WO2015166901A1 - Aqueous ink composition for writing instruments - Google Patents

Aqueous ink composition for writing instruments Download PDF

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Publication number
WO2015166901A1
WO2015166901A1 PCT/JP2015/062664 JP2015062664W WO2015166901A1 WO 2015166901 A1 WO2015166901 A1 WO 2015166901A1 JP 2015062664 W JP2015062664 W JP 2015062664W WO 2015166901 A1 WO2015166901 A1 WO 2015166901A1
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WO
WIPO (PCT)
Prior art keywords
microcapsule pigment
photochromic
average particle
thermochromic
ink composition
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PCT/JP2015/062664
Other languages
French (fr)
Japanese (ja)
Inventor
市川　秀寿
孝介 小椋
Original Assignee
三菱鉛筆株式会社
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Publication of WO2015166901A1 publication Critical patent/WO2015166901A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K8/00—Pens with writing-points other than nibs or balls
    • B43K8/02—Pens with writing-points other than nibs or balls with writing-points comprising fibres, felt, or similar porous or capillary material
    • 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
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents

Definitions

  • the present invention relates to an aqueous ink composition for a writing instrument that can easily discriminate problems such as intentional or unexpected writing lines and falsification of recording due to thermochromic coloring materials.
  • thermochromic writing instrument using a thermochromic color material such as a thermochromic microcapsule pigment can easily erase a drawn line by heat such as frictional heat.
  • heat such as frictional heat
  • falsification of intentional or unexpected recording is a problem.
  • it is possible to recolor the drawn lines after writing but since the color temperature for recurrence is generally set to less than 0 ° C, a separate cooling device is required and simplified. It cannot be determined.
  • thermochromic color material for example, 1) a photochromic pigment containing an organic photochromic material, a shear thinning agent, water,
  • a photochromic pigment containing an organic photochromic material, a shear thinning agent, water for example, water-based photochromics for ballpoint pens with excellent temporal stability that can contain white pigments such as titanium dioxide, fluorescent pigments, phosphorescent pigments, thermochromic pigments, and glitter pigments.
  • Ink composition (see, for example, Patent Document 1) 2) An ink containing a colorant selected from a specific reversible thermochromic material, a photochromic organic material, a dye, and a fluorescent pigment is contained in a transparent ink containing tube, and the ink A writing instrument in which a refill formed by adhering a writing tip part directly to a receiving tube tip or via a relay member is contained in a transparent shaft cylinder, and an ultraviolet absorber or the like is provided in the shaft cylinder or the like.
  • Writing instrument with improved light resistance of ink contained for example, see Patent Document 2), 3)
  • a diarylethene photochromic compound and a specific reversible thermochromic and thermochromic color composition are included.
  • a color-changing material comprising a microcapsule pigment, a color-changing liquid composition comprising the color-changing material and a vehicle (see, for example, Patent Document 3) are known.
  • the water-based ink compositions for writing instruments of Patent Documents 1 and 2 described above can be used in combination with a thermochromic color material and a photochromic color material, and there is no support for the examples in each document.
  • the object of the invention is to improve the stability over time and the light resistance of the ink.
  • the subject and the object of the invention are completely different from the aqueous ink composition for writing instruments, which can easily discriminate problems such as intentional or unexpected writing lines and falsification of recording due to the thermochromic coloring material of the present invention.
  • Patent Document 3 discloses the proximity technique of the present invention, but uses a microcapsule pigment containing a diarylethene-based photochromic compound and a two-component encapsulating a specific reversible thermochromic composition. Therefore, it is difficult to maintain the photochromic and thermochromic functions at a certain level of quality, and one or both of the photochromic and thermochromic functions may deteriorate over time. The current situation is that there is room for further improvement.
  • JP 2005-314659 A (claims, paragraph 0016, etc.)
  • JP-A-2006-103212 (Claims etc.)
  • JP 2007-63433 A (claims, examples, etc.)
  • the present invention is to solve this problem in view of the problems and current state of the prior art, Falsify intentional or unexpected writing lines and recordings with thermochromic coloring materials by making the functions of thermochromic coloring materials and photochromic coloring materials highly compatible without compromising aging stability and writing performance. It is an object of the present invention to provide a water-based ink composition for a writing instrument that can easily determine the above problem.
  • thermochromic microcapsule pigment as a thermochromic color material, and are colorless in an indoor lighting environment as a photochromic color material.
  • it contains at least a photochromic microcapsule pigment having a property of developing in an ultraviolet irradiation environment, and the average particle diameter of the thermochromic microcapsule pigment and the photochromic microcapsule pigment is both within a specific range, By identifying the difference between the average particle diameters of the two, it was found that the above-mentioned aqueous ink composition for writing instruments can be obtained, and the present invention has been completed.
  • the present invention resides in the following (1) and (2).
  • (1) It contains at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and has a property of coloring in an ultraviolet irradiation environment,
  • the average particle size of both the thermochromic microcapsule pigment and the photochromic microcapsule pigment is 0.2 to 3 ⁇ m, and the average particle size of both is 50% or more of the average particle with respect to the large average particle size
  • a water-based ink composition for a writing instrument having a diameter A writing instrument comprising the aqueous ink composition for a writing instrument described in (1) above.
  • an aqueous ink composition for a writing instrument that can easily determine problems such as intentional or unexpected writing lines and falsification of recording due to a thermochromic color material without impairing stability over time and writing performance. Provided.
  • the aqueous ink composition for a writing instrument of the present invention contains at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and is used in an ultraviolet irradiation environment.
  • Both of the thermochromic microcapsule pigment and the photochromic microcapsule pigment have an average particle size of 0.2 to 3 ⁇ m, and the average particle size of both is a particle having a large average particle size. On the other hand, it has an average particle diameter of 50% or more.
  • thermochromic microcapsule pigment used as the thermochromic color material used in the present invention is one that changes color by heat such as frictional heat, for example, a function that changes from colored to colorless, colored to colored, colorless to colored, etc. If it is, it will not specifically limit, A various thing can be used, What microencapsulated the thermochromic composition containing a leuco dye, a color developer, and a color-change temperature regulator at least.
  • the leuco dye that can be used is not particularly limited as long as it is an electron donating dye and functions as a color former.
  • conventionally known ones such as triphenylmethane, spiropyran, fluoran, diphenylmethane, rhodamine lactam, indolylphthalide, leucooramine, It can be used alone (one kind) or in a mixture of two or more kinds (hereinafter simply referred to as “at least one kind”).
  • leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, etc., and develop color when these skeletons (rings) are opened. It is preferable to use a leuco dye that changes from colored to colorless by heat.
  • the developer that can be used is a component having the ability to develop the leuco dye, such as a phenol resin compound, a salicylic acid metal chloride, a salicylic acid resin metal salt compound, a solid acid compound, etc. Is mentioned.
  • Specific examples of the developer that can be used include o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, hexafluorobisphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4′-hydroxyphenyl) propane, 4,4 -Dihydroxydiphenylsulfone, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2-bis
  • the amount of the developer to be used may be arbitrarily selected according to the desired color density and is not particularly limited, but is usually 0.1 to 1 part by weight with respect to 1 part by mass of the leuco dye. It is preferable to select within a range of about 100 parts by mass.
  • the color change temperature adjusting agent that can be used is a substance that controls the color change temperature in the coloration of the leuco dye and the developer.
  • Conventionally known color change temperature adjusting agents can be used. Specific examples include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.
  • bis (4-hydroxyphenyl) phenylmethane dicaprylate C 7 H 15
  • bis (4-hydroxyphenyl) phenylmethane dilaurate C 11 H 23
  • bis (4-hydroxyphenyl) phenylmethane dimyristate C 13 H 27
  • bis (4-hydroxyphenyl) phenylethane dimyristate C 13 H 27
  • bis (4-hydroxyphenyl) phenylmethane dipalmitate C 15 H 30
  • bis (4-hydroxy And at least one of phenyl) phenylmethane dibehenate C 21 H 43
  • bis (4-hydroxyphenyl) phenylethylhexylidene dimyristate C 13 H 27
  • the amount of the color-change temperature adjusting agent used may be appropriately selected according to the desired hysteresis width and color density at the time of color development, and is not particularly limited, but is usually based on 1 part by mass of the leuco dye. It is preferably used within the range of about 1 to 100 parts by mass.
  • thermochromic microcapsule pigment of the present invention is obtained by microencapsulating a thermochromic composition containing at least the leuco dye, the developer, and the color change temperature adjusting agent so that the average particle diameter is 0.2 to 3 ⁇ m.
  • a thermochromic composition containing at least the leuco dye, the developer, and the color change temperature adjusting agent so that the average particle diameter is 0.2 to 3 ⁇ m.
  • the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.
  • thermochromic microcapsule pigment For example, in a phase separation method from an aqueous solution, a leuco dye, a developer, and a color change temperature adjusting agent are heated and melted, then charged into an emulsifier solution, heated and stirred to disperse into oil droplets, and then as a capsule film agent,
  • resin raw materials for example, amino resin solution, specifically, each solution such as methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc., gradually add and continue to react, then filter this dispersion
  • the desired thermochromic microcapsule pigment can be produced.
  • the content of these leuco dyes, developer, and color change temperature adjusting agent varies depending on the type of leuco dye, developer, color change temperature adjusting agent used, microencapsulation method, etc.
  • the developer is 0.1 to 100
  • the color change temperature adjusting agent is 1 to 100
  • the capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.
  • the thermochromic microcapsule pigment used in the present invention is a color combination temperature of each color (for example, color development at 0 ° C. or higher) by suitably combining the types, amounts, and the like of the leuco dye, the developer and the color change temperature adjusting agent,
  • the decoloring temperature (for example, decoloring at 50 ° C. or higher) can be set to a suitable temperature, and it is preferable to use a thermochromic microcapsule pigment that changes from colored to colorless by heat such as frictional heat.
  • the wall film is preferably formed of a urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the drawing density, storage stability, and writing property.
  • a urethane resin the compound of isocyanate and a polyol is mentioned, for example.
  • an epoxy resin the compound of an epoxy resin and an amine is mentioned, for example.
  • the amino resin is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, and more preferably formed of a melamine resin from the viewpoints of manufacturability, storage stability, and writing properties.
  • the thickness of the wall film of the microcapsule coloring material is appropriately determined according to the required strength of the wall film and the drawn line density.
  • a suitable amino resin raw material melamine resin, urea resin, benzoguanamine resin, etc.
  • a dispersant a protective colloid, etc. select.
  • the average particle size of the thermochromic microcapsule pigment used in the present invention suppresses adverse effects on colorability, color developability, easy decolorization, stability, fluidity in ink, and writing properties, as described below. From the viewpoint of compatibility with the photochromic microcapsule pigment, it is preferably 0.2 to 3 ⁇ m, more preferably 0.2 to 2.3 ⁇ m.
  • the “average particle size” defined in the present invention is a value obtained by measuring the average particle size with a particle size analyzer [Microtrac HRA9320-X100 (Nikkiso Co., Ltd.)].
  • the average particle size is less than 0.2 ⁇ m, sufficient line density cannot be obtained, while if it exceeds 3 ⁇ m, the writing property is deteriorated and the dispersion stability of the thermochromic microcapsule pigment is reduced. It is not preferable.
  • the microcapsule pigment in the above average particle size range (0.2 to 3 ⁇ m) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution, the stirring conditions for producing the microcapsule pigment Can be prepared by suitably combining them.
  • the photochromic microcapsule pigment used as the photochromic color material for use in the present invention is not particularly limited as long as it is colorless in an indoor lighting environment and has a property of coloring in an ultraviolet irradiation environment.
  • a photochromic dye (compound) having the above characteristics and a microencapsulated fluorescent dye can be used.
  • the “indoor lighting environment” is, for example, a lighting fixture selected from an incandescent lamp, a fluorescent lamp, a lamp, a white LED, etc.
  • the “ultraviolet irradiation environment” Irradiation (with a wavelength of 200 to 400 nm), for example, an irradiation environment with black light, an irradiation environment with sunlight including ultraviolet rays, and the like.
  • photochromic dyes examples include 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride and 2,3-bis (2,4,5-trimethyl).
  • -3-thienyl) maleimide cis-1,2-dicyano-1,2-bis (2,4,5-trimethyl-3-thienyl) ethene, 1,2-bis [2-methylbenzo [b] thiophene-3 -Yl] -3,3,4,4,5,5-hexafluoro-1-cyclopentene, 1,2-bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4, 4,5,5-hexafluoro-1-cyclopentene, 1- (2-hydroxyethyl) -3,3-dimethylindolino-6'-nitrobenzopyrospirane, 1,3,3-trimethylindolinobenzopyri Loss Pyran, 1,3,3-trimethylindolino-6'-nitrobenzopyro
  • photochromic fluorescent dyes examples include anthracene derivatives such as arylamine derivatives and phenylanthracene derivatives, pentacene derivatives, oxadiazole derivatives, oxazole derivatives, triazole derivatives, benzoxazole derivatives, and benzoazatriazole derivatives.
  • azole derivatives such as azole derivatives, thiophene derivatives such as oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, diene derivatives such as tetraphenylbutadiene derivatives, distyrylbenzene derivatives, distyrylpyrazone derivatives, distyrylarylene derivatives, stilbene derivatives, triphenyl Amine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyrazole derivatives, pyrazoline derivatives, pyridi Derivatives, porphyrin derivatives, pyrrole derivatives such as phthalocyanine derivatives, fluorene derivatives, phenanthroline derivatives, pyrene derivatives, phenanthrene derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, benzoxazinone derivatives, quinophthalone derivatives, rubren
  • the photochromic microcapsule pigment of the present invention comprises at least one or more selected from the above-mentioned photochromic dyes (compounds), fluorescent dyes, additives such as organic solvents, antioxidants, light stabilizers, and sensitizers.
  • Photochromic dyes compounds
  • fluorescent dyes additives such as organic solvents, antioxidants, light stabilizers, and sensitizers.
  • additives such as organic solvents, antioxidants, light stabilizers, and sensitizers.
  • the microencapsulation method it can be prepared in the same manner as the production of the above-mentioned thermochromic microcapsule pigment.
  • a photochromic dye (compound) or the like is used as diethylene glycol, methyl ethyl ketone, phenyl glycol.
  • a resin raw material is used as a capsule film agent, for example, an amino resin solution, specifically Then, gradually add each liquid such as methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc., and continue to react, then by filtering this dispersion, it is colorless in the desired indoor lighting environment, and develops color in the ultraviolet irradiation environment
  • a photochromic microcapsule pigment having the following properties can be produced.
  • the average particle size of the photochromic microcapsule pigment used in the present invention is the color erasability in an indoor lighting environment, the color developability that allows a color to be suitably developed in an ultraviolet irradiation environment, the fluidity in ink, the stability, and the writing From the viewpoints of suppressing adverse effects on the properties and compatibility with the above-described thermochromic microcapsule pigments, it is preferably 0.2 to 3 ⁇ m, more preferably 0. A thickness of 2 to 2.3 ⁇ m is desirable. If the average particle diameter is less than 0.2 ⁇ m, sufficient line density cannot be obtained, while if it exceeds 3 ⁇ m, the writing property is deteriorated and the dispersion stability of the photochromic microcapsule pigment is reduced. It is not preferable.
  • the microcapsule pigment in the above average particle size range (0.2 to 3 ⁇ m) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution, the stirring conditions for producing the microcapsule pigment Can be prepared by suitably combining them.
  • thermochromic microcapsule pigment and the photochromic microcapsule pigment to be used both have an average particle diameter of 0.2 to 3 ⁇ m as described above, and the thermochromic microcapsule pigment and the photochromic microcapsule pigment.
  • Each average particle size of the capsule pigment has an average particle size of 50% or more with respect to particles having a large average particle size, and preferably has an average particle size of 70% or more with respect to particles having a large average particle size. Is desirable.
  • the average particle size of the thermochromic microcapsule pigment is large (2 ⁇ m)
  • the average particle size of the photochromic microcapsule pigment is 50% or more, specifically 1 ⁇ m or more, preferably 1.4 ⁇ m or more.
  • the average particle size of the photochromic microcapsule pigment is large (for example, 1.8 ⁇ m)
  • the average particle size of the thermochromic microcapsule pigment is 50% or more, specifically Means 0.9 ⁇ m or more, preferably 1.26 ⁇ m or more. If the average particle size of both of these particles has an average particle size of less than 50% with respect to the large particles, both pigments tend to be in a densely packed state, resulting in a decrease in fluidity and an increase in ink viscosity. This is undesirable.
  • the average particle size of the thermochromic microcapsule pigment and the photochromic microcapsule pigment used are both in the range of 0.2 to 3 ⁇ m, and the average particle size of both microcapsule pigments within this range.
  • the water-based ink composition for a writing instrument of the present invention contains at least the thermochromic microcapsule pigment having the above-described configuration and the photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment, and has ultraviolet rays.
  • the thermochromic microcapsule pigment and the photochromic microcapsule pigment both have a property of coloring in an irradiation environment, and both have an average particle size of 0.2 to 3 ⁇ m. It has an average particle size of 50% or more with respect to large particles, and can be used as a water-based ink composition for writing instruments such as ballpoint pens and marking pens. It can be suitably used for fake discrimination, hidden messages, and the like.
  • thermochromic microcapsule pigment of the present invention varies depending on the use of the water-based ink composition for writing instruments and cannot be generally set.
  • the thermochromic microcapsule pigment is 5 to 50% by mass, preferably 5 to 30% by mass
  • the photochromic microcapsule pigment is 0.1 to 10% by mass, preferably based on the total amount of the ink composition. 0.5 to 7% by mass is desirable.
  • the thermochromic microcapsule pigment is 0.1 to 10%, preferably 0.5 to 7% by mass
  • the photochromic microcapsule pigment is 5 to 50% by mass with respect to the total amount of the ink composition. %, Preferably 5 to 30% by mass.
  • the balance is water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.).
  • water-soluble organic solvents, thickeners, lubricants, rust preventives, antiseptics or antibacterials are used as long as the effects of the present invention are not impaired.
  • An agent or the like can be appropriately contained.
  • water-soluble organic solvents examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, ethylene glycol monomethyl ether, and diethylene glycol monomethyl. Ethers can be used alone or in combination.
  • the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, celluloses and polysaccharides is desirable. Specifically, gum arabic, gum tragacanth, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, diutane gum, dextran, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch glycolic acid and Its salt, propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid and its salt, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinyl pyrrolidone, cross-linked acrylic acid polymer and its Salt, non-crosslinked acrylic acid polymer and its salt, styrene acrylic acid copolymer and its salt, etc
  • Lubricants include nonionics such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphates, which are also used in pigment surface treatment agents, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones.
  • thermochromic and photochromic microcapsule pigments In order to produce this water-based ink composition for writing instruments, a conventionally known method can be employed. For example, in addition to the thermochromic and photochromic microcapsule pigments, a predetermined amount of each component in the water is used. It is obtained by mixing and stirring and mixing with a homomixer or a stirrer such as a disper. Furthermore, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
  • the water-based ink composition for a writing instrument of the present invention configured as described above is mounted on a marking pen body having a fiber chip, a felt chip, and a plastic chip at the writing tip, and a ballpoint pen body having a ball pen tip at the writing tip.
  • the aqueous ink composition for a writing instrument and the writing instrument of the present invention contain at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and is irradiated with ultraviolet rays.
  • thermochromic microcapsule pigment and the photochromic microcapsule pigment has the property of coloring in the environment, and the average particle size of the thermochromic microcapsule pigment and the photochromic microcapsule pigment is both 0.2 to 3 ⁇ m, and the average particle size of both is large.
  • water-based inks including those having an average particle diameter of 50% or more to the particles, and writing or drawing on paper, documents, etc.
  • thermochromic microcapsule pigments that become thermochromic colorants without compromising aging stability and writing performance
  • a writing instrument such as a ballpoint pen or marking pen equipped with this ink Intentional or unexpected writing with thermochromic microcapsule pigments that become thermochromic colorants without compromising aging stability and writing performance
  • photochromic microcapsule pigments which are colorless in indoor lighting environments and have the property of developing colors in an ultraviolet irradiation environment, can be easily identified. It can be suitably used for a hidden message or the like.
  • the sender side writes a hidden message, a password, or the like in a specific part such as a document, and then thermally erases the drawn line. Examples include a usage mode in which a message can be read by placing the specific part in an ultraviolet irradiation environment such as ultraviolet irradiation.
  • the water-based ink composition for a writing instrument of the present invention comprises a thermochromic microcapsule pigment and a photochromic microcapsule pigment as separate two components, so that a dye such as a leuco dye or a photochromic dye contained in each microcapsule. It is possible to use an additive according to the above characteristics, and it is possible to further individually form fine particles.
  • thermochromic colorant and photochromic colorant for example, when thermochromic microcapsules contain an antioxidant useful in photochromic microcapsule pigments, thermal temperature characteristics Therefore, it becomes difficult to make a design that maintains a constant quality, and it is difficult to make fine particles.
  • thermochromic microcapsule pigment and the photochromic microcapsule pigment are essential, and further, the thermochromic microcapsule pigment and the photochromic microcapsule.
  • Both the average particle diameter of the pigment is set to 0.2 to 3 ⁇ m, and the average particle diameter of both has an average particle diameter of 50% or more with respect to particles having a large average particle diameter.
  • the function according to the characteristics of photo-discoloration can be effectively exhibited, and further finer particles can be formed.
  • the hue concentration of each pigment is higher, and heat stability is maintained without impairing stability over time and writing performance.
  • An aqueous ink composition for a writing instrument that can easily determine the erasure history or the like with a photochromic color material for problems such as intentional or unexpected writing lines or falsification of recording due to the color-changing color material is obtained.
  • thermochromic microcapsule pigments were obtained by combinations of leuco dyes, color developers, and color-changing temperature regulators in the amounts shown in A-1, A-2 and A-7 in Table 1 below. Specifically, in A-1, 1 part of methyl-3 ′, 6′-bisdiphenylaminofluorane as the leuco dye, 2 parts of 1,1-bis (4-hydroxyphenyl) cyclohexane as the developer, As a color change temperature adjusting agent, 24 parts of bis (4-hydroxyphenyl) phenylmethane dicaprylate was heated and melted to 100 ° C. to obtain 27 parts of a homogeneous composition.
  • a capsule film agent 10 parts of an isocyanate and 10 parts of a polyol were added to a uniform hot solution of 27 parts of the composition obtained above and stirred and mixed. Subsequently, 60 parts of 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Next, using 5 parts of 5% polyvalent amine, treatment was performed at 80 ° C. for 60 minutes to obtain microcapsules. The microencapsulated aqueous dispersion obtained by the above procedure was spray-dried to prepare a powder of A-1 thermochromic microcapsule pigment.
  • thermochromic microcapsule pigments shown in A-2 and A-7 of Table 1 below were produced.
  • the average particle diameters of the obtained A-1, A-2, and A-7 and the hue (color development state) (decolored at 50 ° C. or higher) in a bright place (25 ° C.) are shown in Table 1 below.
  • Photochromic microcapsule pigments were obtained by combining photochromic dyes (photochromic dyes, fluorescent dyes) and solvents in the amounts shown in A-3 to A-6 and A-8 in Table 1 below. Specifically, in A-3, as a photochromic dye, 3 parts of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) spironafusozazine, 10 parts of diethylene glycol dibenzoate, and 10 of methyl ethyl ketone The parts were heated and melted to 80 ° C. to obtain 23 parts of a homogeneous composition.
  • a capsule film agent 10 parts of isocyanate and 10 parts of polyol were added to a uniform hot solution of 23 parts of the composition obtained above and stirred and mixed. Subsequently, 60 parts of 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Next, using 5 parts of 5% polyvalent amine, treatment was performed at 80 ° C. for 60 minutes to obtain microcapsules. The microencapsulated water dispersion obtained by the above procedure was spray-dried to obtain a powder-like A-3 photochromic microcapsule pigment.
  • thermochromic microcapsule having the property of being colorless in the indoor lighting environment shown in Table 1 and being colored in the ultraviolet irradiation environment shown in Table 1 below.
  • a pigment was produced.
  • the average particle diameters of the obtained A-3 to A-6 and A-8 and the hue (color development state) in the ultraviolet irradiation environment are shown in Table 1 below.
  • thermochromic and photochromic microcapsule pigment (A-1 to A-8) obtained in the above production example was used in accordance with the formulation shown in Table 2 below (total amount: 100% by mass) according to a conventional method.
  • a water-based aqueous ink composition for ballpoint pens was prepared.
  • a water-based ballpoint pen was produced using each ink composition obtained above. Specifically, using an axis of a ballpoint pen (Mitsubishi Pencil Co., Ltd., trade name: UF-202), an inner diameter of 3.8 mm, a length of 90 mm, a polypropylene ink containing tube, and a stainless tip (a cemented carbide ball, a ball A water ballpoint pen was manufactured by filling each water-based ink with a refill composed of a joint connecting the receiving tube and the tip with a diameter of 0.5 mm) and an ink follower mainly composed of mineral oil at the rear end of the ink. . Using the obtained water-based ballpoint pens of Examples 1 to 6 and Comparative Examples 1 and 2, the decoloring property and color developability were evaluated by the following evaluation methods. These results are shown in Table 2 below.
  • Evaluation method of color development The paper erased by the above-described evaluation of decoloring property was irradiated with sunlight and black light (315 to 400 nm) for 3 seconds, respectively, and then evaluated based on the following evaluation criteria. Evaluation criteria: ⁇ : A drawn line derived from a photochromic dye can be strongly recognized. X: A drawn line derived from a photochromic dye cannot be recognized.
  • the aqueous ink compositions for writing instruments of Examples 1 to 6 according to the present invention are the aqueous ink compositions for writing instruments of Comparative Examples 1 and 2 that are outside the scope of the present invention. It was found that satisfactory thermal decolorization and photochromic properties were obtained compared to the product.
  • the average particle diameters of the thermochromic microcapsule pigment and the photochromic microcapsule pigment are 2 ⁇ m and 0.1 ⁇ m, and 50% or more of the particles having a large average particle diameter of both. Since there is no average particle size and the difference is large, the ink fluidity is poor and the evaluation is impossible (evaluation “ ⁇ ”).
  • the average particle size of the photochromic microcapsule pigment is Since it falls outside the scope of the present invention, the color developability of the photochromic microcapsule pigment was inferior. Therefore, the water-based ink composition for a writing instrument according to the present invention eliminates problems such as intentional or unexpected writing lines and falsification of recording due to a thermochromic color material without impairing the temporal stability and writing performance. It was confirmed that erasure history and the like can be easily discriminated by the material, and it is suitable for history confirmation, forgery prevention, authenticity discrimination, hidden message and the like.

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Abstract

Provided is an aqueous ink composition for writing instruments, whereby, without losing long-term stability or writing performance, issues such as intentional or unintentional written lines or alteration of records that are caused by thermochromic colorants can be easily determined by an photochromic colorant, said aqueous ink composition for writing instruments being suitable for applications such as history verification, forgery prevention, authentication, and hidden messages.　The aqueous ink composition for writing instruments is characterized by: containing at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment; having properties whereby the photochromic microcapsule pigment is colorless in an indoor illuminated environment and emits color in an ultraviolet irradiation environment; the average particle diameter of the thermochromic microcapsule pigment and the photochromic microcapsule pigment being 0.2-3 µm; and the average particle diameter of both having the average particle diameter of at least 50% of particles having a large average particle diameter.

Description

筆記具用水性インク組成物Water-based ink composition for writing instruments
　本発明は、熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を簡易に判別できる筆記具用水性ンク組成物に関する。 The present invention relates to an aqueous ink composition for a writing instrument that can easily discriminate problems such as intentional or unexpected writing lines and falsification of recording due to thermochromic coloring materials.
　従来より、熱変色性マイクロカプセル顔料などの熱変色性色材を用いた熱変色筆記具は、摩擦熱等の熱により容易に描線を消去することができるものである。
　しかしながら、摩擦熱等の熱により容易に描線を消去できるため、意図的もしくは予期せぬ記録の改竄が問題となっている。
　このような改竄を簡易に判別するためには、筆記後の描線を再発色させることで可能となるが、再発色温度は概ね０℃未満に設定されているため、別途冷却装置が必要となり簡易に判別できないものである。 Conventionally, a thermochromic writing instrument using a thermochromic color material such as a thermochromic microcapsule pigment can easily erase a drawn line by heat such as frictional heat.
However, since the drawn lines can be easily erased by heat such as frictional heat, falsification of intentional or unexpected recording is a problem.
In order to easily identify such alterations, it is possible to recolor the drawn lines after writing, but since the color temperature for recurrence is generally set to less than 0 ° C, a separate cooling device is required and simplified. It cannot be determined.
　一方、熱変色性色材と光変色性色材を併用した筆記具用水性インク組成物としては、例えば、１）有機フォトクロミック材料を含有する光変色性顔料と、剪断減粘性付与剤と、水とを少なくとも含有し、光変色性顔料の他に、更に、二酸化チタンなどの白色顔料、蛍光顔料、蓄光性顔料、熱変色性顔料、光輝性顔料が配合できる経時安定性に優れたボールペン用水性フォトクロミックインク組成物（例えば、特許文献１参照）、２）特定の可逆熱変色性材料、フォトクロミック有機材料、染料、蛍光顔料から選ばれる着色剤を含むインクを透明性インク収容管に収容し、前記インク収容管先端に直接又は中継部材を介して筆記先端部を固着してなるレフィルを透明性軸筒内に収容してなる筆記具であって、前記軸筒などに紫外線吸収剤などを含有せしめたインクの耐光性を向上させた筆記具（例えば、特許文献２参照）、３）ジアリールエテン系フォトクロミック化合物と、特定の可逆熱変光変色性と熱変色性の色性組成物を共に内包したマイクロカプセル顔料を含んでなる変色性材料、該変色性材料とビヒクルとからなる変色性液状組成物（例えば、特許文献３参照）などが知られている。 On the other hand, as a water-based ink composition for a writing instrument using a thermochromic color material and a photochromic color material in combination, for example, 1) a photochromic pigment containing an organic photochromic material, a shear thinning agent, water, In addition to photochromic pigments, water-based photochromics for ballpoint pens with excellent temporal stability that can contain white pigments such as titanium dioxide, fluorescent pigments, phosphorescent pigments, thermochromic pigments, and glitter pigments. Ink composition (see, for example, Patent Document 1) 2) An ink containing a colorant selected from a specific reversible thermochromic material, a photochromic organic material, a dye, and a fluorescent pigment is contained in a transparent ink containing tube, and the ink A writing instrument in which a refill formed by adhering a writing tip part directly to a receiving tube tip or via a relay member is contained in a transparent shaft cylinder, and an ultraviolet absorber or the like is provided in the shaft cylinder or the like. Writing instrument with improved light resistance of ink contained (for example, see Patent Document 2), 3) A diarylethene photochromic compound and a specific reversible thermochromic and thermochromic color composition are included. A color-changing material comprising a microcapsule pigment, a color-changing liquid composition comprising the color-changing material and a vehicle (see, for example, Patent Document 3) are known.
　しかしながら、上記特許文献１、２の筆記具用水性インク組成物などは、熱変色性色材と光変色性色材を単に併用が可能となるものであり、各文献には実施例のサポートはなく、また、これらを併用した場合には、流動性などの低下によりインクの粘度が上がりやすくなるなどの課題があり、更に、発明の目的なども経時安定性やインクの耐光性の向上であり、本発明の熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を簡易に判別できる筆記具用水性ンク組成物とはその発明の課題や目的が全く異なるものである。
　上記特許文献３は、本発明の近接技術を開示するものであるが、ジアリールエテン系フォトクロミック化合物と、特定の可逆熱変色性組成物を共に内包した二成分が内包されたマイクロカプセル顔料を使用するものであるので、光変色性と熱変色性の各機能を一定以上の品質に維持することが難しく、また、経時的に光変色性と熱変色性の各機能の一方、または両方が低下したりする課題があり、更なる改善等の余地があるのが現状であった。 However, the water-based ink compositions for writing instruments of Patent Documents 1 and 2 described above can be used in combination with a thermochromic color material and a photochromic color material, and there is no support for the examples in each document. In addition, when these are used in combination, there is a problem that the viscosity of the ink tends to increase due to a decrease in fluidity and the like, and the object of the invention is to improve the stability over time and the light resistance of the ink, The subject and the object of the invention are completely different from the aqueous ink composition for writing instruments, which can easily discriminate problems such as intentional or unexpected writing lines and falsification of recording due to the thermochromic coloring material of the present invention.
Patent Document 3 discloses the proximity technique of the present invention, but uses a microcapsule pigment containing a diarylethene-based photochromic compound and a two-component encapsulating a specific reversible thermochromic composition. Therefore, it is difficult to maintain the photochromic and thermochromic functions at a certain level of quality, and one or both of the photochromic and thermochromic functions may deteriorate over time. The current situation is that there is room for further improvement.
特開２００５－３１４６５９号公報（特許請求の範囲、段落００１６等）JP 2005-314659 A (claims, paragraph 0016, etc.) 特開２００６－１０３２１２号公報（特許請求の範囲等）JP-A-2006-103212 (Claims etc.) 特開２００７－６３４３３号公報（特許請求の範囲、実施例等）JP 2007-63433 A (claims, examples, etc.)
　本発明は、上記従来技術の課題及び現状に鑑み、これを解消しようとするものであり、
経時安定性、筆記性能を損なうことなく、熱変色性色材と光変色性色材の各機能を高度に両立せしめて熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を簡易に判別できる筆記具用水性インク組成物を提供することを目的とする。 The present invention is to solve this problem in view of the problems and current state of the prior art,
Falsify intentional or unexpected writing lines and recordings with thermochromic coloring materials by making the functions of thermochromic coloring materials and photochromic coloring materials highly compatible without compromising aging stability and writing performance. It is an object of the present invention to provide a water-based ink composition for a writing instrument that can easily determine the above problem.
　本発明者らは、上記従来の課題等に鑑み、鋭意研究を行った結果、熱変色性色材として熱変色性マイクロカプセル顔料を用いると共に、光変色性色材として、室内照明環境において無色であり、紫外線照射環境で発色する性質を有する光変色性マイクロカプセル顔料とを少なくとも含有せしめ、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径を、共に特定の範囲とし、両者の平均粒子径の差を特定することにより、上記目的の筆記具用水性インク組成物が得られることを見出し、本発明を完成するに至ったのである。 As a result of diligent research in view of the above-described conventional problems, the present inventors have used a thermochromic microcapsule pigment as a thermochromic color material, and are colorless in an indoor lighting environment as a photochromic color material. Yes, it contains at least a photochromic microcapsule pigment having a property of developing in an ultraviolet irradiation environment, and the average particle diameter of the thermochromic microcapsule pigment and the photochromic microcapsule pigment is both within a specific range, By identifying the difference between the average particle diameters of the two, it was found that the above-mentioned aqueous ink composition for writing instruments can be obtained, and the present invention has been completed.
　すなわち、本発明は、次の（１）及び（２）に存する。
（１）　熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを少なくとも含有し、光変色性マイクロカプセル顔料は室内照明環境において無色であり、紫外線照射環境で発色する性質を有し、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径が、共に０．２～３μｍであり、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有することを特徴とする筆記具用水性インク組成物。
（２）　上記（１）に記載の筆記具用水性インク組成物を搭載したことを特徴とする筆記具。 That is, the present invention resides in the following (1) and (2).
(1) It contains at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and has a property of coloring in an ultraviolet irradiation environment, The average particle size of both the thermochromic microcapsule pigment and the photochromic microcapsule pigment is 0.2 to 3 μm, and the average particle size of both is 50% or more of the average particle with respect to the large average particle size A water-based ink composition for a writing instrument having a diameter.
(2) A writing instrument comprising the aqueous ink composition for a writing instrument described in (1) above.
　本発明によれば、経時安定性、筆記性能を損なうことなく、熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を簡易に判別できる筆記具用水性インク組成物が提供される。 According to the present invention, there is provided an aqueous ink composition for a writing instrument that can easily determine problems such as intentional or unexpected writing lines and falsification of recording due to a thermochromic color material without impairing stability over time and writing performance. Provided.
　以下に、本発明の実施形態を詳しく説明する。
　本発明の筆記具用水性ンク組成物は、熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを少なくとも含有し、光変色性マイクロカプセル顔料は室内照明環境において無色であり、紫外線照射環境で発色する性質を有し、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径が、共に０．２～３μｍであり、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有することを特徴とするものである。 Hereinafter, embodiments of the present invention will be described in detail.
The aqueous ink composition for a writing instrument of the present invention contains at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and is used in an ultraviolet irradiation environment. Both of the thermochromic microcapsule pigment and the photochromic microcapsule pigment have an average particle size of 0.2 to 3 μm, and the average particle size of both is a particle having a large average particle size. On the other hand, it has an average particle diameter of 50% or more.
〈熱変色性マイクロカプセル顔料〉
　本発明に用いる熱変色性色材となる熱変色性マイクロカプセル顔料としては、摩擦熱等の熱により変色するもの、例えば、有色から無色、有色から有色、無色から有色などとなる機能を有するものであれば、特に限定されず、種々のものを用いることができ、少なくともロイコ色素、顕色剤、変色温度調整剤を含む熱変色性組成物を、マイクロカプセル化したものが挙げられる。 <Thermochromic microcapsule pigment>
The thermochromic microcapsule pigment used as the thermochromic color material used in the present invention is one that changes color by heat such as frictional heat, for example, a function that changes from colored to colorless, colored to colored, colorless to colored, etc. If it is, it will not specifically limit, A various thing can be used, What microencapsulated the thermochromic composition containing a leuco dye, a color developer, and a color-change temperature regulator at least.
　用いることができるロイコ色素としては、電子供与性染料で、発色剤としての機能するものであれば、特に限定されものではない。具体的には、発色特性に優れるインクを得る点から、トリフェニルメタン系、スピロピラン系、フルオラン系、ジフェニルメタン系、ローダミンラクタム系、インドリルフタリド系、ロイコオーラミン系等従来公知のものが、単独（１種）で又は２種以上を混合して（以下、単に「少なくとも１種」という）用いることができる。
　具体的には、６－（ジメチルアミノ）－３，３－ビス[４－（ジメチルアミノ）フェニル]－１（３Ｈ）－イソベンゾフラノン、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、３－（４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド、１，３－ジメチル－６－ジエチルアミノフルオラン、２－クロロ－３－メチル－６－ジメチルアミノフルオラン、３－ジブチルアミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－メチル－７－キシリジノフルオラン、２－（２－クロロアニリノ）－６－ジブチルアミノフルオラン、３，６－ジメトキシフルオラン、３，６－ジ－ｎ－ブトキシフルオラン、１，２－ベンツ－６－ジエチルアミノフルオラン、１，２－ベンツ－６－ジブチルアミノフルオラン、１，２－ベンツ－６－エチルイソアミルアミノフルオラン、２－メチル－６－（Ｎ－ｐ－トリル－Ｎ－エチルアミノ）フルオラン、２－（Ｎ－フェニル－Ｎ-－メチルアミノ）－６－（Ｎ－ｐ－トリル－Ｎ－エチルアミノ）フルオラン、２－（３'－トリフルオロメチルアニリノ）－６－ジエチルアミノフルオラン、３－クロロ－６－シクロヘキシルアミノフルオラン、２－メチル－６－シクロヘキシルアミノフルオラン、３－ジ（ｎ－ブチル）アミノ－６－メトキシ－７－アニリノフルオラン、３，６－ビス（ジフェニルアミノ）フルオラン、メチル－３'，６'－ビスジフェニルアミノフルオラン、クロロ－３'，６'－ビスジフェニルアミノフルオラン、３－メトキシ－４－ドデコキシスチリノキノリン、などが挙げられ、これらは、少なくとも１種用いることができる。
　これらのロイコ染料は、ラクトン骨格、ピリジン骨格、キナゾリン骨格、ビスキナゾリン骨格等を有するものであり、これらの骨格（環）が開環することで発色を発現するものである。
　好ましくは、熱により有色から無色となるロイコ色素の使用が望ましい。 The leuco dye that can be used is not particularly limited as long as it is an electron donating dye and functions as a color former. Specifically, from the viewpoint of obtaining an ink having excellent color development characteristics, conventionally known ones such as triphenylmethane, spiropyran, fluoran, diphenylmethane, rhodamine lactam, indolylphthalide, leucooramine, It can be used alone (one kind) or in a mixture of two or more kinds (hereinafter simply referred to as “at least one kind”).
Specifically, 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone, 3,3-bis (p-dimethylaminophenyl) -6 -Dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1 -Ethyl-2-methylindol-3-yl) -4-azaphthalide, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6 -Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluor Lan, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 1,2-benz-6-diethylaminofluorane, , 2-Benz-6-dibutylaminofluorane, 1,2-benz-6-ethylisoamylaminofluorane, 2-methyl-6- (Np-tolyl-N-ethylamino) fluorane, 2- (N -Phenyl-N-methylamino) -6- (Np-tolyl-N-ethylamino) fluorane, 2- (3'-trifluoromethylanilino) -6-diethylaminofluorane, 3-chloro-6 -Cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-di (n-butyl) amino-6-methoxy-7-anilinofluorane, , 6-bis (diphenylamino) fluorane, methyl-3 ′, 6′-bisdiphenylaminofluorane, chloro-3 ′, 6′-bisdiphenylaminofluorane, 3-methoxy-4-dodecoxystylinoquinoline These can be used, and at least one of them can be used.
These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, etc., and develop color when these skeletons (rings) are opened.
It is preferable to use a leuco dye that changes from colored to colorless by heat.
　用いることができる顕色剤は、上記ロイコ色素を発色させる能力を有する成分となるものであり、例えば、フェノール樹脂系化合物、サリチル酸系金属塩化物、サリチル酸樹脂系金属塩化合物、固体酸系化合物等が挙げられる。
　用いることができる顕色剤としては、具体的には、ｏ－クレゾール、ターシャリーブチルカテコール、ノニルフェノール、ｎ－オクチルフェノール、ｎ－ドデシルフェノール、ｎ－ステアリルフェノール、ｐ－クロロフェノール、ｐ－ブロモフェノール、ｏ－フェニルフェノール、ヘキサフルオロビスフェノール、ｐ－ヒドロキシ安息香酸ｎ－ブチル、ｐ－ヒドロキシ安息香酸ｎ－オクチル、レゾルシン、没食子酸ドデシル、２，２－ビス（４'－ヒドロキシフェニル）プロパン、４，４－ジヒドロキシジフェニルスルホン、１，１－ビス（４'－ヒドロキシフェニル）エタン、２，２－ビス（４'－ヒドロキシ－３－メチルフェニル）プロパン、ビス（４－ヒドロキシフェニル）スルフィド、１－フェニル－１，１－ビス（ ４'－ヒドロキシフェニル）エタン、１，１－ビス（４'－ヒドロキシフェニル）－３－メチルブタン、１，１－ビス（４'－ヒドロキシフェニル）－２－メチルプロパン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－ヘキサン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－ヘプタン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－オクタン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－ノナン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－デカン、１，１－ビス（４'－ヒドロキシフェニル）ｎ－ドデカン、２，２－ビス（４'－ヒドロキシフェニル）ブタン、２，２－ビス（４'－ヒドロキシフェニル）エチルプロピオネート、２，２－ビス（４'－ヒドロキシフェニル）－４－メチルペンタン、２，２－ビス（４'－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４'－ヒドロキシフェニル）ｎ－ヘプタン、２，２－ビス（４'－ヒドロキシフェニル）ｎ－ノナンなどの少なくとも１種が挙げられる。 The developer that can be used is a component having the ability to develop the leuco dye, such as a phenol resin compound, a salicylic acid metal chloride, a salicylic acid resin metal salt compound, a solid acid compound, etc. Is mentioned.
Specific examples of the developer that can be used include o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, hexafluorobisphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4′-hydroxyphenyl) propane, 4,4 -Dihydroxydiphenylsulfone, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl- 1,1-bis (4'-hydroxyl Nyl) ethane, 1,1-bis (4′-hydroxyphenyl) -3-methylbutane, 1,1-bis (4′-hydroxyphenyl) -2-methylpropane, 1,1-bis (4′-hydroxyphenyl) ) N-hexane, 1,1-bis (4′-hydroxyphenyl) n-heptane, 1,1-bis (4′-hydroxyphenyl) n-octane, 1,1-bis (4′-hydroxyphenyl) n -Nonane, 1,1-bis (4'-hydroxyphenyl) n-decane, 1,1-bis (4'-hydroxyphenyl) n-dodecane, 2,2-bis (4'-hydroxyphenyl) butane, , 2-bis (4′-hydroxyphenyl) ethyl propionate, 2,2-bis (4′-hydroxyphenyl) -4-methylpentane, 2,2-bis (4′-hydroxyphenyl) hexafluoro Examples thereof include at least one of propane, 2,2-bis (4′-hydroxyphenyl) n-heptane, 2,2-bis (4′-hydroxyphenyl) n-nonane, and the like.
　用いる顕色剤の使用量は、所望される色彩濃度に応じて任意に選択すればよく、特に限定されるものではないが、通常、前記したロイコ色素１質量部に対して、０．１～１００質量部程度の範囲内で選択するのが好適である。 The amount of the developer to be used may be arbitrarily selected according to the desired color density and is not particularly limited, but is usually 0.1 to 1 part by weight with respect to 1 part by mass of the leuco dye. It is preferable to select within a range of about 100 parts by mass.
　用いることができる変色温度調整剤は、前記ロイコ色素と顕色剤の呈色において変色温度をコントロールする物質である。
　用いることができる変色温度調整剤は、従来公知のものが使用可能である。具体的には、アルコール類、エステル類、ケトン類、エーテル類、酸アミド類、アゾメチン類、脂肪酸類、炭化水素類などが挙げられる。
　例えば、ビス（４－ヒドロキシフェニル）フェニルメタンジカプリレート（Ｃ７Ｈ１５）、ビス（４－ヒドロキシフェニル）フェニルメタンジラウレート（Ｃ１１Ｈ２３）、ビス（４－ヒドロキシフェニル）フェニルメタンジミリステート（Ｃ１３Ｈ２７）、ビス（４－ヒドロキシフェニル）フェニルエタンジミリステート（Ｃ１３Ｈ２７）、ビス（４－ヒドロキシフェニル）フェニルメタンジパルミテート（Ｃ１５Ｈ３０）、ビス（４－ヒドロキシフェニル）フェニルメタンジベヘネート（Ｃ２１Ｈ４３）、ビス（４－ヒドロキシフェニル）フェニルエチルヘキシリデンジミリステート（Ｃ１３Ｈ２７）等の少なくとも１種が挙げられる。 The color change temperature adjusting agent that can be used is a substance that controls the color change temperature in the coloration of the leuco dye and the developer.
Conventionally known color change temperature adjusting agents can be used. Specific examples include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.
For example, bis (4-hydroxyphenyl) phenylmethane dicaprylate (C 7 H 15 ), bis (4-hydroxyphenyl) phenylmethane dilaurate (C 11 H 23 ), bis (4-hydroxyphenyl) phenylmethane dimyristate (C 13 H 27 ), bis (4-hydroxyphenyl) phenylethane dimyristate (C 13 H 27 ), bis (4-hydroxyphenyl) phenylmethane dipalmitate (C 15 H 30 ), bis (4-hydroxy And at least one of phenyl) phenylmethane dibehenate (C 21 H 43 ), bis (4-hydroxyphenyl) phenylethylhexylidene dimyristate (C 13 H 27 ), and the like.
　この変色温度調整剤の使用量は、所望されるヒステリシス幅及び発色時の色彩濃度等に応じて適宜選択すればよく、特に限定されるものではないが、通常、ロイコ色素１質量部に対して、１～１００質量部程度の範囲内で使用するのが好ましい。 The amount of the color-change temperature adjusting agent used may be appropriately selected according to the desired hysteresis width and color density at the time of color development, and is not particularly limited, but is usually based on 1 part by mass of the leuco dye. It is preferably used within the range of about 1 to 100 parts by mass.
　本発明の熱変色性マイクロカプセル顔料は、少なくとも上記ロイコ色素、顕色剤、変色温度調整剤を含む熱変色性組成物を、平均粒子径が０．２～３μｍとなるように、マイクロカプセル化することにより製造することができる。
　マイクロカプセル化法としては、例えば、界面重合法、界面重縮合法、ｉｎｓｉｔｕ重合法、液中硬化被覆法、水溶液からの相分離法、有機溶媒からの相分離法、融解分散冷却法、気中懸濁被覆法、スプレードライニング法などを挙げることができ、用途に応じて適宜選択することができる。 The thermochromic microcapsule pigment of the present invention is obtained by microencapsulating a thermochromic composition containing at least the leuco dye, the developer, and the color change temperature adjusting agent so that the average particle diameter is 0.2 to 3 μm. Can be manufactured.
Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.
　例えば、水溶液からの相分離法では、ロイコ色素、顕色剤、変色温度調整剤を加熱溶融後、乳化剤溶液に投入し、加熱攪拌して油滴状に分散させ、次いで、カプセル膜剤として、樹脂原料などを使用、例えば、アミノ樹脂溶液、具体的には、メチロールメラミン水溶液、尿素溶液、ベンゾグアナミン溶液などの各液を徐々に投入し、引き続き反応させて調製後、この分散液を濾過することにより目的の熱変色性のマイクロカプセル顔料を製造することができる。 For example, in a phase separation method from an aqueous solution, a leuco dye, a developer, and a color change temperature adjusting agent are heated and melted, then charged into an emulsifier solution, heated and stirred to disperse into oil droplets, and then as a capsule film agent, Use resin raw materials, for example, amino resin solution, specifically, each solution such as methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc., gradually add and continue to react, then filter this dispersion Thus, the desired thermochromic microcapsule pigment can be produced.
　これらのロイコ色素、顕色剤、変色温度調整剤の含有量は、用いるロイコ色素、顕色剤、変色温度調整剤の種類、マイクロカプセル化法などにより変動するが、当該色素１に対して、質量比で顕色剤０．１～１００、変色温度調整剤１～１００である。また、カプセル膜剤は、カプセル内容物に対して、質量比で０．１～１である。
　本発明に用いる熱変色性マイクロカプセル顔料は、上記ロイコ色素、顕色剤及び変色温度調整剤の種類、量などを好適に組み合わせることにより、各色の発色温度（例えば、０℃以上で発色）、消色温度（例えば、５０℃以上で消色）を好適な温度に設定することができ、好ましくは、摩擦熱等の熱により有色から無色となる熱変色性マイクロカプセル顔料の使用が望ましい。 The content of these leuco dyes, developer, and color change temperature adjusting agent varies depending on the type of leuco dye, developer, color change temperature adjusting agent used, microencapsulation method, etc. In terms of mass ratio, the developer is 0.1 to 100, and the color change temperature adjusting agent is 1 to 100. The capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.
The thermochromic microcapsule pigment used in the present invention is a color combination temperature of each color (for example, color development at 0 ° C. or higher) by suitably combining the types, amounts, and the like of the leuco dye, the developer and the color change temperature adjusting agent, The decoloring temperature (for example, decoloring at 50 ° C. or higher) can be set to a suitable temperature, and it is preferable to use a thermochromic microcapsule pigment that changes from colored to colorless by heat such as frictional heat.
　本発明に用いる熱変色性マイクロカプセル顔料では、描線濃度、保存安定性、筆記性の更なる向上の点から、壁膜がウレタン樹脂、エポキシ樹脂、あるいはアミノ樹脂で形成されることが好ましい。ウレタン樹脂としては、例えば、イソシアネートとポリオールとの化合物が挙げられる。エポキシ樹脂としては、例えば、エポキシ樹脂とアミンの化合物が挙げられる。アミノ樹脂としては、例えば、メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂などで形成されること、更に好ましくは、製造性、保存安定性、筆記性の点から、メラミン樹脂で形成されることが望ましい。
　マイクロカプセル色材の壁膜の厚さは、必要とする壁膜の強度や描線濃度に応じて適宜決められる。
　なお、壁膜がアミノ樹脂で形成するためには、各マイクロカプセル化法を用いる際に、好適なアミノ樹脂原料（メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂等）、並びに、分散剤、保護コロイドなどを選択する。 In the thermochromic microcapsule pigment used in the present invention, the wall film is preferably formed of a urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the drawing density, storage stability, and writing property. As a urethane resin, the compound of isocyanate and a polyol is mentioned, for example. As an epoxy resin, the compound of an epoxy resin and an amine is mentioned, for example. The amino resin is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, and more preferably formed of a melamine resin from the viewpoints of manufacturability, storage stability, and writing properties.
The thickness of the wall film of the microcapsule coloring material is appropriately determined according to the required strength of the wall film and the drawn line density.
In order to form the wall film with an amino resin, when using each microencapsulation method, a suitable amino resin raw material (melamine resin, urea resin, benzoguanamine resin, etc.), a dispersant, a protective colloid, etc. select.
　本発明に用いる熱変色性マイクロカプセル顔料の平均粒子径は、着色性、発色性、易消色性、安定性、インク中での流動性の点、並びに、筆記性への悪影響を抑制、後述する光変色性マイクロカプセル顔料との相用性などの点から、好ましくは、０．２～３μｍ、更に好ましくは、０．２～２．３μｍであるものが望ましい。なお、本発明（実施例等含む）で規定する「平均粒子径」は、粒度分析計〔マイクロトラックＨＲＡ９３２０－Ｘ１００（日機装社製）〕にて、平均粒子径を測定した値である。
　この平均粒子径が０．２μｍ未満であると、十分な描線濃度が得られず、一方、３μｍを越えると、筆記性の劣化や熱変色性マイクロカプセル顔料の分散安定性の低下が発生し、好ましくない。
　なお、上記平均粒子径の範囲（０．２～３μｍ）となるマイクロカプセル顔料は、マイクロカプセル化法により変動するが、水溶液からの相分離法などでは、マイクロカプセル顔料を製造する際の攪拌条件を好適に組み合わせることにより調製することができる。 The average particle size of the thermochromic microcapsule pigment used in the present invention suppresses adverse effects on colorability, color developability, easy decolorization, stability, fluidity in ink, and writing properties, as described below. From the viewpoint of compatibility with the photochromic microcapsule pigment, it is preferably 0.2 to 3 μm, more preferably 0.2 to 2.3 μm. The “average particle size” defined in the present invention (including examples and the like) is a value obtained by measuring the average particle size with a particle size analyzer [Microtrac HRA9320-X100 (Nikkiso Co., Ltd.)].
If the average particle size is less than 0.2 μm, sufficient line density cannot be obtained, while if it exceeds 3 μm, the writing property is deteriorated and the dispersion stability of the thermochromic microcapsule pigment is reduced. It is not preferable.
The microcapsule pigment in the above average particle size range (0.2 to 3 μm) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution, the stirring conditions for producing the microcapsule pigment Can be prepared by suitably combining them.
〈光変色性マイクロカプセル顔料〉
　本発明に用いる光変色性色材となる光変色性マイクロカプセル顔料としては、室内照明環境において無色であり、紫外線照射環境で発色する性質を有するものであれば、特に限定されず、種々のものを用いることができ、例えば、光変色性色素となり、上記特性を有するフォトクロミック色素（化合物）、蛍光色素を、マイクロカプセル化したものが挙げられる。
　本発明において、「室内照明環境」としては、例えば、部屋などの室内での白熱灯、蛍光灯、ランプ、白色ＬＥＤなどから選ばれる照明器具によるものであり、「紫外線照射環境」としては、紫外線（２００～４００ｎｍ波長）の照射、例えば、ブラックライトによる照射環境、紫外線を含む太陽光での照射環境などが挙げられる。 <Photochromic microcapsule pigment>
The photochromic microcapsule pigment used as the photochromic color material for use in the present invention is not particularly limited as long as it is colorless in an indoor lighting environment and has a property of coloring in an ultraviolet irradiation environment. For example, a photochromic dye (compound) having the above characteristics and a microencapsulated fluorescent dye can be used.
In the present invention, the “indoor lighting environment” is, for example, a lighting fixture selected from an incandescent lamp, a fluorescent lamp, a lamp, a white LED, etc. in a room, and the “ultraviolet irradiation environment” Irradiation (with a wavelength of 200 to 400 nm), for example, an irradiation environment with black light, an irradiation environment with sunlight including ultraviolet rays, and the like.
　用いることができるフォトクロミック色素（化合物）としては、例えば、２，３－ビス（２，４，５－トリメチル－３－チエニル）マレイン酸無水物、２，３－ビス（２，４，５－トリメチル－３－チエニル）マレイミド、ｃｉｓ－１，２－ジシアノ－１，２－ビス（２，４，５－トリメチル－３－チエニル）エテン、１，２－ビス［２－メチルベンゾ［ｂ］チオフェン－３－イル］－３，３，４，４，５，５－ヘキサフルオロ－１－シクロペンテン、１，２－ビス（２，４－ジメチル－５－フェニル－３－チエニル）－３，３，４，４，５，５－ヘキサフルオロ－１－シクロペンテン、１－（２－ヒドロキシエチル）－３，３－ジメチルインドリノ－６'－ニトロベンゾピリロスピラン、１，３，３－トリメチルインドリノベンゾピリロスピラン、１，３，３－トリメチルインドリノ－６'－ニトロベンゾピリロスピラン、１，３，３－トリメチルインドリノ－６'－ブロモベンゾピリロスピラン、１，３，３－トリメチルインドリノ－８'－メトキシベンゾピリロスピラン、１，３，３－トリメチルインドリノ－β－ナフトピリロスピラン、１，３，３－トリメチルインドリノナフトスピロオキサジン、２，３－ジヒドロ－２－スピロ－４'－［８'－アミノナフタレン－１'（４'Ｈ）－オン］ペリミジン（ｏ－体含む）、２，３－ジヒドロ－２－スピロ－７'－［８'－イミノ－７'，８'－ジヒドロナフタレン－１'－アミン］ペリミジン、アゾベンゼン、３，３－ジフェニル－３Ｈ－ナフト［２，１－ｂ］ピラン、２，５－ノルボルナジエン、チオインジゴなどの少なくとも１種が挙げられる。 Examples of photochromic dyes (compounds) that can be used include 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride and 2,3-bis (2,4,5-trimethyl). -3-thienyl) maleimide, cis-1,2-dicyano-1,2-bis (2,4,5-trimethyl-3-thienyl) ethene, 1,2-bis [2-methylbenzo [b] thiophene-3 -Yl] -3,3,4,4,5,5-hexafluoro-1-cyclopentene, 1,2-bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4, 4,5,5-hexafluoro-1-cyclopentene, 1- (2-hydroxyethyl) -3,3-dimethylindolino-6'-nitrobenzopyrospirane, 1,3,3-trimethylindolinobenzopyri Loss Pyran, 1,3,3-trimethylindolino-6'-nitrobenzopyrospirane, 1,3,3-trimethylindolino-6'-bromobenzopyrispirane, 1,3,3-trimethylindolino- 8'-methoxybenzopyrospirane, 1,3,3-trimethylindolino-β-naphthopyrilospirane, 1,3,3-trimethylindolinonaphthospiroxazine, 2,3-dihydro-2-spiro-4 '-[8'-Aminonaphthalene-1' (4'H) -one] perimidine (including o-isomer), 2,3-dihydro-2-spiro-7 '-[8'-imino-7', 8 At least one of '-dihydronaphthalene-1'-amine] perimidine, azobenzene, 3,3-diphenyl-3H-naphtho [2,1-b] pyran, 2,5-norbornadiene, thioindigo and the like It is.
　用いることができる光変色性となる蛍光色素としては、例えば、アリールアミン誘導体、フェニルアントラセン誘導体などのアントラセン誘導体、ペンタセン誘導体、オキサジアゾール誘導体、オキサゾール誘導体、トリアゾール誘導体、ベンゾオキサゾール誘導体、ベンゾアザトリアゾール誘導体などのアゾール誘導体、オリゴチオフェン誘導体などのチオフェン誘導体、カルバゾール誘導体、シクロペンタジエン誘導体、テトラフェニルブタジエン誘導体などのジエン誘導体、ジスチリルベンゼン誘導体、ジスチリルピラゾン誘導体、ジスチリルアリーレン誘導体、スチルベン誘導体、トリフェニルアミン誘導体、トリフマニルアミン誘導体、ピラゾロキノリン誘導体、ヒドラゾン誘導体、ピラゾール誘導体、ピラゾリン誘導体、ピリジン誘導体、ポルフィリン誘導体、フタロシアニン誘導体などのピロール誘導体、フルオレン誘導体、フェナントロリン誘導体、ピレン誘導体、フェナントレン誘導体、ペリノン誘導体、クマリン誘導体、ナフタルイミド誘導体、ベンゾオキサジノン誘導体、キノフタロン誘導体、ルブレン誘導体、キナドリン誘導体などの少なくとも１種が挙げられる。
　本発明では、上記フォトクロミック色素（化合物）、蛍光色素などから選択される１種以上を好適に用いることができ、市販品があれば、それを使用してもよいものである。 Examples of photochromic fluorescent dyes that can be used include anthracene derivatives such as arylamine derivatives and phenylanthracene derivatives, pentacene derivatives, oxadiazole derivatives, oxazole derivatives, triazole derivatives, benzoxazole derivatives, and benzoazatriazole derivatives. Such as azole derivatives, thiophene derivatives such as oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, diene derivatives such as tetraphenylbutadiene derivatives, distyrylbenzene derivatives, distyrylpyrazone derivatives, distyrylarylene derivatives, stilbene derivatives, triphenyl Amine derivatives, trifumanylamine derivatives, pyrazoloquinoline derivatives, hydrazone derivatives, pyrazole derivatives, pyrazoline derivatives, pyridi Derivatives, porphyrin derivatives, pyrrole derivatives such as phthalocyanine derivatives, fluorene derivatives, phenanthroline derivatives, pyrene derivatives, phenanthrene derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, benzoxazinone derivatives, quinophthalone derivatives, rubrene derivatives, quinadrine derivatives, etc. One type is mentioned.
In this invention, 1 or more types selected from the said photochromic pigment | dye (compound), a fluorescent pigment | dye, etc. can be used conveniently, and if there exists a commercial item, you may use it.
　本発明の光変色性マイクロカプセル顔料は、少なくとも上記フォトクロミック色素（化合物）、蛍光色素などから選択される１種以上と、有機溶媒と、酸化防止剤、光安定剤、増感剤などの添加剤とを含む光変色性組成物を、平均粒子径が０．２～３μｍとなるように、マイクロカプセル化することにより製造することができる。
　マイクロカプセル化法としては、上述の熱変色性マイクロカプセル顔料の製造と同様に調製することができ、例えば、水溶液からの相分離法では、フォトクロミック色素（化合物）などを、ジエチレングリコール、メチルエチルケトン、フェニルグリコールなど有機溶剤などと共に、加熱溶融後、乳化剤溶液に投入し、加熱攪拌して油滴状に分散させ、次いで、カプセル膜剤として、樹脂原料などを使用、例えば、アミノ樹脂溶液、具体的には、メチロールメラミン水溶液、尿素溶液、ベンゾグアナミン溶液などの各液を徐々に投入し、引き続き反応させて調製後、この分散液を濾過することにより目的の室内照明環境において無色であり、紫外線照射環境で発色する性質を有する光変色性のマイクロカプセル顔料を製造することができる。 The photochromic microcapsule pigment of the present invention comprises at least one or more selected from the above-mentioned photochromic dyes (compounds), fluorescent dyes, additives such as organic solvents, antioxidants, light stabilizers, and sensitizers. Can be produced by microencapsulation so that the average particle size is 0.2 to 3 μm.
As the microencapsulation method, it can be prepared in the same manner as the production of the above-mentioned thermochromic microcapsule pigment. For example, in a phase separation method from an aqueous solution, a photochromic dye (compound) or the like is used as diethylene glycol, methyl ethyl ketone, phenyl glycol. After heating and melting together with an organic solvent, etc., it is put into an emulsifier solution, heated and stirred to disperse into oil droplets, and then a resin raw material is used as a capsule film agent, for example, an amino resin solution, specifically Then, gradually add each liquid such as methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc., and continue to react, then by filtering this dispersion, it is colorless in the desired indoor lighting environment, and develops color in the ultraviolet irradiation environment A photochromic microcapsule pigment having the following properties can be produced.
　本発明に用いる光変色性マイクロカプセル顔料の平均粒子径は、室内照明環境における消色性、紫外線照射環境で好適に発色せしめる発色性、インク中での流動性、安定性の点、並びに、筆記性への悪影響を抑制、上述の熱変色性マイクロカプセル顔料との相用性などの点から、好ましくは、熱変色性マイクロカプセル顔料と同様に、０．２～３μｍ、更に好ましくは、０．２～２．３μｍであるものが望ましい。
　この平均粒子径が０．２μｍ未満であると、十分な描線濃度が得られず、一方、３μｍを越えると、筆記性の劣化や光変色性マイクロカプセル顔料の分散安定性の低下が発生し、好ましくない。
　なお、上記平均粒子径の範囲（０．２～３μｍ）となるマイクロカプセル顔料は、マイクロカプセル化法により変動するが、水溶液からの相分離法などでは、マイクロカプセル顔料を製造する際の攪拌条件を好適に組み合わせることにより調製することができる。 The average particle size of the photochromic microcapsule pigment used in the present invention is the color erasability in an indoor lighting environment, the color developability that allows a color to be suitably developed in an ultraviolet irradiation environment, the fluidity in ink, the stability, and the writing From the viewpoints of suppressing adverse effects on the properties and compatibility with the above-described thermochromic microcapsule pigments, it is preferably 0.2 to 3 μm, more preferably 0. A thickness of 2 to 2.3 μm is desirable.
If the average particle diameter is less than 0.2 μm, sufficient line density cannot be obtained, while if it exceeds 3 μm, the writing property is deteriorated and the dispersion stability of the photochromic microcapsule pigment is reduced. It is not preferable.
The microcapsule pigment in the above average particle size range (0.2 to 3 μm) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution, the stirring conditions for producing the microcapsule pigment Can be prepared by suitably combining them.
　本発明では、用いる熱変色性マイクロカプセル顔料と光変色性マイクロカプセル顔料とは、上述の如く、その平均粒子径は共に０．２～３μｍであり、熱変色性マイクロカプセル顔料と光変色性マイクロカプセル顔料の各平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有すること、好ましくは、平均粒子径が大きい粒子に対して７０％以上の平均粒子径を有することが望ましい。
　例えば、熱変色性マイクロカプセル顔料の平均粒子径が大きい場合（２μｍ）であると、光変色性マイクロカプセル顔料の平均粒子径が５０％以上、具体的には１μｍ以上、好ましくは１．４μｍ以上であることを意味し、また、光変色性マイクロカプセル顔料の平均粒子径が大きい場合（例えば１．８μｍ）であると、熱変色性マイクロカプセル顔料の平均粒子径が５０％以上、具体的には０．９μｍ以上、好ましくは１．２６μｍ以上であることを意味するものである。
　この両者の平均粒子径が大きい粒子に対して５０％未満となる平均粒子径を有するものであると、両顔料が密充填状態となりやすく流動性の低下が生じ、インクの粘度が上がりやすくなり、好ましくないものとなる。
　このため、本発明において、用いる熱変色性マイクロカプセル顔料と光変色性マイクロカプセル顔料との平均粒子径は、共に０．２～３μｍの範囲となり、この範囲内の両マイクロカプセル顔料の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径となるものを選択してインク組成物中に含有せしめることにより、本発明の効果を好適に発揮せしめることができるものとなる。 In the present invention, the thermochromic microcapsule pigment and the photochromic microcapsule pigment to be used both have an average particle diameter of 0.2 to 3 μm as described above, and the thermochromic microcapsule pigment and the photochromic microcapsule pigment. Each average particle size of the capsule pigment has an average particle size of 50% or more with respect to particles having a large average particle size, and preferably has an average particle size of 70% or more with respect to particles having a large average particle size. Is desirable.
For example, when the average particle size of the thermochromic microcapsule pigment is large (2 μm), the average particle size of the photochromic microcapsule pigment is 50% or more, specifically 1 μm or more, preferably 1.4 μm or more. In addition, when the average particle size of the photochromic microcapsule pigment is large (for example, 1.8 μm), the average particle size of the thermochromic microcapsule pigment is 50% or more, specifically Means 0.9 μm or more, preferably 1.26 μm or more.
If the average particle size of both of these particles has an average particle size of less than 50% with respect to the large particles, both pigments tend to be in a densely packed state, resulting in a decrease in fluidity and an increase in ink viscosity. This is undesirable.
For this reason, in the present invention, the average particle size of the thermochromic microcapsule pigment and the photochromic microcapsule pigment used are both in the range of 0.2 to 3 μm, and the average particle size of both microcapsule pigments within this range. By selecting a particle having an average particle size of 50% or more with respect to particles having a large average particle size and incorporating it into the ink composition, the effects of the present invention can be suitably exhibited.
＜筆記具用水性インク組成物＞
　本発明の筆記具用水性インク組成物は、上記構成の熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを少なくとも含有し、光変色性マイクロカプセル顔料は室内照明環境において無色であり、紫外線照射環境で発色する性質を有し、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径が、共に０．２～３μｍであり、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径となることを特徴とするものであり、ボールペン、マーキングペン等の筆記具用水性インク組成物として用いることをでき、履歴確認用、偽造防止用、真偽判別用、隠しメッセージ用などとして好適に用いることができる。 <Water-based ink composition for writing instruments>
The water-based ink composition for a writing instrument of the present invention contains at least the thermochromic microcapsule pigment having the above-described configuration and the photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment, and has ultraviolet rays. The thermochromic microcapsule pigment and the photochromic microcapsule pigment both have a property of coloring in an irradiation environment, and both have an average particle size of 0.2 to 3 μm. It has an average particle size of 50% or more with respect to large particles, and can be used as a water-based ink composition for writing instruments such as ballpoint pens and marking pens. It can be suitably used for fake discrimination, hidden messages, and the like.
　本発明の熱変色性マイクロカプセル顔料の含有量は、筆記具用水性インク組成物の用途などにより変動するものであり、一概には設定できるものでないが、例えば、履歴確認用、偽造防止用、真偽判別用では、インク組成物全量に対して、熱変色マイクロカプセル顔料が５～５０質量％、好ましくは、５～３０質量％、光変色マイクロカプセル顔料が０．１～１０質量％、好ましくは、０．５～７質量％とすることが望ましい。また、隠しメッセージ用では、インク組成物全量に対して、熱変色マイクロカプセル顔料が０．１～１０％、好ましくは、０．５～７質量％、光変色マイクロカプセル顔料が、５～５０質量％、好ましくは、５～３０質量％とすることが望ましい。
　これらの上記用途（タイプ）別の各含有量が上記範囲の下限（０．１質量％、５質量％）未満であると、一般的に、着色力、発色性が不十分となることがあり、一方、上記用途（タイプ）別の合計含有量が６０質量％を超えると、一般的に、インクの流動性が悪くなることがある。 The content of the thermochromic microcapsule pigment of the present invention varies depending on the use of the water-based ink composition for writing instruments and cannot be generally set. For example, for history confirmation, forgery prevention, For false discrimination, the thermochromic microcapsule pigment is 5 to 50% by mass, preferably 5 to 30% by mass, and the photochromic microcapsule pigment is 0.1 to 10% by mass, preferably based on the total amount of the ink composition. 0.5 to 7% by mass is desirable. For the hidden message, the thermochromic microcapsule pigment is 0.1 to 10%, preferably 0.5 to 7% by mass, and the photochromic microcapsule pigment is 5 to 50% by mass with respect to the total amount of the ink composition. %, Preferably 5 to 30% by mass.
If the content of each of these uses (types) is less than the lower limit (0.1% by mass, 5% by mass) of the above range, generally coloring power and color developability may be insufficient. On the other hand, if the total content by use (type) exceeds 60% by mass, the fluidity of the ink may generally deteriorate.
　本発明の筆記具用水性インク組成物において、上記熱変色、光変色性マイクロカプセル顔料の他、残部として溶媒である水（水道水、精製水、蒸留水、イオン交換水、純水等）の他、各筆記具用（ボールペン用、マーキングペン用等）の用途に応じて、本発明の効果を損なわない範囲で、水溶性有機溶剤、増粘剤、潤滑剤、防錆剤、防腐剤もしくは防菌剤などを適宜含有することができる。 In the water-based ink composition for a writing instrument of the present invention, in addition to the thermochromic and photochromic microcapsule pigments, the balance is water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.). Depending on the application for each writing instrument (for ballpoint pens, marking pens, etc.), water-soluble organic solvents, thickeners, lubricants, rust preventives, antiseptics or antibacterials are used as long as the effects of the present invention are not impaired. An agent or the like can be appropriately contained.
　用いることができる水溶性有機溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、３－ブチレングリコール、チオジエチレングリコール、グリセリン等のグリコール類や、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、単独或いは混合して使用することができる。 Examples of water-soluble organic solvents that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, ethylene glycol monomethyl ether, and diethylene glycol monomethyl. Ethers can be used alone or in combination.
　用いることができる増粘剤としては、例えば、合成高分子、セルロースおよび多糖類からなる群から選ばれた少なくとも一種が望ましい。具体的には、アラビアガム、トラガカントガム、グアーガム、ローカストビーンガム、アルギン酸、カラギーナン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、ダイユータンガム、デキストラン、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプングリコール酸及びその塩、アルギン酸プロピレングリコールエステル、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、ポリアクリル酸及びその塩、カルボキシビニルポリマー、ポリエチレンオキサイド、酢酸ビニルとポリビニルピロリドンの共重合体、架橋型アクリル酸重合体及びその塩、非架橋型アクリル酸重合体及びその塩、スチレンアクリル酸共重合体及びその塩などが挙げられる。 As the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, celluloses and polysaccharides is desirable. Specifically, gum arabic, gum tragacanth, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, diutane gum, dextran, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch glycolic acid and Its salt, propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid and its salt, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinyl pyrrolidone, cross-linked acrylic acid polymer and its Salt, non-crosslinked acrylic acid polymer and its salt, styrene acrylic acid copolymer and its salt, etc. That.
　潤滑剤としては、顔料の表面処理剤にも用いられる多価アルコールの脂肪酸エステル、糖の高級脂肪酸エステル、ポリオキシアルキレン高級脂肪酸エステル、アルキル燐酸エステルなどのノニオン系や、高級脂肪酸アミドのアルキルスルホン酸塩、アルキルアリルスルホン酸塩などのアニオン系、ポリアルキレングリコールの誘導体やフッ素系界面活性剤、ポリエーテル変性シリコーンなどが挙げられる。また、防錆剤としては、ベンゾトリアゾール、トリルトリアゾール、ジシクロへキシルアンモニウムナイトライト、サポニン類など、防腐剤もしくは防菌剤としては、フェノール、ナトリウムオマジン、安息香酸ナトリウム、ベンズイミダゾール系化合物などが挙げられる。 Lubricants include nonionics such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphates, which are also used in pigment surface treatment agents, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones. In addition, as rust preventives, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc., as antiseptics or fungicides, phenol, sodium omadin, sodium benzoate, benzimidazole compounds, etc. Can be mentioned.
　この筆記具用水性インク組成物を製造するには、従来から知られている方法が採用可能であり、例えば、上記熱変色性、光変色性マイクロカプセル顔料の他、上記水性における各成分を所定量配合し、ホモミキサー、もしくはディスパー等の攪拌機により攪拌混合することによって得られる。更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去してもよい。 In order to produce this water-based ink composition for writing instruments, a conventionally known method can be employed. For example, in addition to the thermochromic and photochromic microcapsule pigments, a predetermined amount of each component in the water is used. It is obtained by mixing and stirring and mixing with a homomixer or a stirrer such as a disper. Furthermore, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
　このように構成される本発明の筆記具用水性インク組成物では、繊維チップ、フェルトチップ、プラスチックチップを筆記先端部に備えたマーキングペン体や、ボールペンチップを筆記先端部に備えたボールペン体に搭載して使用に供される。
　本発明の筆記具用水性インク組成物及び筆記具では、熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを少なくとも含有し、光変色性マイクロカプセル顔料は室内照明環境において無色であり、紫外線照射環境で発色する性質を有し、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径が、共に０．２～３μｍであり、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有するものを含む水性のインクを処方し、このインクを搭載したボールペン体、マーキングペン体などの筆記具にて紙面、書類等に筆記、描画等した場合、経時安定性、筆記性能を損なうことなく、熱変色性色材となる熱変色性マイクロカプセル顔料による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を室内照明環境において無色であり、紫外線照射環境で発色する性質を有する光変色性マイクロカプセル顔料により簡易に判別できるため、履歴確認用、偽造防止用、真偽判別用、隠しメッセージ用などとして好適に用いることができるものとなる。
　上記隠しメッセージ用としては、例えば、送り手側が、隠しメッセージやパスワードなどを書類などの特定箇所に記入後、描線を熱消去させる。受領側が当該特定箇所を紫外線照射等の紫外線照射環境におくことでメッセージが読み取り可能とする使用形態など挙げられる。 The water-based ink composition for a writing instrument of the present invention configured as described above is mounted on a marking pen body having a fiber chip, a felt chip, and a plastic chip at the writing tip, and a ballpoint pen body having a ball pen tip at the writing tip. For use.
The aqueous ink composition for a writing instrument and the writing instrument of the present invention contain at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and is irradiated with ultraviolet rays. It has the property of coloring in the environment, and the average particle size of the thermochromic microcapsule pigment and the photochromic microcapsule pigment is both 0.2 to 3 μm, and the average particle size of both is large. When prescribing water-based inks including those having an average particle diameter of 50% or more to the particles, and writing or drawing on paper, documents, etc. with a writing instrument such as a ballpoint pen or marking pen equipped with this ink Intentional or unexpected writing with thermochromic microcapsule pigments that become thermochromic colorants without compromising aging stability and writing performance For problems such as history confirmation, anti-counterfeiting, and authenticity discrimination, because photochromic microcapsule pigments, which are colorless in indoor lighting environments and have the property of developing colors in an ultraviolet irradiation environment, can be easily identified. It can be suitably used for a hidden message or the like.
For the hidden message, for example, the sender side writes a hidden message, a password, or the like in a specific part such as a document, and then thermally erases the drawn line. Examples include a usage mode in which a message can be read by placing the specific part in an ultraviolet irradiation environment such as ultraviolet irradiation.
　本発明の筆記具用水性インク組成物は、熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを別個の二成分とすることで、それぞれのマイクロカプセルに含まれるロイコ色素、フォトクロミック色素など染料の特性に応じた添加剤を用いることが可能となり、また、更なる個別的に微粒子化も可能となるものである。
　従来の熱変色性色材と光変色色材の二成分内包のマイクロカプセル顔料では、例えば、光変色性マイクロカプセル顔料で有用な酸化防止剤を熱変色性マイクロカプセルに含有せしめると、熱温度特性が変化してしまうため、好ましくない形態となり、一定品質を保つ設計とすることが難しくなり、また、微粒子化も難しくなるものであった。
　これに対して、本発明では、熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料との二成分を必須とした上で、更に、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径を、共に０．２～３μｍとすると共に、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有するものとすることにより、熱変色、光変色の特性に応じた機能を効果的に発揮でき、また、更なる微粒子化も可能となるものであり、より各顔料の色相濃度が高く、経時安定性、筆記性能を損なうことなく、熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を光変色性色材で消去履歴等を簡易に判別できる筆記具用水性ンク組成物が得られるものとなる。 The water-based ink composition for a writing instrument of the present invention comprises a thermochromic microcapsule pigment and a photochromic microcapsule pigment as separate two components, so that a dye such as a leuco dye or a photochromic dye contained in each microcapsule. It is possible to use an additive according to the above characteristics, and it is possible to further individually form fine particles.
In conventional microcapsule pigments with two-component inclusion of thermochromic colorant and photochromic colorant, for example, when thermochromic microcapsules contain an antioxidant useful in photochromic microcapsule pigments, thermal temperature characteristics Therefore, it becomes difficult to make a design that maintains a constant quality, and it is difficult to make fine particles.
On the other hand, in the present invention, the two components of the thermochromic microcapsule pigment and the photochromic microcapsule pigment are essential, and further, the thermochromic microcapsule pigment and the photochromic microcapsule. Both the average particle diameter of the pigment is set to 0.2 to 3 μm, and the average particle diameter of both has an average particle diameter of 50% or more with respect to particles having a large average particle diameter. The function according to the characteristics of photo-discoloration can be effectively exhibited, and further finer particles can be formed.The hue concentration of each pigment is higher, and heat stability is maintained without impairing stability over time and writing performance. An aqueous ink composition for a writing instrument that can easily determine the erasure history or the like with a photochromic color material for problems such as intentional or unexpected writing lines or falsification of recording due to the color-changing color material is obtained.
　次に、実施例及び比較例により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。なお、表１、２中の配合単位は質量部であり、下記処方中の「部」は質量部を意味する。 Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, the compounding unit in Tables 1 and 2 is part by mass, and “part” in the following prescription means part by mass.
〔熱変色性マイクロカプセル顔料の処方〕
　下記表１のＡ－１、Ａ－２及びＡ－７に示される各量となるロイコ色素、顕色剤、及び変色性温度調整剤の組み合わせにて熱変色性マイクロカプセル顔料を得た。
　具体的には、Ａ－１では、ロイコ色素として、メチル－３'，６'－ビスジフェニルアミノフルオラン１部、顕色剤として、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン２部、及び変色性温度調整剤として、ビス（４－ヒドロキシフェニル）フェニルメタンジカプリレート２４部を１００℃に加熱溶融して、均質な組成物２７部を得た。
　上記で得た組成物２７部の均一な熱溶液にカプセル膜剤として、イソシアネート１０部及びポリオール１０部を加えて攪拌混合した。次いで、保護コロイドとして１２％ポリビニルアルコール水溶液６０部を用いて、２５℃で乳化して分散液を調製した。次いで、５％の多価アミン５部を用いて、８０℃で６０分間処理してマイクロカプセルを得た。
　以上の手順により得たマイクロカプセル化した水分散体をスプレードライすることでパウダー状にしてＡ－１の熱変色性マイクロカプセル顔料を製造した。
　上記Ａ－１と同様にして、下記表１のＡ－２及びＡ－７に示される熱変色性マイクロカプセル顔料を製造した。
　得られたＡ－１、Ａ－２及びＡ－７の平均粒子径、明所（２５℃）での色相（発色状態）（５０℃以上で消色）を下記表１に示す。 [Formulation of thermochromic microcapsule pigment]
Thermochromic microcapsule pigments were obtained by combinations of leuco dyes, color developers, and color-changing temperature regulators in the amounts shown in A-1, A-2 and A-7 in Table 1 below.
Specifically, in A-1, 1 part of methyl-3 ′, 6′-bisdiphenylaminofluorane as the leuco dye, 2 parts of 1,1-bis (4-hydroxyphenyl) cyclohexane as the developer, As a color change temperature adjusting agent, 24 parts of bis (4-hydroxyphenyl) phenylmethane dicaprylate was heated and melted to 100 ° C. to obtain 27 parts of a homogeneous composition.
As a capsule film agent, 10 parts of an isocyanate and 10 parts of a polyol were added to a uniform hot solution of 27 parts of the composition obtained above and stirred and mixed. Subsequently, 60 parts of 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Next, using 5 parts of 5% polyvalent amine, treatment was performed at 80 ° C. for 60 minutes to obtain microcapsules.
The microencapsulated aqueous dispersion obtained by the above procedure was spray-dried to prepare a powder of A-1 thermochromic microcapsule pigment.
In the same manner as A-1, the thermochromic microcapsule pigments shown in A-2 and A-7 of Table 1 below were produced.
The average particle diameters of the obtained A-1, A-2, and A-7 and the hue (color development state) (decolored at 50 ° C. or higher) in a bright place (25 ° C.) are shown in Table 1 below.
〔光変色性マイクロカプセル顔料の処方〕
　下記表１のＡ－３～Ａ－６及びＡ－８に示される各量となる光変色性色素（フォトクロミック色素、蛍光色素）及び溶剤の組み合わせにて光変色性マイクロカプセル顔料を得た。
　具体的には、Ａ－３では、光変色性色素として、１，３，３－トリメチルインドリノ－６'－（１－ピペリジニル）スピロナフソザジン３部、ジエチレングリコールジベンゾエート１０部、およびメチルエチルケトン１０部を８０℃に加熱溶融して、均質な組成物２３部を得た。
　上記で得た組成物２３部の均一な熱溶液にカプセル膜剤として、イソシアネート１０部及びポリオール１０部を加えて攪拌混合した。次いで、保護コロイドとして１２％ポリビニルアルコール水溶液６０部を用いて、２５℃で乳化して分散液を調製した。次いで、５％の多価アミン５部を用いて、８０℃で６０分間処理してマイクロカプセルを得た。
　以上の手順により得たマイクロカプセル化した水分散体をスプレードライすることでパウダー状にしてＡ－３の光変色性マイクロカプセル顔料を製造した。
　上記Ａ－３と同様にして、下記表１のＡ－４～Ａ－６及びＡ－８に示される室内照明環境において無色であり、紫外線照射環境で発色する性質を有する各熱変色性マイクロカプセル顔料を製造した。
　得られたＡ－３～Ａ－６及びＡ－８の平均粒子径、紫外線照射環境での色相（発色状態）を下記表１に示す。 [Prescription of photochromic microcapsule pigment]
Photochromic microcapsule pigments were obtained by combining photochromic dyes (photochromic dyes, fluorescent dyes) and solvents in the amounts shown in A-3 to A-6 and A-8 in Table 1 below.
Specifically, in A-3, as a photochromic dye, 3 parts of 1,3,3-trimethylindolino-6 ′-(1-piperidinyl) spironafusozazine, 10 parts of diethylene glycol dibenzoate, and 10 of methyl ethyl ketone The parts were heated and melted to 80 ° C. to obtain 23 parts of a homogeneous composition.
As a capsule film agent, 10 parts of isocyanate and 10 parts of polyol were added to a uniform hot solution of 23 parts of the composition obtained above and stirred and mixed. Subsequently, 60 parts of 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Next, using 5 parts of 5% polyvalent amine, treatment was performed at 80 ° C. for 60 minutes to obtain microcapsules.
The microencapsulated water dispersion obtained by the above procedure was spray-dried to obtain a powder-like A-3 photochromic microcapsule pigment.
In the same manner as A-3 above, each thermochromic microcapsule having the property of being colorless in the indoor lighting environment shown in Table 1 and being colored in the ultraviolet irradiation environment shown in Table 1 below. A pigment was produced.
The average particle diameters of the obtained A-3 to A-6 and A-8 and the hue (color development state) in the ultraviolet irradiation environment are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例１～６及び比較例１～２）
（インクの処方）
　上記製造例で得られた各熱変色性、光変色性マイクロカプセル顔料（Ａ－１～Ａ－８）を用いて下記表２に示す配合処方（全量１００質量％）にしたがって、常法により各水性のボールペン用水性インク組成物を調製した。 (Examples 1 to 6 and Comparative Examples 1 and 2)
(Ink formula)
Each thermochromic and photochromic microcapsule pigment (A-1 to A-8) obtained in the above production example was used in accordance with the formulation shown in Table 2 below (total amount: 100% by mass) according to a conventional method. A water-based aqueous ink composition for ballpoint pens was prepared.
（水性ボールペンの作製）
　上記で得られた各インク組成物を用いて水性ボールペンを作製した。具体的には、ボールペン〔三菱鉛筆株式会社製、商品名：ＵＦ－２０２〕の軸を使用し、内径３．８ｍｍ、長さ９０ｍｍポリプロピレン製インク収容管とステンレス製チップ（超硬合金ボール、ボール径０．５ｍｍ）及び該収容管と該チップを連結する継手からなるリフィールに上記各水性インクを充填し、インク後端に鉱油を主成分とするインク追従体を装填し、水性ボールペンを作製した。
　得られた実施例１～６及び比較例１～２の各水性ボールペンを用いて、下記評価方法で消色性、発色性の評価を行った。
　これらの結果を下記表２に示す。 (Production of water-based ballpoint pen)
A water-based ballpoint pen was produced using each ink composition obtained above. Specifically, using an axis of a ballpoint pen (Mitsubishi Pencil Co., Ltd., trade name: UF-202), an inner diameter of 3.8 mm, a length of 90 mm, a polypropylene ink containing tube, and a stainless tip (a cemented carbide ball, a ball A water ballpoint pen was manufactured by filling each water-based ink with a refill composed of a joint connecting the receiving tube and the tip with a diameter of 0.5 mm) and an ink follower mainly composed of mineral oil at the rear end of the ink. .
Using the obtained water-based ballpoint pens of Examples 1 to 6 and Comparative Examples 1 and 2, the decoloring property and color developability were evaluated by the following evaluation methods.
These results are shown in Table 2 below.
（消色性の評価方法）
　上記ペンを用いて直径約３ｃｍの円をＰＰＣ用紙に筆記後、６５℃において３分間保管した後、蛍光灯、白色ＬＥＤ、および白熱灯の照射下において下記評価基準に基づいて評価した。
　評価基準：
　　　　○：完全に消色した。
　　　　△：消え残りがやや観察された。
　　　　×：はっきりとした消え残りが観察された。 (Evaluation method for decolorization)
A circle having a diameter of about 3 cm was written on PPC paper using the above-mentioned pen, stored at 65 ° C. for 3 minutes, and then evaluated based on the following evaluation criteria under irradiation of a fluorescent lamp, a white LED, and an incandescent lamp.
Evaluation criteria:
○: Completely decolored.
Δ: Disappearance was slightly observed.
X: A clear disappearance was observed.
（発色性の評価方法）
　上記消色性の評価によって消色した用紙を、太陽光およびブラックライト（３１５～４００ｎｍ）にそれぞれ３秒照射後、下記評価基準に基づいて評価した。
　評価基準：
　　　　○：光発色性色素由来の描線が強く認識できる。
　　　　×：光発色性色素由来の描線が認識できない。 (Evaluation method of color development)
The paper erased by the above-described evaluation of decoloring property was irradiated with sunlight and black light (315 to 400 nm) for 3 seconds, respectively, and then evaluated based on the following evaluation criteria.
Evaluation criteria:
○: A drawn line derived from a photochromic dye can be strongly recognized.
X: A drawn line derived from a photochromic dye cannot be recognized.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表１及び表２の結果から明らかなように、本発明となる実施例１～６の筆記具用水性インク組成物は、本発明の範囲外となる比較例１～２の筆記具用水性インク組成物に較べて、満足のいく十分な熱消色性、光発色性となることが判明した。
　比較例１は、熱変色性マイクロカプセル顔料と光変色性マイクロカプセル顔料の平均粒子径が、２μｍと０．１μｍとなるものであり、両者の平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有せず、その差も大きいため、インク流動性が悪く、評価不能（評価「－」）となるものであり、比較例２は、光変色性マイクロカプセル顔料の平均粒子径が本発明の範囲外となるものであるため、光変色性マイクロカプセル顔料の発色性が劣るものであった。
　従って、本発明の筆記具用水性インク組成物は、経時安定性、筆記性能を損なうことなく、熱変色性色材による意図的若しくは予期せぬ筆記描線や記録の改竄などの問題を光変色性色材で消去履歴等を簡易に判別でき、履歴確認用、偽造防止用、真偽判別用、隠しメッセージ用などとして好適となることが確認された。 As is apparent from the results of Tables 1 and 2, the aqueous ink compositions for writing instruments of Examples 1 to 6 according to the present invention are the aqueous ink compositions for writing instruments of Comparative Examples 1 and 2 that are outside the scope of the present invention. It was found that satisfactory thermal decolorization and photochromic properties were obtained compared to the product.
In Comparative Example 1, the average particle diameters of the thermochromic microcapsule pigment and the photochromic microcapsule pigment are 2 μm and 0.1 μm, and 50% or more of the particles having a large average particle diameter of both. Since there is no average particle size and the difference is large, the ink fluidity is poor and the evaluation is impossible (evaluation “−”). In Comparative Example 2, the average particle size of the photochromic microcapsule pigment is Since it falls outside the scope of the present invention, the color developability of the photochromic microcapsule pigment was inferior.
Therefore, the water-based ink composition for a writing instrument according to the present invention eliminates problems such as intentional or unexpected writing lines and falsification of recording due to a thermochromic color material without impairing the temporal stability and writing performance. It was confirmed that erasure history and the like can be easily discriminated by the material, and it is suitable for history confirmation, forgery prevention, authenticity discrimination, hidden message and the like.
　ボールペン、マーキングペンなどの筆記具に好適な筆記具用水性インク組成物となり、履歴確認用、偽造防止用、真偽判別用、隠しメッセージ用などとして用いることができる。 It becomes a water-based ink composition for writing instruments suitable for writing instruments such as ballpoint pens and marking pens, and can be used for history confirmation, forgery prevention, authenticity discrimination, hidden messages and the like.

Claims (2)

  1. 　熱変色性マイクロカプセル顔料と、光変色性マイクロカプセル顔料とを少なくとも含有し、光変色性マイクロカプセル顔料は室内照明環境において無色であり、紫外線照射環境で発色する性質を有し、前記熱変色性マイクロカプセル顔料と前記光変色性マイクロカプセル顔料の平均粒子径が、共に０．２～３μｍであり、両者の平均粒子径は平均粒子径が大きい粒子に対して５０％以上の平均粒子径を有することを特徴とする筆記具用水性インク組成物。 It contains at least a thermochromic microcapsule pigment and a photochromic microcapsule pigment, and the photochromic microcapsule pigment is colorless in an indoor lighting environment and has a property of coloring in an ultraviolet irradiation environment, and the thermochromic property Both the microcapsule pigment and the photochromic microcapsule pigment have an average particle size of 0.2 to 3 μm, and the average particle size of both has an average particle size of 50% or more with respect to the particles having a large average particle size. A water-based ink composition for a writing instrument.
  2. 　請求項１に記載の筆記具用水性ンク組成物を搭載したことを特徴とする筆記具。 A writing instrument comprising the aqueous nunk composition for a writing instrument according to claim 1 mounted thereon.
PCT/JP2015/062664 2014-05-02 2015-04-27 Aqueous ink composition for writing instruments WO2015166901A1 (en)

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