20% by mass or less, preferably 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass, based on the total mass of the pigment composition.
  • the content of the lake pigment is 20% by mass or less, preferably 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass, based on the total mass of the pigment composition.
  • the pigment dispersant improves the dispersibility of the lake pigment in the dispersion medium.
  • the pigment dispersant is not particularly limited as long as it can improve the dispersibility of the lake pigment and is edible.
  • a pigment dispersant for example, sodium polyacrylate, polyvinyl pyrrolidone, polysaccharide, gelatin, collagen, polyvinyl alcohol, polyvinyl alcohol derivative, aminoalkyl methacrylate copolymer, methacrylic acid copolymer, ammonio alkyl methacrylate copolymer, ethyl acrylate / methacrylic acid And at least one selected from the group consisting of an acid methyl copolymer and vinyl acetate.
  • the content ratio of the lake pigment to the pigment dispersant is preferably 1: 0.2 to 1: 4, and more preferably 1: 0.5 to 1: 1 on a mass basis.
  • the fall of the dispersibility of a lake pigment can be prevented as a content ratio is 1: 0.2 or more.
  • the content ratio is 1: 4 or less, it is possible to prevent the aqueous ink from adhering to the nozzle plate due to the increase in viscosity of the aqueous ink and the discharge stability being lowered due to the adhesion.
  • the dispersion stabilizer has a function of chelating the metal ion in order to prevent the metal ion derived from the lake pigment (for example, aluminum ion etc.) from binding to the pigment dispersant.
  • the dispersion stability of the lake pigment can be improved, and more specifically, the average dispersed particle diameter of the lake pigment is prevented from increasing with the passage of time, and the dispersion is good even after storage for a certain period of time The state can be maintained to prevent gelation of the pigment composition.
  • dispersion stability refers to a pigment composition or an inkjet aqueous ink composition containing the pigment composition (described in detail later) by containing a dispersion stabilizer. It means the property that the dispersibility of the pigment hardly decreases even after a certain time has passed, and is also referred to as storage stability.
  • the dispersion stabilizer is not particularly limited as long as it can improve the dispersion stability of the lake pigment and is edible.
  • examples of such dispersion stabilizers include at least one selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphonic acids, phosphonic acid salts and ethylenediaminetetraacetic acid salts.
  • the carboxylic acid is not particularly limited, and examples thereof include L-tartaric acid, DL-tartaric acid, gluconic acid, citric acid, fumaric acid, DL-malic acid, lactic acid and the like.
  • the carboxylate is not particularly limited.
  • citrate such as calcium citrate, triethyl citrate, sodium citrate, sodium dihydrogen citrate, disodium citrate, etc .
  • Gluconates such as magnesium
  • L-tartrates such as L-sodium tartrate
  • lactates such as aluminum lactate and calcium lactate
  • fumarates such as monosodium fumarate
  • malic acid such as disodium malate
  • succinic acid examples include succinate salts such as disodium; DL-tartrate salts such as sodium DL-tartrate;
  • the phosphonic acid is not particularly limited, and examples thereof include phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phytic acid and the like.
  • the phosphonate is not particularly limited, and examples thereof include potassium dihydrogen phosphate, sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate.
  • the ethylenediaminetetraacetic acid salt is not particularly limited, and examples thereof include ethylenediaminetetraacetic acid disodium and ethylenediaminetetraacetic acid sodium calcium.
  • the exemplified dispersion stabilizers may be used alone or in combination of two or more.
  • the content of the dispersion stabilizer is 10% by mass or less, preferably 0.1% by mass to 6% by mass, and more preferably 1% by mass to 2% by mass, based on the total mass of the pigment composition.
  • the content of the dispersion stabilizer is 10% by mass or less, preferably 0.1% by mass to 6% by mass, and more preferably 1% by mass to 2% by mass, based on the total mass of the pigment composition.
  • the pigment composition according to the present embodiment includes a dispersion medium for dispersing the lake pigment.
  • the dispersion medium include water, and more specifically, those obtained by removing ionic impurities such as deionized water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water. .
  • water sterilized by ultraviolet irradiation or hydrogen peroxide addition is preferable because it can prevent the generation of mold and bacteria over a long period of time.
  • the content of the dispersion medium is not particularly limited, and can be set as necessary.
  • a mixed solution of water and a water-soluble organic solvent may be used as the dispersion medium.
  • the water-soluble organic solvent is not particularly limited as long as it meets the criteria such as the Pharmaceutical Affairs Law. Specifically, examples thereof include ethyl alcohol, n-butyl alcohol, isobutyl alcohol, n-propyl alcohol, isopropyl alcohol, acetone, propylene glycol, polyethylene glycol, glycerin and the like.
  • the compounding amount in the case of using a water-soluble organic solvent in combination with the dispersion medium is not particularly limited, and can be appropriately set as needed.
  • the pH of the pigment composition at 25 ° C. is preferably in the range of 2 to 10, more preferably in the range of 5 to 9, and particularly preferably in the range of 6 to 8 from the viewpoint of dispersion stability of the lake pigment.
  • the particle size (D10) of 10% in cumulative particle size in volume-based cumulative particle size distribution of the lake pigment in the pigment composition is preferably in the range of 50 nm to 300 nm immediately after preparation of the pigment composition and after a certain period.
  • the range of 70 nm to 150 nm is more preferable.
  • the particle size (D50) of 50% of the integrated particle size in the volume-based integrated particle size distribution of the lake pigment in the dispersed state is preferably in the range of 50 nm to 700 nm immediately after preparation of the pigment composition and after a certain period.
  • the range of 60 nm to 500 nm is more preferable, and the range of 70 nm to 150 nm is particularly preferable.
  • D50 By setting D50 to 50 nm or more, it is possible to prevent the deterioration of the dispersion stability, the light resistance, and the discharge stability, and to prevent the reduction of the printing density.
  • D50 to 700 nm or less separation and sedimentation of the lake pigment can be prevented, and the dispersion stability can be maintained.
  • the particle size (D99) of 99% of the cumulative particle size in the volume-based cumulative particle size distribution of the lake pigment is preferably in the range of 50 nm to 3000 nm, 60 nm to 800 nm immediately after preparation of the pigment composition and after a certain period. Is more preferably in the range of 100 nm to 600 nm.
  • D10, D50, and D99 of each lake pigment should just be contained in the said numerical range.
  • the values of D10, D50 and D99 of the lake pigment are values measured by a dynamic light scattering method using Microtrac UPA-EX 150 (trade name, manufactured by Nikkiso Co., Ltd.).
  • the mixing method and the addition order of the lake pigment, the pigment dispersant, the dispersion stabilizer, the dispersion medium, and the other additives to be blended if necessary are not particularly limited.
  • a lake pigment, a pigment dispersant, a dispersion stabilizer, water as a dispersion medium, etc. may be mixed at one time, and the mixture may be subjected to dispersion treatment using a conventional disperser.
  • the dispersion time in the dispersion process is not particularly limited, and can be set as needed.
  • the disperser used in the dispersion treatment of the lake pigment is not particularly limited as long as it is a commonly used disperser. Specifically, for example, a ball mill, a roll mill, a sand mill, a bead mill, a paint shaker, a nanomizer and the like can be mentioned.
  • the pigment composition of the present embodiment also includes the form of a pigment dispersion for preparing the aqueous ink composition. It is.
  • aqueous ink composition for inkjet is an aqueous ink containing at least a pigment composition and the main solvent being water.
  • the aqueous ink composition of the present embodiment is edible and is suitably used for inkjet recording.
  • the water-based ink composition uses a lake pigment as a coloring agent, it is excellent in color development as compared to a conventional pigment-based water-based ink composition.
  • the content of the pigment composition is 20% by mass or less in terms of pigment content based on the total mass of the aqueous ink composition, preferably in the range of 1% by mass to 20% by mass, and in the range of 2% by mass to 15% by mass.
  • the range of 2% by mass to 10% by mass is more preferable, and the range of 4% by mass to 8% by mass is particularly preferable.
  • the coloring power can be improved by setting the content of the pigment composition to 1% by mass or more.
  • “pigment part conversion” means converting only by the content of the lake pigment.
  • water water as a main solvent
  • water it is preferable to use pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water or the like, or from which ionic impurities such as ultrapure water have been removed.
  • water sterilized by ultraviolet irradiation or hydrogen peroxide addition is preferable because it can prevent the generation of mold and bacteria over a long period of time.
  • it does not specifically limit as content of water It can set suitably as needed.
  • additives may be blended as long as it meets the criteria of the pharmaceutical additive, the Japanese Pharmacopoeia, or the official regulations of the food additive prescribed by the Pharmaceutical Affairs Law.
  • additives include surface tension modifiers, wetting agents, water-soluble resins, organic amines, surfactants, preservatives, viscosity modifiers, antifoaming agents, antioxidants, reduction inhibitors and the like.
  • the content of these additives is not particularly limited except for the surface tension regulator and the wetting agent, and can be appropriately set as necessary (the content of the surface tension regulator and the wetting agent will be described later, respectively). ).
  • the surface tension regulator is not particularly limited as long as it conforms to the standards of the Pharmaceutical Affairs Law, and specific examples thereof include glycerin fatty acid ester and the like.
  • glycerin fatty acid esters include decaglyceryl caprylate, decaglyceryl laurate and the like.
  • the content of the surface tension regulator is preferably in the range of 0.1% by mass to 5% by mass, and more preferably in the range of 1% by mass to 2% by mass, with respect to the total mass of the aqueous ink composition. Is more preferred.
  • the content of the surface tension adjusting agent is 0.1% by mass or more, discharge failure due to meniscus formation failure or the like in the nozzle of the ink jet head is prevented, and clogging of the nozzle Can be prevented. As a result, the ejection stability can be improved.
  • the content of the surface tension regulator is 5% by mass or less, it is possible to prevent the adverse effect on the discharge due to the insoluble portion of the surface tension regulator or the emulsification failure.
  • the wetting agent is not particularly limited as long as it meets the standards of the Pharmaceutical Affairs Law, and specific examples thereof include propylene glycol and glycerin.
  • the amount of the wetting agent added is preferably 1% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, with respect to the total mass of the aqueous ink composition.
  • the aqueous ink composition of the present embodiment can be suitably used for an inkjet ink.
  • the water-based ink composition of the present embodiment is edible because it uses a material conforming to the standards such as the Pharmaceutical Affairs Law, and can be printed directly on the surface of a tablet such as a supplement.
  • non-contact printing by ink jet method is enabled even for tablets having poor surface smoothness such as uncoated tablets and OD tablets.
  • the aqueous ink composition of the present embodiment uses a lake pigment, an image excellent in light resistance and color developability can be printed directly on the surface of a solid preparation such as a medicine or a supplement.
  • the aqueous ink composition of the present embodiment is at least contained in an inkjet aqueous ink as a final product, and can also be used as the aqueous inkjet ink itself.
  • the aqueous ink composition of the present embodiment can be produced by mixing the above-mentioned components by an appropriate method. That is, for example, the above-described additives and the like are added to the dispersion of the pigment composition, and then diluted with water. After that, the solution is sufficiently stirred, and if necessary, filtration is performed to remove coarse particles and foreign substances that cause clogging. Thus, the aqueous ink composition according to the present embodiment can be obtained.
  • each material does not specifically limit as a mixing method of each material, For example, materials are sequentially added to the container provided with stirring apparatuses, such as a mechanical stirrer and a magnetic stirrer, and stirring and mixing are performed.
  • stirring apparatuses such as a mechanical stirrer and a magnetic stirrer
  • filtration method For example, centrifugal filtration, filter filtration, etc. are employable.
  • the aqueous ink composition of the present embodiment is excellent in the dispersibility and the dispersion stability (storage stability) of the lake pigment, and therefore, can be suitably used for an ink jet ink.
  • the aqueous ink composition of the present embodiment is edible since it uses a lake pigment, a dispersion stabilizer and the like conforming to the standards of the Pharmaceutical Affairs Law and the like, and is on the surface of solid preparations such as pharmaceuticals and supplements. It is possible to print directly.
  • non-contact printing by ink jet method is enabled even for tablets having poor surface smoothness such as uncoated tablets and OD tablets.
  • the aqueous ink composition is also excellent in light resistance, the occurrence of bleeding can be prevented even when printed directly on the surface of a solid preparation such as a medicine or a supplement.
  • solid preparation is meant to include food preparations and pharmaceutical preparations, and as a solid preparation form, for example, OD tablets (orally disintegrating tablets), plain tablets, FC (film coated) tablets, sugar-coated tablets And tablets or capsules. Also, the solid preparation may be for pharmaceutical use or food use. Examples of tablets for food use include health foods such as tablets and supplements.
  • a print image consisting of a dried film directly printed by an inkjet recording method is formed on the surface of the solid preparation.
  • the dry film is at least constituted by the lake pigment contained in the aqueous ink composition.
  • the solid preparation of the present embodiment since the printed image formed of the dried film is excellent in light resistance, it is possible to prevent, for example, the deterioration of the image of various information such as product information. In addition, since the printed image is also excellent in color development, it is possible to improve the identification of the user. As a result, the solid preparation of the present embodiment maintains good visibility over a long period of time, making it possible to prevent dispensing errors and accidental ingestion.
  • the inkjet recording method for the surface of the solid preparation is not particularly limited.
  • the aqueous ink can be discharged as droplets from a fine nozzle, and the droplets can be attached to the tablet surface.
  • the discharge method is not particularly limited, and for example, known methods such as continuous injection type (charge control type, spray type, etc.), on demand type (piezo type, thermal type, electrostatic suction type, etc.) can be adopted. .
  • each material of the pigment composition conforms to the standard of pharmaceutical additives, Japanese Pharmacopoeia or Food Additives Official Standards stipulated by the Pharmaceutical Affairs Law.
  • Example 1 In this example, 8 g of yellow No. 4 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 1 g of disodium hydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the vessel, and 45 g of ion exchanged water was further added.
  • TEGO registered trademark
  • Dispers 715 W manufactured by Evonik, mass 6 g of average molecular weight 3000
  • disodium hydrogen phosphate manufactured by Wako Pure Chemical Industries, Ltd.
  • the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion
  • Example 2 In this example, the content of disodium hydrogen phosphate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g.
  • a pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 3 In this example, disodium succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 4 In this example, the content of disodium succinate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g.
  • a pigment composition according to this example was produced in the same manner as in Example 3 except for the above.
  • Example 5 In this example, disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 6 In this example, the content of disodium malate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g.
  • a pigment composition according to this example was produced in the same manner as in Example 5 except for the above.
  • Example 7 In this example, ethylenediaminetetraacetic acid disodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 8 In this example, the content of disodium ethylenediaminetetraacetate as a dispersion stabilizer was changed to 2 g, and the content of ion exchange water to 44 g.
  • a pigment composition according to this example was produced in the same manner as in Example 7 except for the above.
  • Comparative example 1 In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 1 except for the above.
  • Example 9 In this example, citric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer.
  • a pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 10 In this example, malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer.
  • a pigment composition according to this example was produced in the same manner as in Example 9 except for the above.
  • Example 11 In this example, 1 g of citric acid was used as a dispersion stabilizer, and 0.1 g of polyvinyl pyrrolidone (trade name: Kollidon 12PF, manufactured by BASF Japan Ltd.) was used as a pigment dispersant. Furthermore, the content of ion exchange water was changed to 50.9 g. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
  • Example 12 In this example, malic acid was used as a dispersion stabilizer.
  • a pigment composition according to this example was produced in the same manner as in Example 11 except for the above.
  • Example 13 In this example, 2 g of disodium malate was used as a dispersion stabilizer. Furthermore, the content of ion exchange water was changed to 49.9 g. A pigment composition according to this example was produced in the same manner as in Example 11 except for the above.
  • Comparative example 2 In this comparative example, the dispersion stabilizer was not blended, and the content of ion exchange water was changed to 51.9 g. A pigment composition according to this comparative example was produced in the same manner as in Example 11 except for the above.
  • Example 14 In this example, 8 g of red No. 3 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 2 g of disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the container, and further 44 g of ion exchange water was added.
  • TEGO registered trademark
  • Dispers 715 W manufactured by Evonik, mass 6 g of average molecular weight 3000
  • disodium malate manufactured by Wako Pure Chemical Industries, Ltd.
  • the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion
  • Comparative example 3 In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 14 except for the above.
  • Example 15 In the present example, a green No. 3 aluminum lake (manufactured by Daiwa Kasei Co., Ltd.) was used as a lake pigment.
  • a pigment composition according to this example was produced in the same manner as Example 14 except for the above.
  • Comparative example 4 In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 15 except for the above.
  • Example 16 In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) was used as a lake pigment.
  • a pigment composition according to this example was produced in the same manner as Example 14 except for the above.
  • Comparative example 5 In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 16 except for the above.
  • Example 17 In this example, 8 g of red No. 40 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 2 g of disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the container, and further 44 g of ion exchange water was added.
  • TEGO registered trademark
  • Dispers 715 W manufactured by Evonik, mass 6 g of average molecular weight 3000
  • disodium malate manufactured by Wako Pure Chemical Industries, Ltd.
  • the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion
  • Comparative example 6 In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 17 except for the above.
  • Example 18 In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.06 g, and the content of ion exchanged water to 45.94 g.
  • a pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
  • Example 19 In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.1 g, and the content of ion exchanged water to 45.9 g.
  • a pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
  • Example 20 In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.6 g and the content of ion exchanged water to 45.4 g.
  • a pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
  • Example 21 In this example, the content of disodium malate as a dispersion stabilizer was changed to 5.7 g and the content of ion exchanged water to 40.3 g.
  • a pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
  • Example 22 In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass average) Molecular weight 3000), disodium malate (made by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer, and ion-exchanged water as a dispersion medium in a container, using a disperser (paint shaker, made by Asada Iron Works Ltd.), Dispersion was carried out at normal temperature for 6 hours (dispersion time). Moreover, in the case of dispersion
  • TEGO registered trademark
  • aqueous ink composition for inkjet
  • Example 23 In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass average) Molecular weight 3000), disodium malate (made by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer, and ion-exchanged water as a dispersion medium in a container, using a disperser (paint shaker, made by Asada Iron Works Ltd.), Dispersion was carried out at normal temperature for 6 hours (dispersion time). Moreover, in the case of dispersion
  • TEGO registered trademark
  • caprylic acid decaglyceryl (trade name: SY Glyster MCA 750 (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., HLB value 16)) as a surface tension regulator, propylene glycol as a wetting agent and ions Exchanged water was added, and an aqueous ink composition was prepared so as to achieve the blending ratio shown in Table 6, and stirred with a disper.
  • the aqueous ink composition of this example was produced.
  • Example 24 In the present Example, the compounding quantity of each component was changed into the value shown in Table 6.
  • An aqueous ink composition according to this example was produced in the same manner as in Example 23 except for the above.
  • each pigment composition was stored in a sealed container, respectively, and was allowed to stand and stored for a certain period in an environment of 25 ° C. Thereafter, the lake pigments D10, D50 and D99 were again measured in the same manner as described above.
  • the storage period was 3 days for the pigment compositions of Examples 1 to 16 and 18 to 21 and Comparative Examples 1 to 5, and was 10 days for the pigment compositions of Example 17 and Comparative Example 6. The results are shown in Tables 1 to 6.
  • D10 is 50 nm to 300 nm
  • D50 is 50 nm to 700 nm
  • D99 is 50 nm to 3000 nm in each of the lake pigments, and the ejection stability is excellent. It was confirmed that an aqueous ink composition was obtained.

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Abstract

Provided are: a pigment composition having excellent dispersion stability (storage stability) of a lake pigment, and which can be applied for printing an image having excellent color development on a medicine, food, or other solid formulation; an inkjet water-based ink composition; and a solid formulation. The pigment composition pertaining to the present invention is an edible pigment composition including, at least, one or more types of lake pigments, a pigment dispersant, and a dispersion stabilizer, the dispersion stabilizer being at least one species selected from the group consisting of carboxylic acids, carboxylates, phosphonic acids, phosphonates, and ethylene diamine tetraacetates, the content of the lake pigment being 20% by mass or less with respect to the total mass of the pigment composition, and the content of the dispersion stabilizer being 10% by mass or less with respect to the total mass of the pigment composition.

Description

顔料組成物、インクジェット用水性インク組成物及び固体製剤Pigment composition, aqueous ink composition for inkjet and solid preparation
　本発明は顔料組成物、インクジェット用水性インク組成物及び固体製剤に関し、より詳細には、医薬品や食品等の固体製剤に対する画像印刷に適用可能であり、レーキ顔料の分散安定性（保存安定性）に優れた顔料組成物、インクジェット用水性インク組成物及び固体製剤に関する。 The present invention relates to a pigment composition, an aqueous ink composition for inkjet, and a solid preparation, and more specifically, it is applicable to image printing for solid preparations such as pharmaceuticals and foods, and dispersion stability of lake pigment (storage stability) Pigment composition, an aqueous ink composition for inkjet, and a solid preparation.
　医薬品や食品等の固体製剤（例えば、錠剤やカプセル剤等）への印刷に用いるインクジェット用インクは、染料を用いた染料インクと、顔料を分散させた顔料インク（例えば、特許文献１）とに大別される。一般に、染料インクは色彩が多様で、鮮やかな発色性に優れるという長所を持つ一方、褪色し易く耐光性に劣るという短所を持つ。これに対して、顔料インクは、染料インクと比べ褪色し難く、耐光性に優れるという長所を持つ一方、染料インクと比べ発色性に劣るという短所を持つ。従って、耐光性に優れた画像を固体製剤に印刷するとの観点からは、顔料インクを採用するのが好適である。 Ink-jet inks used for printing on solid preparations (for example, tablets, capsules, etc.) such as pharmaceuticals and foods are classified into a dye ink using a dye and a pigment ink (for example, patent document 1) in which a pigment is dispersed. It is divided roughly. In general, dye inks have the advantage that they have various colors and are excellent in vivid color developability, but they have the disadvantage of being easily discolored and inferior in light resistance. On the other hand, pigment inks have the advantage of being hardly faded compared to dye inks and having excellent light resistance, but have the disadvantage of being inferior in color development to dye inks. Therefore, from the viewpoint of printing an image excellent in light resistance on a solid preparation, it is preferable to use a pigment ink.
　ここで、顔料は有機顔料と無機顔料に大きく分類され、当該有機顔料としては、例えば、溶媒に可溶な染料をレーキ化して得られるレーキ顔料が挙げられる。レーキ顔料は染料のような鮮やかな色を呈し、水に対して不溶性の性質を有する。そこで、このレーキ顔料を用いた顔料インクで固体製剤の表面に印刷を行えば、発色性に優れ、かつ耐光性及び耐水性を有する印刷画像を形成することが可能になる。 Here, the pigments are roughly classified into organic pigments and inorganic pigments, and examples of the organic pigments include lake pigments obtained by laked dyes soluble in a solvent. Lake pigments exhibit bright colors like dyes and have the property of being insoluble in water. Therefore, if printing is performed on the surface of a solid preparation with a pigment ink using this lake pigment, it becomes possible to form a printed image having excellent color developability and having light resistance and water resistance.
特開２０１５－１４０４１４号公報JP, 2015-140414, A
　しかし、ペイントシェーカーを用いて、所望の平均分散粒子径でレーキ顔料が分散した顔料組成物を作製したところ、レーキ顔料の平均分散粒子径が時間の経過と共に増大し、顔料組成物がゲル化することが判明した。 However, when a pigment composition in which a lake pigment is dispersed with a desired average dispersion particle size is prepared using a paint shaker, the average dispersion particle size of the lake pigment increases with the passage of time, and the pigment composition gels. It has been found.
　本発明は前記問題点に鑑みなされたものであり、その目的は、医薬品や食品等の固体製剤に対し発色性に優れた画像の印刷に適用可能であり、レーキ顔料の分散安定性（保存安定性）に優れた顔料組成物、インクジェット用水性インク組成物及び固体製剤を提供することにある。 The present invention has been made in view of the above problems, and the object of the present invention is applicable to the printing of an image excellent in color development for solid preparations such as pharmaceuticals and foods, and the dispersion stability of the lake pigment (storage stability Pigment composition, an aqueous ink composition for inkjet, and a solid preparation.
　本発明に係る顔料組成物は、前記の課題を解決するために、少なくとも１種のレーキ顔料、顔料分散剤、及び分散安定剤を少なくとも含む可食性の顔料組成物であって、前記分散安定剤が、カルボン酸、カルボン酸塩、ホスホン酸、ホスホン酸塩及びエチレンジアミン四酢酸塩からなる群より選ばれる少なくとも１種であり、前記レーキ顔料の含有量が、前記顔料組成物の全質量に対し２０質量％以下であり、前記分散安定剤の含有量が、前記顔料組成物の全質量に対し１０質量％以下である。 The pigment composition according to the present invention is an edible pigment composition comprising at least one of a lake pigment, a pigment dispersant, and a dispersion stabilizer, in order to solve the problems described above, wherein the dispersion stabilizer is And at least one selected from the group consisting of carboxylic acid, carboxylic acid salt, phosphonic acid, phosphonic acid salt and ethylenediaminetetraacetic acid salt, and the content of the lake pigment is 20% of the total weight of the pigment composition. The content of the dispersion stabilizer is 10% by mass or less based on the total mass of the pigment composition.
　レーキ顔料においては、例えば、ペイントシェーカーを用いて、所望の平均分散粒子径で分散させた顔料組成物を作製したところ、時間の経過と共に平均分散粒子径が増大し、顔料組成物がゲル化するという問題が判明した。これは、レーキ顔料に由来する金属イオンが顔料分散剤と結合する結果生じるものと考えられ、このゲル化の問題に対し、本発明においては、前記構成の通り、レーキ顔料の分散状態を安定的に維持させる分散安定剤として、カルボン酸、カルボン酸塩、ホスホン酸、ホスホン酸塩及びエチレンジアミン四酢酸塩からなる群より選ばれる少なくとも１種を含有させる。これにより、本発明においては、これらの化合物がレーキ顔料由来の金属イオンをキレート化する結果、当該金属イオンと顔料分散剤との結合を防止し、顔料組成物のゲル化を防止することができる。すなわち、前記の構成によれば、カルボン酸等をレーキ顔料の分散安定剤として含有させることにより、当該レーキ顔料の平均分散粒子径が時間の経過と共に増大するのを抑制し、レーキ顔料の分散安定性（保存安定性）を向上させることができる。 In the case of a lake pigment, for example, when a pigment composition dispersed with a desired average dispersed particle size is produced using a paint shaker, the average dispersed particle size increases with the passage of time, and the pigment composition gels. The problem was found. This is considered to be the result of metal ions derived from the lake pigment binding to the pigment dispersant, and in the present invention, the dispersion state of the lake pigment is stabilized in the present invention as described above, against the problem of gelation. And at least one selected from the group consisting of carboxylic acid, carboxylic acid salt, phosphonic acid, phosphonic acid salt and ethylenediaminetetraacetic acid salt as a dispersion stabilizer to be maintained in the above. As a result, in the present invention, as a result of these compounds chelating metal ions derived from lake pigments, bonding between the metal ions and the pigment dispersant can be prevented, and gelation of the pigment composition can be prevented. . That is, according to the above configuration, by containing a carboxylic acid or the like as a dispersion stabilizer of the lake pigment, the increase of the average dispersed particle diameter of the lake pigment with the passage of time is suppressed, and the dispersion stability of the lake pigment The stability (storage stability) can be improved.
　尚、分散安定剤の含有量は、顔料組成物の全質量に対し１０質量％以下であり、これにより、分散安定剤が過剰に存在することによるレーキ顔料の分散性の低下を抑制することができる。また、レーキ顔料の含有量を顔料組成物の全質量に対し２０質量％以下とすることにより、当該顔料組成物を含む水性インク組成物をインクジェットノズルから吐出させる際の吐出安定性を良好に維持することができる。 The content of the dispersion stabilizer is 10% by mass or less with respect to the total mass of the pigment composition, thereby suppressing the decrease in the dispersibility of the lake pigment due to the presence of an excess of the dispersion stabilizer. it can. Further, by setting the content of the lake pigment to 20% by mass or less with respect to the total mass of the pigment composition, the ejection stability at the time of ejecting the aqueous ink composition containing the pigment composition from the inkjet nozzle is favorably maintained. can do.
　前記の構成においては、前記レーキ顔料の含有量が、前記顔料組成物の全質量に対し１５質量％以下であることが好ましい。 In the above configuration, the content of the lake pigment is preferably 15% by mass or less based on the total mass of the pigment composition.
　また前記の構成においては、前記レーキ顔料が、赤色２号、赤色３号、赤色４０号、赤色１０２号、黄色４号、黄色５号、緑色３号、青色１号及び青色２号からなる群より選ばれる何れか１種の染料をレーキ化したものであることが好ましい。 In the above-mentioned configuration, the lake pigment is a group consisting of Red No. 2, Red No. 3, Red No. 40, Red No. 102, Yellow No. 4, Yellow No. 5, Yellow No. 3, Green No. 3, Blue No. 1 and Blue No. 2. It is preferable that it is what rake-ized any one kind of dye selected more.
　前記の構成においては、前記顔料分散剤が、ポリアクリル酸ナトリウム、ポリビニルピロリドン、多糖類、ゼラチン、コラーゲン、ポリビニルアルコール、ポリビニルアルコール誘導体、アミノアルキルメタクリレートコポリマー、メタクリル酸コポリマー、アンモニオアルキルメタクリレートコポリマー、アクリル酸エチル・メタクリル酸メチルコポリマー及び酢酸ビニルからなる群より選ばれる少なくとも１種であってもよい。 In the above construction, the pigment dispersant is sodium polyacrylate, polyvinyl pyrrolidone, polysaccharide, gelatin, collagen, polyvinyl alcohol, polyvinyl alcohol derivative, aminoalkyl methacrylate copolymer, methacrylic acid copolymer, ammonio alkyl methacrylate copolymer, acrylic It may be at least one selected from the group consisting of ethyl acid / methyl methacrylate copolymer and vinyl acetate.
　また、本発明に係るインクジェット用水性インク組成物は、前記の課題を解決するために、顔料組成物を含み、かつ、可食性を有するものである。 Moreover, the aqueous ink composition for inkjet according to the present invention contains a pigment composition and has edible properties in order to solve the above-mentioned problems.
　前記の構成によれば、顔料組成物には、レーキ顔料の分散状態を安定的に維持させるための分散安定剤として、顔料組成物の全質量に対し１０質量％以下のカルボン酸等が含まれている。本発明のインクジェット用水性インク組成物はそのような顔料組成物を含み構成されるものであるため、これにより、本発明においては、レーキ顔料の平均分散粒子径が時間の経過に伴って増大するのを抑制し、顔料組成物がゲル化するのを防止したインクジェット用水性インク組成物を提供することができる。また、レーキ顔料の含有量を顔料組成物の全質量に対し２０質量％以下とするので、インクジェットノズルからの吐出安定性が良好なインクジェット用水性インク組成物を提供することができる。 According to the above configuration, the pigment composition contains 10% by mass or less of carboxylic acid or the like with respect to the total mass of the pigment composition as a dispersion stabilizer for stably maintaining the dispersed state of the lake pigment. ing. The aqueous ink composition for inkjet according to the present invention comprises such a pigment composition, whereby the average dispersed particle size of the lake pigment in the present invention increases with the passage of time. It is possible to provide an aqueous ink composition for ink jet that suppresses the gelation of the pigment composition and suppresses the gelation of the pigment composition. In addition, since the content of the lake pigment is 20% by mass or less based on the total mass of the pigment composition, it is possible to provide an aqueous ink composition for inkjet having good ejection stability from the inkjet nozzle.
　また、本発明に係る固体製剤は、前記の課題を解決するために、インクジェット用水性インクの乾燥皮膜を表面に有する固体製剤であって、前記インクジェット用水性インクは、前記インクジェット用水性インク組成物を含むものである。 Moreover, the solid preparation according to the present invention is a solid preparation having a dry film of an aqueous ink for ink jet on the surface to solve the above-mentioned problems, wherein the aqueous ink for ink jet is the aqueous ink composition for ink jet Is included.
　前記の構成によれば、インクジェット用インクの乾燥皮膜中には、少なくとも１種のレーキ顔料が含まれるため、乾燥皮膜により形成される印刷画像は、良好な耐光性を維持しつつ発色性に優れている。また、水性インク組成物は、レーキ顔料の分散状態を安定的に維持させる分散安定剤を含むものであるので、インクジェット方式で固体製剤の表面に水性インク組成物を吐出させる際に、その吐出不良を抑制することができる。その結果、固体製剤の表面に吐出不良なく乾燥被膜を形成することができ、視認性に優れた画像の形成を可能にする。これにより、例えば、製品情報を印刷した場合には、調剤ミスや誤飲等を防止することが可能な固体製剤を提供することができる。 According to the above configuration, the dried film of the inkjet ink contains at least one type of lake pigment, so the printed image formed by the dried film is excellent in color development while maintaining good light resistance. ing. In addition, since the aqueous ink composition contains a dispersion stabilizer that stably maintains the dispersed state of the lake pigment, when the aqueous ink composition is ejected onto the surface of the solid preparation by the inkjet method, the ejection failure is suppressed. can do. As a result, a dry film can be formed on the surface of the solid preparation without discharge failure, and an image with excellent visibility can be formed. Thereby, for example, when product information is printed, it is possible to provide a solid preparation capable of preventing dispensing errors, accidental ingestion, and the like.
　本発明によれば、カルボン酸、カルボン酸塩、ホスホン酸、ホスホン酸塩及びエチレンジアミン四酢酸塩からなる群より選ばれる少なくとも１種からなる分散安定剤を、顔料組成物の全質量に対し１０質量％以下で含有させることにより、レーキ顔料の平均分散粒子径が時間の経過と共に増大するのを抑制し、顔料組成物がゲル化するのを防止することができる。すなわち、本発明によれば、カルボン酸等の分散安定剤を含有させることにより、レーキ顔料の分散安定性（保存安定性）を向上させることができる。また、レーキ顔料を顔料組成物の全質量に対し２０質量％以下で含有させるので、医薬品や食品等の固体製剤に対し、インクジェット方式で吐出安定性を損なうことなく良好に直接印刷することができる。さらに、着色剤としてレーキ顔料を用いることで、印刷画像の耐光性及び発色性を優れたものにすることができる。 According to the present invention, a dispersion stabilizer consisting of at least one selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphonic acids, phosphonic acid salts and ethylenediaminetetraacetic acid salts is used in an amount of 10% relative to the total mass of the pigment composition. By containing at% or less, it is possible to suppress the increase of the average dispersed particle diameter of the lake pigment with the passage of time, and to prevent the pigment composition from being gelled. That is, according to the present invention, the dispersion stability (storage stability) of the lake pigment can be improved by containing a dispersion stabilizer such as a carboxylic acid. In addition, since the lake pigment is contained at 20% by mass or less based on the total mass of the pigment composition, direct printing can be favorably performed on solid preparations such as pharmaceuticals and foods by the inkjet method without impairing the ejection stability. . Furthermore, by using a lake pigment as a coloring agent, it is possible to make the light resistance and color development of the printed image excellent.
　（顔料組成物）
　本実施の形態に係る顔料組成物は、着色剤として少なくとも１種のレーキ顔料と、顔料分散剤と、分散安定剤とを少なくとも含む顔料分散体の組成物である。また、本実施の形態の顔料組成物は、薬事法で定める医薬品添加物、日本薬局方又は食品添加物公定書の基準に適合した材料を用いることにより、可食性を有するものにすることができ、これにより、医薬品や食品等の固体製剤へのインクジェット方式での画像等の記録に好適に用いることができる。 (Pigment composition)
The pigment composition according to the present embodiment is a composition of a pigment dispersion containing at least one lake pigment as a colorant, a pigment dispersant, and a dispersion stabilizer. In addition, the pigment composition of the present embodiment can be made edible by using a material conforming to the pharmaceutical additive defined by the Pharmaceutical Affairs Law, the Japanese Pharmacopoeia, or the standard of food additives. Thus, it can be suitably used for recording an image or the like by an inkjet method on a solid preparation such as a medicine or food.
　ここで、本明細書において「可食性」とは、医薬品若しくは医薬品添加物として経口投与が認められている物質、及び／又は食品若しくは食品添加物として認められているものを意味する。また、本明細書において「インクジェット方式」とは、水性インク組成物を微細なインクジェットヘッドより液滴として吐出して、その液滴を固体製剤に定着させ、画像形成させる方式を意味する。尚、固体製剤の詳細については、後述する。 Here, the term "edible" as used herein means a substance approved for oral administration as a pharmaceutical product or pharmaceutical additive, and / or a substance recognized as a food or food additive. Further, in the present specification, the "ink jet system" means a system in which an aqueous ink composition is discharged as droplets from a fine ink jet head, and the droplets are fixed on a solid preparation to form an image. The details of the solid preparation will be described later.
　レーキ顔料は、顔料組成物中に分散状態で存在する。レーキ顔料としては可食性を有するものであれば特に限定されない。ここで、「レーキ顔料」とは、主溶媒に可溶性の染料をレーキ化して得られる顔料を意味し、より詳細には、金属塩等の沈殿剤を加えることにより染料を沈殿剤に吸着させ、不溶性塩（不溶性の微粒子）として沈殿させた沈殿物である。主溶媒に可溶性を示す染料については特に限定されないが、好ましくは、赤色２号、赤色３号、赤色４０号、赤色１０２号、黄色４号、黄色５号、緑色３号、青色１号及び青色２号からなる群より選ばれる少なくとも１種である。 The lake pigment is present in the pigment composition in a dispersed state. The lake pigment is not particularly limited as long as it is edible. Here, "lake pigment" means a pigment obtained by lake forming a dye soluble in a main solvent, and more specifically, the dye is adsorbed to the precipitant by adding a precipitant such as a metal salt, It is a precipitate precipitated as an insoluble salt (insoluble fine particles). The dye that is soluble in the main solvent is not particularly limited, but preferably red 2, red 3, red 40, red 102, yellow 4, yellow 5, yellow 5, green 3, blue 1, and blue. It is at least one selected from the group consisting of No. 2.
　レーキ顔料のより具体的な例としては、赤色２号アルミニウムレーキ、赤色３号アルミニウムレーキ、赤色４号アルミニウムレーキ、赤色４０号アルミニウムレーキ、赤色１０２号アルミニウムレーキ、黄色４号アルミニウムレーキ、黄色４号バリウムレーキ、黄色４号ジルコニウムレーキ、黄色５号アルミニウムレーキ、黄色５号バリウムレーキ、黄色５号ジルコニウムレーキ、緑色３号アルミニウムレーキ、青色１号アルミニウムレーキ、青色１号バリウムレーキ、青色１号ジルコニウムレーキ、青色２号アルミニウムレーキ等が挙げられる。これらのレーキ顔料は１種単独で、又は２種以上を混合して用いることができる。 More specific examples of the lake pigment include red No. 2 aluminum lake, red No. 3 aluminum lake, red No. 4 aluminum lake, red No. 40 aluminum lake, red No. 102 aluminum lake, yellow No. 4 aluminum lake, yellow No. 4 Barium lake, yellow No. 4 zirconium lake, yellow No. 5 aluminum lake, yellow No. 5 barium lake, yellow No. 5 zirconium lake, green No. 3 aluminum lake, blue No. 1 aluminum lake, blue No. 1 barium lake, blue No. 1 zirconium lake , Blue No. 2 aluminum lake, and the like. These lake pigments can be used alone or in combination of two or more.
　レーキ顔料の含有量は、顔料組成物の全質量に対し２０質量％以下であり、好ましくは１質量％～２０質量％、より好ましくは５質量％～１５質量％である。レーキ顔料の含有量を２０質量％以下にすることにより、顔料組成物を用いた水性インクのインクジェットノズルからの吐出安定性を良好に維持することができる。尚、レーキ顔料の含有量を１質量％以上にすることより、印刷画像の視認性の向上が図れる。また、レーキ顔料が顔料組成物中に複数種含まれる場合は、全てのレーキ顔料の含有量の合計が前記数値範囲に含まれていればよい。 The content of the lake pigment is 20% by mass or less, preferably 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass, based on the total mass of the pigment composition. By setting the content of the lake pigment to 20% by mass or less, the ejection stability of the aqueous ink using the pigment composition from the ink jet nozzle can be favorably maintained. The visibility of the printed image can be improved by setting the content of the lake pigment to 1% by mass or more. Moreover, when multiple types of lake pigment are contained in a pigment composition, the sum total of content of all the lake pigments should just be contained in the said numerical range.
　顔料分散剤は、分散媒におけるレーキ顔料の分散性を向上させる。顔料分散剤としては、レーキ顔料の分散性を向上させることができ、かつ、可食性を有するものであれば特に限定されない。顔料分散剤としては、例えば、ポリアクリル酸ナトリウム、ポリビニルピロリドン、多糖類、ゼラチン、コラーゲン、ポリビニルアルコール、ポリビニルアルコール誘導体、アミノアルキルメタクリレートコポリマー、メタクリル酸コポリマー、アンモニオアルキルメタクリレートコポリマー、アクリル酸エチル・メタクリル酸メチルコポリマー及び酢酸ビニルからなる群より選ばれる少なくとも１種が挙げられる。 The pigment dispersant improves the dispersibility of the lake pigment in the dispersion medium. The pigment dispersant is not particularly limited as long as it can improve the dispersibility of the lake pigment and is edible. As a pigment dispersant, for example, sodium polyacrylate, polyvinyl pyrrolidone, polysaccharide, gelatin, collagen, polyvinyl alcohol, polyvinyl alcohol derivative, aminoalkyl methacrylate copolymer, methacrylic acid copolymer, ammonio alkyl methacrylate copolymer, ethyl acrylate / methacrylic acid And at least one selected from the group consisting of an acid methyl copolymer and vinyl acetate.
　レーキ顔料と顔料分散剤の含有比は、質量基準で１：０．２～１：４であることが好ましく、１：０．５～１：１であることがより好ましい。含有比が１：０．２以上であると、レーキ顔料の分散性の低下を防止することができる。その一方、含有比が１：４以下であると、水性インクの粘度増大によりノズルプレートに水性インクが付着し、それに起因して吐出安定性が低下するのを防止することができる。 The content ratio of the lake pigment to the pigment dispersant is preferably 1: 0.2 to 1: 4, and more preferably 1: 0.5 to 1: 1 on a mass basis. The fall of the dispersibility of a lake pigment can be prevented as a content ratio is 1: 0.2 or more. On the other hand, when the content ratio is 1: 4 or less, it is possible to prevent the aqueous ink from adhering to the nozzle plate due to the increase in viscosity of the aqueous ink and the discharge stability being lowered due to the adhesion.
　分散安定剤は、レーキ顔料に由来する金属イオン（例えば、アルミニウムイオン等）が顔料分散剤と結合するのを防止するため、当該金属イオンをキレート化する機能を有する。これにより、レーキ顔料の分散安定性を向上させることができ、より詳細には、レーキ顔料の平均分散粒子径が時間の経過と共に増大するのを防止し、一定期間の保管後においても良好な分散状態を維持し、顔料組成物のゲル化を防止することができる。 The dispersion stabilizer has a function of chelating the metal ion in order to prevent the metal ion derived from the lake pigment (for example, aluminum ion etc.) from binding to the pigment dispersant. Thereby, the dispersion stability of the lake pigment can be improved, and more specifically, the average dispersed particle diameter of the lake pigment is prevented from increasing with the passage of time, and the dispersion is good even after storage for a certain period of time The state can be maintained to prevent gelation of the pigment composition.
　尚、本明細書において「分散安定性」とは、顔料組成物又は当該顔料組成物を含むインクジェット用水性インク組成物（詳細については、後述する。）に分散安定剤を含有させることにより、レーキ顔料の分散性が一定時間経過した後においても低下し難い性質を意味し、保存安定性ともいう。 In the present specification, “dispersion stability” refers to a pigment composition or an inkjet aqueous ink composition containing the pigment composition (described in detail later) by containing a dispersion stabilizer. It means the property that the dispersibility of the pigment hardly decreases even after a certain time has passed, and is also referred to as storage stability.
　分散安定剤としては、レーキ顔料の分散安定性を向上させることができ、かつ、可食性を有するものであれば特に限定されない。そのような分散安定剤としては、例えば、カルボン酸、カルボン酸塩、ホスホン酸、ホスホン酸塩及びエチレンジアミン四酢酸塩からなる群より選ばれる少なくとも１種が挙げられる。 The dispersion stabilizer is not particularly limited as long as it can improve the dispersion stability of the lake pigment and is edible. Examples of such dispersion stabilizers include at least one selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphonic acids, phosphonic acid salts and ethylenediaminetetraacetic acid salts.
　カルボン酸としては特に限定されず、例えば、Ｌ－酒石酸、ＤＬ－酒石酸、グルコン酸、クエン酸、フマル酸、ＤＬ－リンゴ酸、乳酸等が挙げられる。 The carboxylic acid is not particularly limited, and examples thereof include L-tartaric acid, DL-tartaric acid, gluconic acid, citric acid, fumaric acid, DL-malic acid, lactic acid and the like.
　カルボン酸塩としては特に限定されず、例えば、クエン酸カルシウム、クエン酸トリエチル、クエン酸ナトリウム、クエン酸二水素ナトリウム、クエン酸二ナトリウム等のクエン酸塩；グルコン酸カルシウム、グルコン酸ナトリウム、グルコン酸マグネシウム等のグルコン酸塩；Ｌ－酒石酸ナトリウム等のＬ－酒石酸塩；乳酸アルミニウム、乳酸カルシウム等の乳酸塩；フマル酸一ナトリウム等のフマル酸塩；リンゴ酸二ナトリウム等のリンゴ酸塩；コハク酸二ナトリウム等のコハク酸塩；ＤＬ－酒石酸ナトリウム等のＤＬ－酒石酸塩等が挙げられる。 The carboxylate is not particularly limited. For example, citrate such as calcium citrate, triethyl citrate, sodium citrate, sodium dihydrogen citrate, disodium citrate, etc .; calcium gluconate, sodium gluconate, gluconic acid Gluconates such as magnesium; L-tartrates such as L-sodium tartrate; lactates such as aluminum lactate and calcium lactate; fumarates such as monosodium fumarate; malic acid such as disodium malate; succinic acid Examples include succinate salts such as disodium; DL-tartrate salts such as sodium DL-tartrate;
　ホスホン酸としては特に限定されず、例えば、リン酸、ピロリン酸、メタリン酸、フィチン酸等が挙げられる。 The phosphonic acid is not particularly limited, and examples thereof include phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phytic acid and the like.
　ホスホン酸塩としては特に限定されず、例えば、リン酸二水素カリウム、リン酸二水素ナトリウム、ピロリン酸二水素二ナトリウム、リン酸水素二カリウム、リン酸水素二ナトリウム等が挙げられる。 The phosphonate is not particularly limited, and examples thereof include potassium dihydrogen phosphate, sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate, dipotassium hydrogen phosphate, and disodium hydrogen phosphate.
　エチレンジアミン四酢酸塩としては特に限定されず、例えば、エチレンジアミン四酢酸二ナトリウム、エチレンジアミン四酢酸塩ナトリウムカルシウム等が挙げられる。 The ethylenediaminetetraacetic acid salt is not particularly limited, and examples thereof include ethylenediaminetetraacetic acid disodium and ethylenediaminetetraacetic acid sodium calcium.
　尚、例示した分散安定剤は、それぞれ１種単独で、又は２種以上を混合して用いることができる。 The exemplified dispersion stabilizers may be used alone or in combination of two or more.
　分散安定剤の含有量は、顔料組成物の全質量に対し１０質量％以下であり、好ましくは０．１質量％～６質量％、より好ましくは１質量％～２質量％である。分散安定剤の含有量を１０質量％以下にすることにより、分散安定剤が過剰に存在することによるレーキ顔料の分散安定性の低下を抑制することができる。尚、分散安定剤の含有量を０．１質量％以上にすることより、レーキ顔料の分散安定性を向上させることができる。また、分散安定剤が顔料組成物中に複数種含まれる場合は、全ての分散安定剤の含有量の合計が数値範囲に含まれていればよい。 The content of the dispersion stabilizer is 10% by mass or less, preferably 0.1% by mass to 6% by mass, and more preferably 1% by mass to 2% by mass, based on the total mass of the pigment composition. By setting the content of the dispersion stabilizer to 10% by mass or less, it is possible to suppress a decrease in the dispersion stability of the lake pigment due to the presence of the dispersion stabilizer in excess. In addition, the dispersion stability of a lake pigment can be improved by making content of a dispersion stabilizer into 0.1 mass% or more. Moreover, when multiple types of dispersion stabilizers are contained in a pigment composition, the sum total of content of all the dispersion stabilizers should just be contained in a numerical range.
　本実施の形態に係る顔料組成物に於いては、レーキ顔料を分散させるための分散媒が含まれる。分散媒としては水が挙げられ、より詳細には、イオン交換水、限外ろ過水、逆浸透水、蒸留水等の純水、又は超純水等のイオン性不純物を除去したものが挙げられる。特に、紫外線照射又は過酸化水素添加等により滅菌処理した水は、長期間にわたってカビやバクテリアの発生を防止することができるので好適である。また、分散媒の含有量としては特に限定されず、適宜必要に応じて設定することができる。 The pigment composition according to the present embodiment includes a dispersion medium for dispersing the lake pigment. Examples of the dispersion medium include water, and more specifically, those obtained by removing ionic impurities such as deionized water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water. . In particular, water sterilized by ultraviolet irradiation or hydrogen peroxide addition is preferable because it can prevent the generation of mold and bacteria over a long period of time. Further, the content of the dispersion medium is not particularly limited, and can be set as necessary.
　また、分散媒としては、水と水溶性有機溶剤の混合溶液を用いてもよい。水溶性有機溶剤としては薬事法等の基準に該当するものであれば特に限定されない。具体的には、例えば、エチルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、アセトン、プロピレングリコール、ポリエチレングリコール、グリセリン等が挙げられる。さらに、分散媒に水溶性有機溶剤を併用する場合の配合量としては特に限定されず、適宜必要に応じて設定することができる。 Moreover, as the dispersion medium, a mixed solution of water and a water-soluble organic solvent may be used. The water-soluble organic solvent is not particularly limited as long as it meets the criteria such as the Pharmaceutical Affairs Law. Specifically, examples thereof include ethyl alcohol, n-butyl alcohol, isobutyl alcohol, n-propyl alcohol, isopropyl alcohol, acetone, propylene glycol, polyethylene glycol, glycerin and the like. Furthermore, the compounding amount in the case of using a water-soluble organic solvent in combination with the dispersion medium is not particularly limited, and can be appropriately set as needed.
　顔料組成物の２５℃におけるｐＨは、レーキ顔料の分散安定性の観点から、２～１０の範囲内が好ましく、５～９の範囲内がより好ましく、６～８の範囲内が特に好ましい。 The pH of the pigment composition at 25 ° C. is preferably in the range of 2 to 10, more preferably in the range of 5 to 9, and particularly preferably in the range of 6 to 8 from the viewpoint of dispersion stability of the lake pigment.
　顔料組成物中のレーキ顔料の体積基準積算粒度分布における積算粒度で１０％の粒子径（Ｄ１０）は、顔料組成物の作製直後及び一定期間の経過後において、５０ｎｍ～３００ｎｍの範囲内が好ましく、７０ｎｍ～１５０ｎｍの範囲内がより好ましい。Ｄ１０を５０ｎｍ以上にすることにより、過分散による凝集を抑制することができる。その一方、Ｄ１０を３００ｎｍ以下にすることにより、吐出安定性の低下を防止することができる。 The particle size (D10) of 10% in cumulative particle size in volume-based cumulative particle size distribution of the lake pigment in the pigment composition is preferably in the range of 50 nm to 300 nm immediately after preparation of the pigment composition and after a certain period. The range of 70 nm to 150 nm is more preferable. By making D10 50 nm or more, aggregation due to overdispersion can be suppressed. On the other hand, the fall of discharge stability can be prevented by making D10 300 nm or less.
　また、分散状態にあるレーキ顔料の体積基準積算粒度分布における積算粒度で５０％の粒子径（Ｄ５０）は、顔料組成物の作製直後及び一定期間の経過後において、５０ｎｍ～７００ｎｍの範囲内が好ましく、６０ｎｍ～５００ｎｍの範囲内がより好ましく、７０ｎｍ～１５０ｎｍの範囲内が特に好ましい。Ｄ５０を５０ｎｍ以上にすることにより、分散安定性、耐光性及び吐出安定性の低下を防止し、印刷濃度の低下も防止することができる。その一方、Ｄ５０を７００ｎｍ以下にすることにより、レーキ顔料の分離や沈降を防止し、分散安定性の維持が図れる。 In addition, the particle size (D50) of 50% of the integrated particle size in the volume-based integrated particle size distribution of the lake pigment in the dispersed state is preferably in the range of 50 nm to 700 nm immediately after preparation of the pigment composition and after a certain period. The range of 60 nm to 500 nm is more preferable, and the range of 70 nm to 150 nm is particularly preferable. By setting D50 to 50 nm or more, it is possible to prevent the deterioration of the dispersion stability, the light resistance, and the discharge stability, and to prevent the reduction of the printing density. On the other hand, by setting D50 to 700 nm or less, separation and sedimentation of the lake pigment can be prevented, and the dispersion stability can be maintained.
　さらに、レーキ顔料の体積基準積算粒度分布における積算粒度で９９％の粒子径（Ｄ９９）は、顔料組成物の作製直後及び一定期間の経過後において、５０ｎｍ～３０００ｎｍの範囲内が好ましく、６０ｎｍ～８００ｎｍの範囲内がより好ましく、１００ｎｍ～６００ｎｍの範囲内が特に好ましい。Ｄ９９を５０ｎｍ以上にすることにより、分散安定性、耐光性及び吐出安定性の低下を防止し、印刷濃度の低下も防止することができる。その一方、Ｄ９９を３０００ｎｍ以下にすることにより、吐出安定性の低下を防止することができる。 Furthermore, the particle size (D99) of 99% of the cumulative particle size in the volume-based cumulative particle size distribution of the lake pigment is preferably in the range of 50 nm to 3000 nm, 60 nm to 800 nm immediately after preparation of the pigment composition and after a certain period. Is more preferably in the range of 100 nm to 600 nm. By setting D99 to 50 nm or more, it is possible to prevent the deterioration of the dispersion stability, the light resistance, and the discharge stability, and to prevent the reduction of the printing density. On the other hand, the fall of discharge stability can be prevented by making D99 3000 nm or less.
　尚、レーキ顔料が顔料組成物中に複数種含まれる場合は、各々のレーキ顔料のＤ１０、Ｄ５０及びＤ９９が前記数値範囲に含まれていればよい。また、レーキ顔料のＤ１０、Ｄ５０及びＤ９９の値は、マイクロトラックＵＰＡ－ＥＸ１５０（商品名、日機装(株)製）を用いて動的光散乱法により測定した値である。 In addition, when multiple types of lake pigment are contained in a pigment composition, D10, D50, and D99 of each lake pigment should just be contained in the said numerical range. The values of D10, D50 and D99 of the lake pigment are values measured by a dynamic light scattering method using Microtrac UPA-EX 150 (trade name, manufactured by Nikkiso Co., Ltd.).
　本実施の形態の顔料組成物の製造方法において、レーキ顔料、顔料分散剤、分散安定剤、分散媒及び必要に応じて配合するその他の添加剤の混合方法や添加順序は、特に限定されない。例えば、レーキ顔料、顔料分散剤、分散安定剤及び分散媒としての水等を一度に混合し、この混合液に対し通常の分散機を用いて分散処理を施してもよい。 In the method for producing the pigment composition of the present embodiment, the mixing method and the addition order of the lake pigment, the pigment dispersant, the dispersion stabilizer, the dispersion medium, and the other additives to be blended if necessary are not particularly limited. For example, a lake pigment, a pigment dispersant, a dispersion stabilizer, water as a dispersion medium, etc. may be mixed at one time, and the mixture may be subjected to dispersion treatment using a conventional disperser.
　分散処理における分散時間は特に限定されず、適宜必要に応じて設定することができる。レーキ顔料の分散処理の際に使用される分散機としては、一般に使用される分散機であれば特に限定されない。具体的には、例えば、ボールミル、ロールミル、サンドミル、ビーズミル、ペイントシェーカー、ナノマイザー等が挙げられる。 The dispersion time in the dispersion process is not particularly limited, and can be set as needed. The disperser used in the dispersion treatment of the lake pigment is not particularly limited as long as it is a commonly used disperser. Specifically, for example, a ball mill, a roll mill, a sand mill, a bead mill, a paint shaker, a nanomizer and the like can be mentioned.
　尚、本実施の形態の顔料組成物は、インクジェット用水性インク組成物（詳細については後述する）の形態のほか、当該水性インク組成物を調製するための顔料分散液の形態をも包含するものである。 In addition to the form of the aqueous ink composition for inkjet (details will be described later), the pigment composition of the present embodiment also includes the form of a pigment dispersion for preparing the aqueous ink composition. It is.
　（インクジェット用水性インク組成物）
　本実施の形態に係るインクジェット用水性インク組成物（以下、「水性インク組成物」という。）は、少なくとも顔料組成物を含み、主溶媒が水である水性インクである。また、本実施の形態の水性インク組成物は可食性を有し、インクジェット記録用として好適に用いられるものである。さらに、水性インク組成物は着色剤としてレーキ顔料が用いられることから、通常の顔料を用いた水性インク組成物と比較して発色性に優れている。 (Water-based ink composition for inkjet)
An aqueous ink composition for inkjet according to the present embodiment (hereinafter referred to as "aqueous ink composition") is an aqueous ink containing at least a pigment composition and the main solvent being water. In addition, the aqueous ink composition of the present embodiment is edible and is suitably used for inkjet recording. Furthermore, since the water-based ink composition uses a lake pigment as a coloring agent, it is excellent in color development as compared to a conventional pigment-based water-based ink composition.
　顔料組成物の含有量は、水性インク組成物の全質量に対し顔料分換算で２０質量％以下であり、１質量％～２０質量％の範囲が好ましく、２質量％～１５質量％の範囲がより好ましく、２質量％～１０質量％の範囲がさらに好ましく、４質量％～８質量％の範囲内が特に好ましい。顔料組成物の含有量を２０質量％以下にすることにより、分散性を向上させることができる。尚、顔料組成物の含有量を１質量％以上にすることにより、着色力を向上させることができる。また、「顔料分換算」とは、レーキ顔料の含有量のみで換算することを意味する。 The content of the pigment composition is 20% by mass or less in terms of pigment content based on the total mass of the aqueous ink composition, preferably in the range of 1% by mass to 20% by mass, and in the range of 2% by mass to 15% by mass. The range of 2% by mass to 10% by mass is more preferable, and the range of 4% by mass to 8% by mass is particularly preferable. By setting the content of the pigment composition to 20% by mass or less, the dispersibility can be improved. The coloring power can be improved by setting the content of the pigment composition to 1% by mass or more. Moreover, "pigment part conversion" means converting only by the content of the lake pigment.
　本実施の形態の水性インク組成物に於いては、水（主溶媒としての水）を含有する。水としては、イオン交換水、限外ろ過水、逆浸透水、蒸留水等の純水、又は超純水等のイオン性不純物を除去したものを用いるのが好ましい。特に、紫外線照射又は過酸化水素添加等により滅菌処理した水は、長期間にわたってカビやバクテリアの発生を防止することができるので好適である。また、水の含有量としては特に限定されず、適宜必要に応じて設定することができる。 In the aqueous ink composition of the present embodiment, water (water as a main solvent) is contained. As water, it is preferable to use pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water or the like, or from which ionic impurities such as ultrapure water have been removed. In particular, water sterilized by ultraviolet irradiation or hydrogen peroxide addition is preferable because it can prevent the generation of mold and bacteria over a long period of time. Moreover, it does not specifically limit as content of water, It can set suitably as needed.
　本実施の形態の水性インク組成物においては、薬事法で定める医薬品添加物、日本薬局方又は食品添加物公定書の基準に適合するものであれば、その他の添加剤が配合されていてもよい。添加剤としては、表面張力調整剤、湿潤剤、水溶性樹脂、有機アミン、界面活性剤、防腐剤、粘度調整剤、消泡剤、酸化防止剤、還元防止剤等が挙げられる。表面張力調整剤及び湿潤剤を除き、これらの添加剤の含有量は特に限定されず、適宜必要に応じて設定することができる（表面張力調整剤及び湿潤剤の含有量については、それぞれ後述する。）。 In the aqueous ink composition of the present embodiment, other additives may be blended as long as it meets the criteria of the pharmaceutical additive, the Japanese Pharmacopoeia, or the official regulations of the food additive prescribed by the Pharmaceutical Affairs Law. . Examples of additives include surface tension modifiers, wetting agents, water-soluble resins, organic amines, surfactants, preservatives, viscosity modifiers, antifoaming agents, antioxidants, reduction inhibitors and the like. The content of these additives is not particularly limited except for the surface tension regulator and the wetting agent, and can be appropriately set as necessary (the content of the surface tension regulator and the wetting agent will be described later, respectively). ).
　表面張力調整剤としては、薬事法等の基準に適合するものであれば特に限定されず、具体的には、例えば、グリセリン脂肪酸エステル等が挙げられる。グリセリン脂肪酸エステルとしては、例えば、カプリル酸デカグリセリル、ラウリン酸デカグリセリル等が挙げられる。 The surface tension regulator is not particularly limited as long as it conforms to the standards of the Pharmaceutical Affairs Law, and specific examples thereof include glycerin fatty acid ester and the like. Examples of glycerin fatty acid esters include decaglyceryl caprylate, decaglyceryl laurate and the like.
　表面張力調整剤の含有量は、水性インク組成物の全質量に対し、０．１質量％～５質量％の範囲内であることが好ましく、１質量％～２質量％の範囲内であることがより好ましい。表面張力調整剤の含有量が０．１質量％以上であると、インクジェット方式で印刷を行った場合に、インクジェットヘッドにおけるノズルでのメニスカス形成不良等による吐出不良を防止し、当該ノズルの目詰まりが発生するのを防止することができる。その結果、吐出安定性の向上が図れる。その一方、表面張力調整剤の含有量が５質量％以下であると、表面張力調整剤の不溶分や乳化不良による吐出への悪影響を防止することができる。 The content of the surface tension regulator is preferably in the range of 0.1% by mass to 5% by mass, and more preferably in the range of 1% by mass to 2% by mass, with respect to the total mass of the aqueous ink composition. Is more preferred. When printing is performed by the inkjet method when the content of the surface tension adjusting agent is 0.1% by mass or more, discharge failure due to meniscus formation failure or the like in the nozzle of the ink jet head is prevented, and clogging of the nozzle Can be prevented. As a result, the ejection stability can be improved. On the other hand, when the content of the surface tension regulator is 5% by mass or less, it is possible to prevent the adverse effect on the discharge due to the insoluble portion of the surface tension regulator or the emulsification failure.
　湿潤剤としては、薬事法等の基準に適合するものであれば特に限定されず、具体的には、例えば、プロピレングリコール、グリセリン等が挙げられる。 The wetting agent is not particularly limited as long as it meets the standards of the Pharmaceutical Affairs Law, and specific examples thereof include propylene glycol and glycerin.
　湿潤剤の添加量は、水性インク組成物の全質量に対し、１質量％～５０質量％が好ましく、１０質量％～４０質量％がより好ましい。湿潤剤の含有量を１質量％以上にすることにより、インクジェットヘッドのノズル近傍での目詰まりを防止し、吐出性能の一層の向上が図れる。その一方、湿潤剤の含有量を５０質量％以下にすることにより、水性インク組成物の粘度を適性に制御することができる。 The amount of the wetting agent added is preferably 1% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass, with respect to the total mass of the aqueous ink composition. By setting the content of the wetting agent to 1% by mass or more, clogging in the vicinity of the nozzle of the inkjet head can be prevented, and the discharge performance can be further improved. On the other hand, by setting the content of the wetting agent to 50% by mass or less, the viscosity of the aqueous ink composition can be appropriately controlled.
　本実施の形態の水性インク組成物は、インクジェット用インクに好適に使用することができる。さらに、本実施の形態の水性インク組成物は、薬事法等の基準に適合した材料を用いるので、可食性を有しており、サプリメント等の錠剤の表面に直接印刷することが可能である。また、素錠及びＯＤ錠など表面の平滑性が悪い錠剤に対しても、インクジェット方式による非接触印刷を可能にする。さらに、本実施の形態の水性インク組成物は、レーキ顔料を用いるので、耐光性及び発色性に優れた画像を、医薬品又はサプリメント等の固体製剤表面に直接印刷することができる。 The aqueous ink composition of the present embodiment can be suitably used for an inkjet ink. Furthermore, the water-based ink composition of the present embodiment is edible because it uses a material conforming to the standards such as the Pharmaceutical Affairs Law, and can be printed directly on the surface of a tablet such as a supplement. In addition, non-contact printing by ink jet method is enabled even for tablets having poor surface smoothness such as uncoated tablets and OD tablets. Furthermore, since the aqueous ink composition of the present embodiment uses a lake pigment, an image excellent in light resistance and color developability can be printed directly on the surface of a solid preparation such as a medicine or a supplement.
　尚、本実施の形態の水性インク組成物は、最終製品たるインクジェット用水性インクに少なくとも含まれるものであるほか、当該インクジェット用水性インクそのものとしても用いることができる。 The aqueous ink composition of the present embodiment is at least contained in an inkjet aqueous ink as a final product, and can also be used as the aqueous inkjet ink itself.
　本実施の形態の水性インク組成物は、前述の各成分を適宜な方法で混合することよって製造することができる。即ち、例えば、顔料組成物の分散液に、別途前述した添加剤等を加え、更に水にて希釈する。その後、十分に撹拌し、必要に応じて目詰まりの原因となる粗大粒子及び異物を除去するための濾過を行う。これにより、本実施の形態に係る水性インク組成物を得ることができる。 The aqueous ink composition of the present embodiment can be produced by mixing the above-mentioned components by an appropriate method. That is, for example, the above-described additives and the like are added to the dispersion of the pigment composition, and then diluted with water. After that, the solution is sufficiently stirred, and if necessary, filtration is performed to remove coarse particles and foreign substances that cause clogging. Thus, the aqueous ink composition according to the present embodiment can be obtained.
　尚、各材料の混合方法としては特に限定されず、例えば、メカニカルスターラー、マグネチックスターラー等の撹拌装置を備えた容器に順次材料を添加して撹拌混合を行う。また、濾過方法としては特に限定されず、例えば、遠心濾過、フィルター濾過等を採用することができる。 In addition, it does not specifically limit as a mixing method of each material, For example, materials are sequentially added to the container provided with stirring apparatuses, such as a mechanical stirrer and a magnetic stirrer, and stirring and mixing are performed. Moreover, it does not specifically limit as a filtration method, For example, centrifugal filtration, filter filtration, etc. are employable.
　本実施の形態の水性インク組成物は、レーキ顔料の分散性及び分散安定性（保存安定性）に優れているので、インクジェット用インクに好適に使用することができる。特に、本実施の形態の水性インク組成物は、薬事法等の基準に適合したレーキ顔料及び分散安定剤等を用いるので、可食性を有しており、医薬品やサプリメント等の固体製剤の表面に直接印刷することが可能である。また、素錠やＯＤ錠など表面の平滑性が悪い錠剤に対しても、インクジェット方式による非接触印刷を可能にする。さらに、水性インク組成物は耐光性にも優れているので、医薬品やサプリメント等の固体製剤の表面に直接印刷しても滲みの発生を防止することができる。 The aqueous ink composition of the present embodiment is excellent in the dispersibility and the dispersion stability (storage stability) of the lake pigment, and therefore, can be suitably used for an ink jet ink. In particular, the aqueous ink composition of the present embodiment is edible since it uses a lake pigment, a dispersion stabilizer and the like conforming to the standards of the Pharmaceutical Affairs Law and the like, and is on the surface of solid preparations such as pharmaceuticals and supplements. It is possible to print directly. In addition, non-contact printing by ink jet method is enabled even for tablets having poor surface smoothness such as uncoated tablets and OD tablets. Furthermore, since the aqueous ink composition is also excellent in light resistance, the occurrence of bleeding can be prevented even when printed directly on the surface of a solid preparation such as a medicine or a supplement.
　（固体製剤）
　本明細書において、「固体製剤」とは食品製剤及び医薬製剤を含む意味であり、固体製剤の形態としては、例えばＯＤ錠（口腔内崩壊錠）、素錠、ＦＣ（フィルムコート）錠、糖衣錠等の錠剤又はカプセル剤が挙げられる。また、固体製剤は、医薬品用途であってもよく、食品用途であってもよい。食品用途の錠剤の例としては、錠菓やサプリメント等の健康食品が挙げられる。 (Solid preparation)
In the present specification, "solid preparation" is meant to include food preparations and pharmaceutical preparations, and as a solid preparation form, for example, OD tablets (orally disintegrating tablets), plain tablets, FC (film coated) tablets, sugar-coated tablets And tablets or capsules. Also, the solid preparation may be for pharmaceutical use or food use. Examples of tablets for food use include health foods such as tablets and supplements.
　固体製剤の表面には、水性インク組成物を含む水性インクを用いて、インクジェット記録方法により直接印刷された乾燥皮膜からなる印刷画像が形成される。そして乾燥皮膜は、水性インク組成物中に含まれていたレーキ顔料により少なくとも構成される。 On the surface of the solid preparation, using an aqueous ink containing an aqueous ink composition, a print image consisting of a dried film directly printed by an inkjet recording method is formed. The dry film is at least constituted by the lake pigment contained in the aqueous ink composition.
　本実施の形態の固体製剤において、乾燥皮膜からなる印刷画像は耐光性に優れているため、例えば、製品情報などの各種情報の画像の劣化を防止することが可能である。また、印刷画像は発色性にも優れているため、使用者に対する識別性も向上させることができる。その結果、本実施の形態の固体製剤は、長期にわたって良好な視認性を維持し、調剤ミスや誤飲の防止を可能にする。 In the solid preparation of the present embodiment, since the printed image formed of the dried film is excellent in light resistance, it is possible to prevent, for example, the deterioration of the image of various information such as product information. In addition, since the printed image is also excellent in color development, it is possible to improve the identification of the user. As a result, the solid preparation of the present embodiment maintains good visibility over a long period of time, making it possible to prevent dispensing errors and accidental ingestion.
　固体製剤の表面に対するインクジェット記録方法については、特に限定されない。具体的には、例えば、微細なノズルより水性インクを液滴として吐出し、その液滴を錠剤表面に付着させることにより行うことができる。吐出方法として特に限定されず、例えば、連続噴射型（荷電制御型、スプレー型等）、オンデマンド型（ピエゾ方式、サーマル方式、静電吸引方式等）等の公知の方法を採用することができる。 The inkjet recording method for the surface of the solid preparation is not particularly limited. Specifically, for example, the aqueous ink can be discharged as droplets from a fine nozzle, and the droplets can be attached to the tablet surface. The discharge method is not particularly limited, and for example, known methods such as continuous injection type (charge control type, spray type, etc.), on demand type (piezo type, thermal type, electrostatic suction type, etc.) can be adopted. .
　以下に、この発明の好適な実施例を例示的に詳しく説明する。但し、各実施例に記載されている材料や含有量等は、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定するものではない。また、顔料組成物の各材料は何れも薬事法で定める医薬品添加物、日本薬局方又は食品添加物公定書の基準に適合するものである。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, contents, and the like described in the respective examples do not limit the scope of the present invention to them unless otherwise specified. In addition, each material of the pigment composition conforms to the standard of pharmaceutical additives, Japanese Pharmacopoeia or Food Additives Official Standards stipulated by the Pharmaceutical Affairs Law.
　（実施例１）
　本実施例においては、レーキ顔料としての黄色４号アルミニウムレーキ（三栄源株式会社製）８ｇ、顔料分散剤としてのポリアクリル酸ナトリウム（商品名：ＴＥＧＯ（登録商標）　Ｄｉｓｐｅｒｓ　７１５Ｗ、Ｅｖｏｎｉｋ社製、質量平均分子量３０００）６ｇ、分散安定剤としてのリン酸水素二ナトリウム（和光純薬工業株式会社製）１ｇを容器に添加し、さらにイオン交換水４５ｇを加えた。続いて、容器中の混合液を分散機（ペイントシェーカー、浅田鉄工株式会社製）にて、常温下で３時間（分散時間）分散させた。また、分散の際にはジルコニアビーズ（平均粒径０．８ｍｍ）１３０ｇを混合して行った。これにより、本実施例に係る顔料組成物を作製した。 Example 1
In this example, 8 g of yellow No. 4 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 1 g of disodium hydrogen phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the vessel, and 45 g of ion exchanged water was further added. Subsequently, the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion | distribution, 130 g of zirconia beads (average particle diameter 0.8 mm) were mixed and performed. Thus, a pigment composition according to this example was produced.
　（実施例２）
　本実施例においては、分散安定剤としてのリン酸水素二ナトリウムの含有量を２ｇ、イオン交換水の含有量を４４ｇに変更した。それら以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 2)
In this example, the content of disodium hydrogen phosphate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例３）
　本実施例においては、分散安定剤としてコハク酸二ナトリウム（和光純薬工業株式会社製）を用いた。それ以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 3)
In this example, disodium succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例４）
　本実施例においては、分散安定剤としてのコハク酸二ナトリウムの含有量を２ｇ、イオン交換水の含有量を４４ｇに変更した。それら以外は実施例３と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 4)
In this example, the content of disodium succinate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g. A pigment composition according to this example was produced in the same manner as in Example 3 except for the above.
　（実施例５）
　本実施例においては、分散安定剤としてリンゴ酸二ナトリウム（和光純薬工業株式会社製）を用いた。それ以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 5)
In this example, disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例６）
　本実施例においては、分散安定剤としてのリンゴ酸二ナトリウムの含有量を２ｇ、イオン交換水の含有量を４４ｇに変更した。それら以外は実施例５と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 6)
In this example, the content of disodium malate as a dispersion stabilizer was changed to 2 g, and the content of ion exchanged water to 44 g. A pigment composition according to this example was produced in the same manner as in Example 5 except for the above.
　（実施例７）
　本実施例においては、分散安定剤としてエチレンジアミン四酢酸二ナトリウム（和光純薬工業株式会社製）を用いた。それ以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 7)
In this example, ethylenediaminetetraacetic acid disodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例８）
　本実施例においては、分散安定剤としてのエチレンジアミン四酢酸二ナトリウムの含有量を２ｇ、イオン交換水の含有量を４４ｇに変更した。それら以外は実施例７と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 8)
In this example, the content of disodium ethylenediaminetetraacetate as a dispersion stabilizer was changed to 2 g, and the content of ion exchange water to 44 g. A pigment composition according to this example was produced in the same manner as in Example 7 except for the above.
　（比較例１）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を４６ｇに変更した。それら以外は実施例１と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 1)
In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 1 except for the above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（実施例９）
　本実施例においては、分散安定剤としてクエン酸（和光純薬工業株式会社製）を用いた。それ以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 9)
In this example, citric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例１０）
　本実施例においては、分散安定剤としてリンゴ酸（和光純薬工業株式会社製）を用いた。それ以外は実施例９と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 10)
In this example, malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 9 except for the above.
　（実施例１１）
　本実施例においては、分散安定剤としてクエン酸１ｇを用い、顔料分散剤としてポリビニルピロリドン（商品名；コリドン１２ＰＦ、ＢＡＳＦジャパン株式会社製）０．１ｇを用いた。さらに、イオン交換水の含有量を５０．９ｇに変更した。それら以外は実施例１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 11)
In this example, 1 g of citric acid was used as a dispersion stabilizer, and 0.1 g of polyvinyl pyrrolidone (trade name: Kollidon 12PF, manufactured by BASF Japan Ltd.) was used as a pigment dispersant. Furthermore, the content of ion exchange water was changed to 50.9 g. A pigment composition according to this example was produced in the same manner as in Example 1 except for the above.
　（実施例１２）
　本実施例においては、分散安定剤としてリンゴ酸を用いた。それ以外は実施例１１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 12)
In this example, malic acid was used as a dispersion stabilizer. A pigment composition according to this example was produced in the same manner as in Example 11 except for the above.
　（実施例１３）
　本実施例においては、分散安定剤としてリンゴ酸二ナトリウム２ｇを用いた。さらに、イオン交換水の含有量を４９．９ｇに変更した。それら以外は実施例１１と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 13)
In this example, 2 g of disodium malate was used as a dispersion stabilizer. Furthermore, the content of ion exchange water was changed to 49.9 g. A pigment composition according to this example was produced in the same manner as in Example 11 except for the above.
　（比較例２）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を５１．９ｇに変更した。それら以外は実施例１１と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 2)
In this comparative example, the dispersion stabilizer was not blended, and the content of ion exchange water was changed to 51.9 g. A pigment composition according to this comparative example was produced in the same manner as in Example 11 except for the above.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（実施例１４）
　本実施例においては、レーキ顔料としての赤色３号アルミニウムレーキ（三栄源株式会社製）８ｇ、顔料分散剤としてのポリアクリル酸ナトリウム（商品名：ＴＥＧＯ（登録商標）　Ｄｉｓｐｅｒｓ　７１５Ｗ、Ｅｖｏｎｉｋ社製、質量平均分子量３０００）６ｇ、分散安定剤としてのリンゴ酸二ナトリウム（和光純薬工業株式会社製）２ｇを容器に添加し、さらにイオン交換水４４ｇを加えた。続いて、容器中の混合液を分散機（ペイントシェーカー、浅田鉄工株式会社製）にて、常温下で３時間（分散時間）分散させた。また、分散の際にはジルコニアビーズ（平均粒径０．８ｍｍ）１３０ｇを混合して行った。これにより、本実施例に係る顔料組成物を作製した。 (Example 14)
In this example, 8 g of red No. 3 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 2 g of disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the container, and further 44 g of ion exchange water was added. Subsequently, the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion | distribution, 130 g of zirconia beads (average particle diameter 0.8 mm) were mixed and performed. Thus, a pigment composition according to this example was produced.
　（比較例３）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を４６ｇに変更した。それら以外は実施例１４と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 3)
In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 14 except for the above.
　（実施例１５）
　本実施例においては、レーキ顔料として緑色３号アルミニウムレーキ（ダイワ化成株式会社製）を用いた。それ以外は実施例１４と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 15)
In the present example, a green No. 3 aluminum lake (manufactured by Daiwa Kasei Co., Ltd.) was used as a lake pigment. A pigment composition according to this example was produced in the same manner as Example 14 except for the above.
　（比較例４）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を４６ｇに変更した。それら以外は実施例１５と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 4)
In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 15 except for the above.
　（実施例１６）
　本実施例においては、レーキ顔料として青色１号アルミニウムレーキ（三栄源株式会社製）を用いた。それ以外は実施例１４と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 16)
In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) was used as a lake pigment. A pigment composition according to this example was produced in the same manner as Example 14 except for the above.
　（比較例５）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を４６ｇに変更した。それら以外は実施例１６と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 5)
In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 16 except for the above.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（実施例１７）
　本実施例においては、レーキ顔料としての赤色４０号アルミニウムレーキ（三栄源株式会社製）８ｇ、顔料分散剤としてのポリアクリル酸ナトリウム（商品名：ＴＥＧＯ（登録商標）　Ｄｉｓｐｅｒｓ　７１５Ｗ、Ｅｖｏｎｉｋ社製、質量平均分子量３０００）６ｇ、分散安定剤としてのリンゴ酸二ナトリウム（和光純薬工業株式会社製）２ｇを容器に添加し、さらにイオン交換水４４ｇを加えた。続いて、容器中の混合液を分散機（ペイントシェーカー、浅田鉄工株式会社製）にて、常温下で３時間（分散時間）分散させた。また、分散の際にはジルコニアビーズ（平均粒径０．８ｍｍ）１３０ｇを混合して行った。これにより、本実施例に係る顔料組成物を作製した。 (Example 17)
In this example, 8 g of red No. 40 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass 6 g of average molecular weight 3000) and 2 g of disodium malate (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer were added to the container, and further 44 g of ion exchange water was added. Subsequently, the mixture in the container was dispersed for 3 hours (dispersion time) at normal temperature by a dispersing machine (paint shaker, manufactured by Asada Iron Works Co., Ltd.). Moreover, in the case of dispersion | distribution, 130 g of zirconia beads (average particle diameter 0.8 mm) were mixed and performed. Thus, a pigment composition according to this example was produced.
　（比較例６）
　本比較例においては、分散安定剤を配合せず、イオン交換水の含有量を４６ｇに変更した。それら以外は実施例１７と同様の方法にて本比較例に係る顔料組成物を作製した。 (Comparative example 6)
In the present comparative example, the content of ion exchange water was changed to 46 g without blending the dispersion stabilizer. A pigment composition according to this comparative example was produced in the same manner as in Example 17 except for the above.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（実施例１８）
　本実施例においては、分散安定剤としてのリンゴ酸二ナトリウムの含有量を０．０６ｇ、イオン交換水の含有量を４５．９４ｇに変更した。それ以外は、実施例１６と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 18)
In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.06 g, and the content of ion exchanged water to 45.94 g. A pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
　（実施例１９）
　本実施例においては、分散安定剤としてのリンゴ酸二ナトリウムの含有量を０．１ｇ、イオン交換水の含有量を４５．９ｇに変更した。それ以外は、実施例１６と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 19)
In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.1 g, and the content of ion exchanged water to 45.9 g. A pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
　（実施例２０）
　本実施例においては、分散安定剤としてのリンゴ酸二ナトリウムの含有量を０．６ｇ、イオン交換水の含有量を４５．４ｇに変更した。それ以外は、実施例１６と同様の方法にて本実施例に係る顔料組成物を作製した。 Example 20
In this example, the content of disodium malate as a dispersion stabilizer was changed to 0.6 g and the content of ion exchanged water to 45.4 g. A pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
　（実施例２１）
　本実施例においては、分散安定剤としてのリンゴ酸二ナトリウムの含有量を５．７ｇ、イオン交換水の含有量を４０．３ｇに変更した。それ以外は、実施例１６と同様の方法にて本実施例に係る顔料組成物を作製した。 (Example 21)
In this example, the content of disodium malate as a dispersion stabilizer was changed to 5.7 g and the content of ion exchanged water to 40.3 g. A pigment composition according to this example was produced in the same manner as in Example 16 except for the above.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　（実施例２２）
　本実施例においては、レーキ顔料としての青色１号アルミニウムレーキ（三栄源株式会社製）、顔料分散剤としてのポリアクリル酸ナトリウム（商品名：ＴＥＧＯ（登録商標）　Ｄｉｓｐｅｒｓ　７１５Ｗ、Ｅｖｏｎｉｋ社製、質量平均分子量３０００）、分散安定剤としてのリンゴ酸二ナトリウム（和光純薬工業株式会社製）及び分散媒としてのイオン交換水を容器に入れ、分散機（ペイントシェーカー、浅田鉄工株式会社製）にて、常温下で６時間（分散時間）分散させた。また、分散の際にはジルコニアビーズ（平均粒径０．８ｍｍ）１３０ｇを混合させて行った。これにより、本実施例に係る顔料組成物を作製した。 (Example 22)
In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass average) Molecular weight 3000), disodium malate (made by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer, and ion-exchanged water as a dispersion medium in a container, using a disperser (paint shaker, made by Asada Iron Works Ltd.), Dispersion was carried out at normal temperature for 6 hours (dispersion time). Moreover, in the case of dispersion | distribution, 130 g of zirconia beads (average particle diameter 0.8 mm) were mixed and performed. Thus, a pigment composition according to this example was produced.
　次に、顔料組成物に、表面張力調整剤としてのカプリル酸デカグリセリル（商品名：ＳＹグリスターＭＣＡ７５０（商品名、阪本薬品工業株式会社製、ＨＬＢ値１６））及びイオン交換水を加え、表６に示す配合割合となる様に、インクジェット用水性インク組成物（以下、「水性インク組成物」という。）を調製し、ディスパーにて撹拌した。これにより、本実施例の水性インク組成物を作製した。 Next, to the pigment composition is added caprylic acid decaglyceryl (trade name: SY Glyster MCA 750 (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., HLB value 16)) and ion-exchanged water as a surface tension regulator, and Table 6 An aqueous ink composition for inkjet (hereinafter, referred to as "aqueous ink composition") was prepared so as to have a blending ratio as shown in the above, and stirred with a disper. Thus, the aqueous ink composition of this example was produced.
　（実施例２３）
　本実施例においては、レーキ顔料としての青色１号アルミニウムレーキ（三栄源株式会社製）、顔料分散剤としてのポリアクリル酸ナトリウム（商品名：ＴＥＧＯ（登録商標）　Ｄｉｓｐｅｒｓ　７１５Ｗ、Ｅｖｏｎｉｋ社製、質量平均分子量３０００）、分散安定剤としてのリンゴ酸二ナトリウム（和光純薬工業株式会社製）及び分散媒としてのイオン交換水を容器に入れ、分散機（ペイントシェーカー、浅田鉄工株式会社製）にて、常温下で６時間（分散時間）分散させた。また、分散の際にはジルコニアビーズ（平均粒径０．８ｍｍ）１３０ｇを混合させて行った。これにより、本実施例に係る顔料組成物を作製した。 (Example 23)
In this example, blue No. 1 aluminum lake (manufactured by San-Ei Gen Co., Ltd.) as a lake pigment, sodium polyacrylate as a pigment dispersant (trade name: TEGO (registered trademark) Dispers 715 W, manufactured by Evonik, mass average) Molecular weight 3000), disodium malate (made by Wako Pure Chemical Industries, Ltd.) as a dispersion stabilizer, and ion-exchanged water as a dispersion medium in a container, using a disperser (paint shaker, made by Asada Iron Works Ltd.), Dispersion was carried out at normal temperature for 6 hours (dispersion time). Moreover, in the case of dispersion | distribution, 130 g of zirconia beads (average particle diameter 0.8 mm) were mixed and performed. Thus, a pigment composition according to this example was produced.
　次に、顔料組成物に、表面張力調整剤としてのカプリル酸デカグリセリル（商品名：ＳＹグリスターＭＣＡ７５０（商品名、阪本薬品工業株式会社製、ＨＬＢ値１６））、湿潤剤としてのプロピレングリコール及びイオン交換水を加え、表６に示す配合割合となる様に、水性インク組成物を調製し、ディスパーにて撹拌した。これにより、本実施例の水性インク組成物を作製した。 Next, to the pigment composition, caprylic acid decaglyceryl (trade name: SY Glyster MCA 750 (trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., HLB value 16)) as a surface tension regulator, propylene glycol as a wetting agent and ions Exchanged water was added, and an aqueous ink composition was prepared so as to achieve the blending ratio shown in Table 6, and stirred with a disper. Thus, the aqueous ink composition of this example was produced.
　（実施例２４）
　本実施例においては、各成分の配合量を表６に示す値に変更した。それ以外は、実施例２３と同様の方法にて本実施例に係る水性インク組成物を作製した。 (Example 24)
In the present Example, the compounding quantity of each component was changed into the value shown in Table 6. An aqueous ink composition according to this example was produced in the same manner as in Example 23 except for the above.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　（レーキ顔料の体積基準積算粒度分布における粒子径の測定）
　実施例１～２１及び比較例１～６の各顔料組成物について、それぞれ作製直後のＤ１０、Ｄ５０及びＤ９９を測定した。また、実施例２２～２４の各水性インク組成物についても、それぞれ作製直後のＤ１０、Ｄ５０及びＤ９９を測定した。測定は、マイクロトラックＵＰＡ－ＥＸ１５０（商品名、日機装(株)製）を用いて動的光散乱法により行った。 (Measurement of particle size in volume-based integrated particle size distribution of lake pigment)
For each of the pigment compositions of Examples 1 to 21 and Comparative Examples 1 to 6, D10, D50 and D99 immediately after preparation were measured. In addition, D10, D50 and D99 immediately after preparation of each of the aqueous ink compositions of Examples 22 to 24 were also measured. The measurement was performed by a dynamic light scattering method using Microtrac UPA-EX 150 (trade name, manufactured by Nikkiso Co., Ltd.).
　続いて、各顔料組成物を密閉した容器にそれぞれ保管し、２５℃の環境下で、それぞれ一定期間静置して保存した。その後、再びレーキ顔料のＤ１０、Ｄ５０及びＤ９９について、前述と同様の方法にて測定した。尚、保管期間は、実施例１～１６、１８～２１及び比較例１～５の顔料組成物については３日間とし、実施例１７及び比較例６の顔料組成物については１０日間とした。結果を表１～表６に示す。 Subsequently, each pigment composition was stored in a sealed container, respectively, and was allowed to stand and stored for a certain period in an environment of 25 ° C. Thereafter, the lake pigments D10, D50 and D99 were again measured in the same manner as described above. The storage period was 3 days for the pigment compositions of Examples 1 to 16 and 18 to 21 and Comparative Examples 1 to 5, and was 10 days for the pigment compositions of Example 17 and Comparative Example 6. The results are shown in Tables 1 to 6.
　（結果）
　表１～表５から明らかな通り、実施例１～２１の顔料組成物においては、リン酸水素二ナトリウム等の分散安定剤を添加することにより、顔料組成物を一定期間保管した後においても、各レーキ顔料のＤ１０、Ｄ５０及びＤ９９が大幅に増大するのを抑制し、顔料組成物のゲル化を防止することができた。その一方、比較例１～６の顔料組成物においては、分散安定剤を添加しなかったことから、当該顔料組成物を一定期間保管した後のレーキ顔料のＤ１０、Ｄ５０及びＤ９９は大幅に増加し、本実施例１～２１と比較して分散安定性（保存安定性）に劣ることが確認された。 (result)
As apparent from Tables 1 to 5, in the pigment compositions of Examples 1 to 21, even after the pigment composition is stored for a certain period of time by adding a dispersion stabilizer such as disodium hydrogen phosphate, It was possible to suppress the significant increase of D10, D50 and D99 of each lake pigment and to prevent the gelation of the pigment composition. On the other hand, in the pigment compositions of Comparative Examples 1 to 6, since the dispersion stabilizer was not added, D10, D50 and D99 of the lake pigments after storage of the pigment composition for a certain period of time significantly increased. It was confirmed that the dispersion stability (storage stability) was inferior to those of Examples 1 to 21.
　また、表６から明らかな通り、実施例２２～２４においては、各レーキ顔料のＤ１０が５０ｎｍ～３００ｎｍ、Ｄ５０が５０ｎｍ～７００ｎｍ、Ｄ９９が５０ｎｍ～３０００ｎｍの範囲にあり、良好な吐出安定性を有する水性インク組成物が得られることが確認された。 Further, as apparent from Table 6, in Examples 22 to 24, D10 is 50 nm to 300 nm, D50 is 50 nm to 700 nm, and D99 is 50 nm to 3000 nm in each of the lake pigments, and the ejection stability is excellent. It was confirmed that an aqueous ink composition was obtained.

Claims (6)

  1. 　少なくとも１種のレーキ顔料、顔料分散剤、及び分散安定剤を少なくとも含む可食性の顔料組成物であって、
    　前記分散安定剤が、カルボン酸、カルボン酸塩、ホスホン酸、ホスホン酸塩及びエチレンジアミン四酢酸塩からなる群より選ばれる少なくとも１種であり、
    　前記レーキ顔料の含有量が、前記顔料組成物の全質量に対し２０質量％以下であり、
    　前記分散安定剤の含有量が、前記顔料組成物の全質量に対し１０質量％以下である顔料組成物。     An edible pigment composition comprising at least one lake pigment, a pigment dispersant, and a dispersion stabilizer.
    The dispersion stabilizer is at least one selected from the group consisting of carboxylic acid, carboxylic acid salt, phosphonic acid, phosphonic acid salt and ethylenediaminetetraacetic acid salt,
    The content of the lake pigment is 20% by mass or less based on the total mass of the pigment composition,
    The pigment composition whose content of the said dispersion stabilizer is 10 mass% or less with respect to the total mass of the said pigment composition.
  2. 　前記レーキ顔料の含有量が、前記顔料組成物の全質量に対し１５質量％以下である請求項１に記載の顔料組成物。 The pigment composition according to claim 1, wherein the content of the lake pigment is 15% by mass or less based on the total mass of the pigment composition.
  3. 　前記レーキ顔料が、赤色２号、赤色３号、赤色４０号、赤色１０２号、黄色４号、黄色５号、緑色３号、青色１号及び青色２号からなる群より選ばれる何れか１種の染料をレーキ化したものである請求項１又は２に記載の顔料組成物。 The lake pigment is any one selected from the group consisting of Red No. 2, Red No. 3, Red No. 40, Red No. 102, Yellow No. 4, Yellow No. 5, Yellow No. 3, Green No. 3, Blue No. 1 and Blue No. 2. The pigment composition according to claim 1 or 2, which is a laked dye.
  4. 　前記顔料分散剤が、ポリアクリル酸ナトリウム、ポリビニルピロリドン、多糖類、ゼラチン、コラーゲン、ポリビニルアルコール、ポリビニルアルコール誘導体、アミノアルキルメタクリレートコポリマー、メタクリル酸コポリマー、アンモニオアルキルメタクリレートコポリマー、アクリル酸エチル・メタクリル酸メチルコポリマー及び酢酸ビニルからなる群より選ばれる少なくとも１種である請求項１～３の何れか１項に記載の顔料組成物。 The pigment dispersant is sodium polyacrylate, polyvinyl pyrrolidone, polysaccharide, gelatin, collagen, polyvinyl alcohol, polyvinyl alcohol derivative, aminoalkyl methacrylate copolymer, methacrylic acid copolymer, ammonio alkyl methacrylate copolymer, ethyl acrylate / methyl methacrylate The pigment composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of a copolymer and vinyl acetate.
  5. 　請求項１～４の何れか１項に記載の顔料組成物を含み、かつ、可食性を有するインクジェット用水性インク組成物。 An aqueous inkjet ink composition comprising the pigment composition according to any one of claims 1 to 4 and being edible.
  6. 　インクジェット用水性インクの乾燥皮膜を表面に有する固体製剤であって、
    　前記インクジェット用水性インクは、請求項５に記載のインクジェット用水性インク組成物を含むものである固体製剤。     A solid preparation having a dry film of an aqueous ink for ink jet on the surface,
    A solid preparation comprising the aqueous inkjet ink composition according to claim 5.
PCT/JP2019/001424 2018-01-19 2019-01-18 Pigment composition, inkjet water-based ink composition, and solid formulation WO2019142899A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62127356A (en) * 1984-10-24 1987-06-09 クロンプトン・アンド・ノウルス・コ−ポレ−シヨン Aqueous lake pigment suspension composition
JP2000297239A (en) * 1999-04-16 2000-10-24 Toyo Ink Mfg Co Ltd Ink jet ink, marking on eggshell using the same and marked egg
WO2011114689A1 (en) * 2010-03-15 2011-09-22 大正製薬株式会社 Pigment composition
WO2011114691A1 (en) * 2010-03-15 2011-09-22 大正製薬株式会社 Pigment composition
JP2015218144A (en) * 2014-05-20 2015-12-07 紀州技研工業株式会社 Printed tablet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62127356A (en) * 1984-10-24 1987-06-09 クロンプトン・アンド・ノウルス・コ−ポレ−シヨン Aqueous lake pigment suspension composition
JP2000297239A (en) * 1999-04-16 2000-10-24 Toyo Ink Mfg Co Ltd Ink jet ink, marking on eggshell using the same and marked egg
WO2011114689A1 (en) * 2010-03-15 2011-09-22 大正製薬株式会社 Pigment composition
WO2011114691A1 (en) * 2010-03-15 2011-09-22 大正製薬株式会社 Pigment composition
JP2015218144A (en) * 2014-05-20 2015-12-07 紀州技研工業株式会社 Printed tablet

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