WO2001005907A1 - Composition fluorescente, composition d'encre et matiere imprimee - Google Patents

Composition fluorescente, composition d'encre et matiere imprimee Download PDF

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Publication number
WO2001005907A1
WO2001005907A1 PCT/JP2000/004790 JP0004790W WO0105907A1 WO 2001005907 A1 WO2001005907 A1 WO 2001005907A1 JP 0004790 W JP0004790 W JP 0004790W WO 0105907 A1 WO0105907 A1 WO 0105907A1
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WIPO (PCT)
Prior art keywords
fluorescent dye
organic fluorescent
ink composition
ink
document
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PCT/JP2000/004790
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English (en)
Japanese (ja)
Inventor
Noriaki Fukushima
Yoshinori Yamamoto
Hiroyuki Mitsuhashi
Yukinori Yamada
Tomohisa Nishimoto
Original Assignee
Hitachi Maxell, Ltd.
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Application filed by Hitachi Maxell, Ltd. filed Critical Hitachi Maxell, Ltd.
Priority to AU58539/00A priority Critical patent/AU5853900A/en
Publication of WO2001005907A1 publication Critical patent/WO2001005907A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Definitions

  • the present invention relates to an organic fluorescent dye that emits light having an emission center in the visible light region when excited by ultraviolet light, and in particular, a fluorescent composition containing an organic fluorescent dye that is substantially invisible or difficult to recognize in the visible light region,
  • An ultraviolet-excited ink composition that contains an organic fluorescent dye and is used for printing with a marker pen, dot-impact pudding, stamp-type pudding, ink-jet pudding, etc., and printed matter created using the ink composition And about.
  • Bar code printing includes contact printing and non-contact printing.
  • the contact printing method includes a method using a marker pen and a bar code writer
  • the non-contact printing method includes an ink jet printing method.
  • the ink jet printing method is a method in which an ink composition is injected onto a surface to be printed through a nozzle to perform printing.Since a non-contact printing method is used, a non-uniform shape surface, such as a plastic sheet. Suitable for printing on cardboard surfaces.
  • the ink compositions used in the ink jet printing method include (1) stable without long-term storage without phase separation or sedimentation, (2) passing without clogging nozzles, and (3) ink composition. Good adhesion to the printing surface; (4) the ink composition dries quickly on the printing surface; and (5) the printed matter after drying has excellent adhesion to the printing surface, and (6) weather resistance Sex and durability must be high. Also, Inkjets (7) The ink composition for ink jet printing needs to be charge-controlled so that printing can be controlled by the ink jet printer, which is a characteristic characteristic of the ink composition for ink jetting, which is not required for other ink compositions. Must have.
  • bar code printing including such an ink jet printing method includes (a) a method of printing a bar code such as black on a white background, and (b) a method of being excited by ultraviolet rays of 300 to 400 nm.
  • a method of printing an ink composition containing an organic fluorescent dye that emits blue, green or red visible light has been used or proposed.
  • the information is read using the difference in reflectance between the bar code and the base.
  • the appearance of the article is inevitably deteriorated because the reflectance in the visible light region is used.
  • character information may be printed in blue, black, or the like, which inevitably impairs the appearance of the article.
  • the organic fluorescent dye to be used is inherently easily decomposed, and has poor light resistance and poor weather resistance. There was a problem that it declined. That is, the above-mentioned conventional ink tends to remarkably decrease in luminous intensity when stored at high temperature and high humidity even if it shows high luminous intensity at the beginning of preparation. Therefore, in order to solve such a problem, various additives are added to the ink, or the above-mentioned organic fluorescent dye dissolved on the surface of inorganic particles such as silica or organic fine particles such as acryl is adsorbed. It has been proposed to improve weather resistance.
  • the method of using additives and particles as described above requires storage in the ink state. It was found that, although effective in improving the printability, when the printed material was printed using this ink on a substrate, the luminescence intensity was reduced only by leaving the printed material at room temperature. In other words, even if the printed matter shows a high luminous intensity immediately after printing, after long-term storage, luminescence cannot be confirmed even if irradiated with excitation light, or the luminous intensity is insufficient, making it impossible to read by a machine. It has been found. For this reason, the method using the above-mentioned organic fluorescent dye has a problem that the conditions of use are extremely limited.
  • an organic fluorescent dye is usually dissolved in a ketone-based organic solvent such as methyl ethyl ketone / methyl isobutyl ketone.
  • a ketone-based organic solvent such as methyl ethyl ketone / methyl isobutyl ketone.
  • An object of the present invention is to print on a product without impairing the appearance of the product, and to detect the printed product with high sensitivity over a long period of time, and furthermore, without affecting the ink occlusion material, UV-excitable ink composition that is safe and does not impose any restrictions on the use environment, a fluorescent composition used for such an ink composition, and a dot-like, thin-film, or thick
  • An object of the present invention is to provide a printed matter or a fluorescent composition printed in a film form.
  • a fluorescent composition comprising a base material and an organic fluorescent dye which emits light in the visible light region when excited by ultraviolet light, wherein the organic fluorescent dye is granular;
  • an ink composition comprising a resin, an organic fluorescent dye which is excited by ultraviolet light and emits light in a visible light region, and a solvent
  • the organic fluorescent dye is in the form of particles having a particle size of 10 to 200 nm.
  • the organic fluorescent dye used in the present invention is a dye that emits light having an emission center in a visible light region (wavelength 400 to 700 nm) when excited by ultraviolet light (wavelength less than 400 nm). It is a dye that is substantially invisible or difficult to recognize.
  • the emission color is not limited, those emitting red (wavelength: around 60 O nm, more preferably 6 15 ⁇ 20 nm) visible light are particularly preferable because of their excellent detectability. Used.
  • the organic fluorescent dye used in the present invention has no absorption in the visible light region, and therefore is invisible in the visible light region in a non-excited state, and is excited by ultraviolet light to have a long wavelength region near 600 nm.
  • a red-emitting organic fluorescent dye having an emission center wavelength is preferably used.
  • a typical example is a ligand having a rare-earth element such as europium or samarium as an emission center and having a large number of 7 ⁇ electrons.
  • a europium compound having a large light emission amount is most preferable.
  • a europium compound having a large light emission amount is most preferable.
  • Examples of the metal complex include ligands, and among them, a europium compound having a ligand of tenoline trifluoroacetone, naphthoyl trifluoroacetone, or methylbenzoyl trifluoroacetone having a large emission amount is preferable.
  • organic fluorescent dyes are disclosed in Melby et al., J. Am. Chem. Soc., Vol. 186, Vol. 5, pp. 117, 1964. It can be synthesized by the method described in the gazette.
  • Commercially available products of such organic fluorescent dyes include “Rumilux CD331”, “Rumilux CD332”, “Rumilux CD335", manufactured by Riedel Dehan, and Mitsui Chemicals, Inc. "ER-120” and "ER-122".
  • organic fluorescent dyes are inferior in storage stability, such as light resistance and weather resistance, as described above, and are in an ink state, in a printed state or in a state of a printed fluorescent composition (hereinafter, simply referred to as “printed state”).
  • the light emission intensity of the printed matter tends to decrease with time, and the storage stability of the printed matter is particularly poor. That is, in the ink state, the ink solvent intervenes between the dye and the outside air, thereby preventing direct contact between the dye and the outside air.However, in the printed state, there is no intervening substance such as the ink solvent, and the dye does not exist. The decomposability directly affects the stability of the printed matter.
  • This phenomenon is the same when the dye is adsorbed on the surface of inorganic or organic particles.
  • the dye is present on the surface of the particles in a molecular state as well as in a dissolved state in the ink solvent. Even in the case of printed matter using ink, deterioration due to decomposition cannot be suppressed because the dye comes into direct contact with the outside air.
  • a certain printing material has various functional groups on the surface, and the functional groups decompose the printed organic fluorescent dye. The light emission output tends to be remarkably reduced even when left at room temperature.
  • the present inventors have developed a method for reducing the influence of the organic fluorescent dye from the outside air and, when a printed material is obtained, reducing the effect of the functional group of the printed material to suppress the decomposability of the organic fluorescent dye.
  • Various studies were made. As a result, by putting the organic fluorescent dye in the bulk state (granular state), not only the ink state but also the printed matter However, it has been found that the long-term storage stability is improved and a high luminous output can be maintained.
  • the above-mentioned organic fluorescent dye when used, it is combined with a base material, and preferably has a particle size of 10 to 2 , 00 O nm granular. By using such a granular material, excellent storage stability can be obtained not only in an ink state using a solvent but also in a printed matter or a luminescent composition.
  • the reason that such storage stability can be obtained by the present invention is considered as follows.
  • the organic fluorescent dye is formed into bulk particles having a particle size of 10 to 200 nm
  • the printed dye or fluorescent composition is prepared using the dye, and the dye comes into contact with the outside air or the functional group of the substrate.
  • the active dye is still present inside, so that the decrease in the luminescence output is suppressed even after long-term storage.
  • the particle size in the above range is good is that a particle size of less than 1 O nm does not sufficiently improve the light stability of the print material and the effect of preservability such as weather resistance, and the dye easily penetrates into the print material. That's why.
  • the dyes fall off from the printed matter, and depending on the viewing angle, the organic fluorescent dyes may be visible, which causes problems.
  • a base material that carries a dye there are an inorganic base material prepared by a sol-gel method or the like, and a resin base material. From the viewpoints of flexibility and adhesion to a printed material, a resin base material is preferable.
  • ketone solvents and the like have been used as solvents capable of dissolving the organic fluorescent dye.
  • ketone-based solvents cannot convert organic fluorescent dyes into particulate matter in bulk, and the dyes dissolve and come into contact with the outside air in molecular form.
  • storage stability that is, light resistance ⁇ weather resistance deteriorates remarkably.
  • a solvent invades an ink occluding material that absorbs ink, that is, a cloth ribbon made of a polyamide resin in a dot impact pudding, and a foamed urethane in a stamp pudding, and significantly reduces the durability. .
  • this solvent generates vapors harmful to the human body, and is restricted for use in offices and the like. Therefore, in one preferred embodiment of the present invention, a solvent containing 94% by weight or more of water or / and ethanol is used. However, from the viewpoint of environmental friendliness, 95% or more of water or / and ethanol is contained. Solvents are more preferably used. More preferably, it is water or / and ethanol only, most preferably water only.
  • the other solvent is preferably one in which the organic fluorescent dye is insoluble, but even if it is slightly soluble, it is mixed with water or / and ethanol. Any combination of these can be used without any particular limitation as long as the organic fluorescent dye can be present as particulate matter in a bulk state.
  • the base material is preferably a resin having low reactivity with an organic fluorescent dye and improving printability and durability of a printed layer, and is usually a resin soluble in the above solvent.
  • a type of emulsifying and dispersing may be used in some cases.
  • Specific examples of such resins include polyvinyl alcohol, phenolic resins, polyester resins, acrylic resins, cellulosic resins, polyamides, and maleic resins. Among them, polyvinyl alcohol which is dissolved in the above-mentioned solvent of the present invention and which has an excellent effect of dispersing the organic fluorescent dye is preferably used.
  • the amount of the base resin used depends on the type thereof, but is usually 50 to 1000 parts by weight, preferably 100 to 100 parts by weight, based on 100 parts by weight of the organic fluorescent dye. 0 parts by weight, more preferably 200 to 300 parts by weight, particularly 500 to 2000 parts by weight.
  • Oxygen permeability coefficient 1 X 10- 19 The (m 2 - - S "1 Pa” 1)
  • the following resin for example other, polyvinyl alcohol resins, polyvinyl alcohol resins (Biniruaru call one vinyl acetate copolymer, etc.) , A polyvinyl resin, a cellulose resin, a polyester resin, a polyester resin, a polyimide resin, a polyamide resin, and the like, and these are used alone or as a mixture of two or more. Considering the solubility in a solvent, the stability of the ink, the dispersibility of the organic fluorescent dye, and the like, a polyvinyl alcohol resin or a polyvinyl alcohol resin is most preferable.
  • the oxygen permeability coefficient depends on the degree of saponification of the polyvinyl alcohol-based resin, a resin having a desired oxygen permeability coefficient can be easily obtained by adjusting the degree of saponification.
  • the saponification degree of 0.2 or more polyvinyl alcohol resin, and at the same time the oxygen permeability coefficient is IX 10- 19 (m 2 ⁇ S- 1 ⁇ Pa- 1) below, soluble in an aqueous solvent is very well It is desirable when applied to inkjet ink.
  • polyvinyl resins such as polyvinyl butyral, polyvinyl pyrrolidone, and vinyl pyrrolidone monovinyl acetate copolymer may be used in combination.
  • urethane resins containing a large amount of hydroxyl groups in the molecular chain and soluble in water and / or ethanol, and urethane resins such as acryl-urethane graft copolymers are also effective in improving the adhesion to pet films. Therefore, it is preferably used.
  • the amount of oxygen permeability coefficient 1 X 10- 19 (m 2 ⁇ S- 1 ⁇ Pa -1) or less of the resin, based on the total weight of the ink composition from 0.05 to 30 wt% Is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight. This range is preferred when less than 05% by weight reduces the oxygen permeation inhibitory effect, and when it exceeds 30% by weight, the viscosity of the ink becomes too high and nozzles are easily clogged. It is because it becomes.
  • the oxygen permeability coefficient of the resin is determined according to ASTM-D1434-75. (Measurement method of gas permeability coefficient in plastic films and sheets) can be measured and evaluated.
  • a medium having a boiling point of 200 ° C. or higher and a medium in which the organic fluorescent dye is insoluble or has low solubility is used as the solvent for the ink composition. This makes it possible to make the above pigment into bulk particulate matter with a particle size of 10 to 2, OO Onm, and there is no fear of generating harmful vapors to the human body, and it is used in offices and the like. This also makes it possible to prepare an ink composition that is not subject to any restrictions on the use environment.
  • hardly volatile solvents having a boiling point of 200 ° C or more used in another preferred embodiment of the present invention those having a boiling point of 250 ° C or more, which is more difficult to volatilize, are more preferable from the viewpoint of environmental friendliness.
  • examples of such media include higher fatty acids that are liquid at room temperature, such as oleic acid, linoleic acid, and linolenic acid, castor oil, liquid paraffin, machine oil, polyoxyethylene (POE), polyoxypropylene (POP), and alkyl ethers.
  • POP alkyl ether POP alkyl ether, POE alkyl ether, polyethylene glycol, polypropylene glycol, glycerin, sorbic acid ester, benzyl alcohol and the like.
  • the organic fluorescent dye is insoluble, but even if the organic fluorescent dye is slightly soluble, the organic fluorescent dye is used in a bulk state in a combined system with a non-volatile medium having a boiling point of 200 ° C or higher. As long as it can be present as a granular material, it can be used without any particular limitation.
  • a resin having low reactivity with an organic fluorescent dye and improving printability and durability of a printed layer is preferable, and is usually soluble in the above-mentioned solvent.
  • a type of emulsifying and dispersing in some cases may be used.
  • Specific examples include a rosin resin, a phenol resin, a shellac resin, a ketone resin, an alkyd resin, a maleic resin, and a rosin-modified maleic resin.
  • a rosin resin, a rosin-modified maleic resin, and the like which dissolve in the above-mentioned solvent of the present invention and have an excellent effect of dispersing an organic fluorescent dye, are preferably used.
  • the amount of the base resin used depends on the type, but is usually 50 to: 100,000 parts by weight of L, preferably 100 to 100,000 parts by weight, per 100 parts by weight of the organic fluorescent dye. Preferably it is 200 to 3000 parts by weight, especially 500 to 2000 parts by weight.
  • the reason why this range is preferable is that if it is less than the above lower limit, the adhesion strength of the printed layer is weak, and if it exceeds the above upper limit, the luminous intensity of the printed matter or the fluorescent composition becomes weak.
  • the organic fluorescent dye is added to the solvent together with the base resin, and the resulting mixture is well dispersed and mixed by a dispersing machine such as a ball mill or a sand mill. A uniform ink composition is obtained.
  • the amount of the organic fluorescent dye to be used is generally 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the solvent. This range is preferable because if the amount is less than 0.01 part by weight, the light emission intensity is low, and if the amount exceeds 30 parts by weight, the light emission intensity cannot be increased due to concentration quenching.
  • the particle size of the organic fluorescent dye before dispersion is usually 10 to 50 zm. However, the organic fluorescent dye is pulverized at the same time as the dispersion so as to have a particle size of 10 to 2, O O Onm after dispersion.
  • the lower limit of the particle size after dispersion is particularly preferably 50 nm or more, and more preferably 100 nm or more.
  • the upper limit of the particle size after dispersion is preferably 80 Onm or less, more preferably 60 Onm or less, and even more preferably 500 nm or less.
  • the upper limit of the particle size of the dye that can stably maintain the dispersed state in the ink composition is mainly determined by the viscosity of the solvent, and 800 nm when a low-viscosity solvent such as water and / or ethanol is used. The following is preferred.
  • the organic fluorescent dye composed of such particulate matter may have a particle diameter after dispersion within the range of 10 to 2,000 nm, and all of the particulate matter has a uniform particle diameter. You don't need to be.
  • the particle diameter of the organic fluorescent dye refers to a sample prepared by diluting the ink composition about 1,000 times with a solvent having the same composition as the solvent contained in the ink composition, and preparing a cell having a diameter of 12 mm. The values were measured by dynamic light scattering at room temperature, using a 5mW He-Ne laser, at a measurement angle of 90 degrees and a total of 100 integrations.
  • the ink composition of the present invention may contain a surfactant together with the base resin.
  • an appropriate amount of a phosphorus-based organic compound or the like can be used as an additive.
  • an appropriate amount of a charge adjusting agent, a pH adjusting agent, and the like can be contained.
  • L i salts such as L in0 3
  • K salts such as KS CN
  • Hosuhoniumu salts represented by the following formula (1) and the like
  • Anmoniumu salt as a charge control agent.
  • phosphonium salts and ammonium salts are more preferable because of high dispersion stability of the ink composition.
  • the addition amount of these charge control agents is preferably from 0.05 to 5% by weight, more preferably from 0.1 to 5% by weight, based on the total weight of the ink composition. . This addition amount is preferred because the charge control effect becomes insufficient when the content is less than 0.05% by weight, and the effect is saturated when the content exceeds 5% by weight.
  • A is a nitrogen atom or a phosphorus atom
  • R to R 4 are the same or different and are each a hydrogen atom or a linear or cyclic hydrocarbon group having 1 to 14 carbon atoms. 1 ⁇ to 11 4 at least two of but it may also be bonded to each other to form a ring.
  • a fluorinated surfactant When printing on plastic sheets, bags, bottles, etc., it is desirable to add 0.05 to 0.5% by weight of a fluorinated surfactant.
  • the fluorine-based surfactant when added, the dot diameter is reduced to about 40% as compared with the case where no fluorine-based surfactant is added.
  • the above-mentioned addition amount range is preferable because the effect of reducing the dot diameter is small when the content is less than 0.05% by weight, and the ink composition tends to foam when the content is more than 0.5% by weight.
  • the ink composition can be used for dot-impact printing, stamp printing, ink-jet printing, stamping, and other forms of mail such as forms and postcards.
  • Printed on the surface of various goods Then, a printing layer made of a desired mark such as a bar code is formed to obtain a printed material.
  • the ink composition contains the above-mentioned solvent, it is safe for the human body, is not restricted in the use environment, and can be safely operated even in an office with insufficient ventilation.
  • the organic fluorescent dye in the printed layer does not have a light-emitting and light-absorbing component in the visible light region, and therefore has no risk of impairing the appearance of the article as a printed layer that is invisible or difficult to recognize.
  • the dye in the print layer is excited and emits light in the visible light region, which can be visually recognized, and a reading reader such as a silicone photodiode as a photoelectric conversion element.
  • Desired mark information can be read with high sensitivity.
  • the most significant feature of the present invention is that the above-mentioned organic fluorescent dye exists as fine particles in an ink state and a printed layer state, and has excellent storage stability, that is, excellent light resistance and weather resistance. Therefore, the mark information can be detected with high sensitivity over a long period of time.
  • parts means “parts by weight”.
  • Example 1 In the same manner as in Example 1 except that the dispersion treatment time by a planetary ball mill was set to 8 hours, an ultraviolet-excited ink composition containing a pigment as particulate matter having a particle size of 120 to 23 O nm was prepared. did. Comparative Example 1
  • Example 2 In 90 parts of methyl ethyl ketone, 0.5 part of the same dye as used in Example 1 was dissolved, and an acrylic resin ("Dianal BR-1" manufactured by Mitsubishi Rayon Co., Ltd.) was further used as a base resin. 0 6 ”) 9.5 parts were added, mixed well with stirring, and dissolved to prepare an ultraviolet-excited ink composition.
  • Example 2 0.5 parts of the same dye used in Example 1 was dissolved in 3 parts of methyl ethyl ketone. Next, this dye solution was mixed with 77 parts of water, 10 parts of silica particles having an average particle diameter of 10 O nm as inorganic particles, and 9.5 parts of polyvinyl alcohol (Kuraray PVA) as a base material resin. The resulting slurry was blended and mixed well with stirring to prepare an ultraviolet-excited ink composition.
  • Kuraray PVA polyvinyl alcohol
  • the fluorescence emission intensity of the ink composition at the initial stage and after storage at high temperature was measured using a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation). However, the values are shown as relative values with the initial light emission intensity of Example 1 being 100%.
  • the ink composition was filled in a marker pen and used to form a print layer on white paper.
  • FP750 fluorescence spectrophotometer
  • both ink compositions of Examples 1 and 2 have the initial fluorescent emission intensity increased because the organic fluorescent dye is present as particulate matter in a bulk state.
  • the decrease in strength after high-temperature storage is suppressed, and the printed matter printed using this is also less reduced in strength after long-term storage. It can be seen that the storage stability is remarkably excellent even in the state where it was used.
  • the ink composition of Comparative Example 1 had a low initial fluorescence emission intensity because the organic fluorescent dye was completely dissolved in the solvent, and the intensity deteriorated after high-temperature storage. In the state of a printed material, the strength is further reduced, and the deterioration after long-term storage is remarkable.
  • the ink composition of Comparative Example 2 had a certain effect of improving the fluorescence emission intensity as compared with Comparative Example 1 by adsorbing the organic fluorescent dye on the surface of the inorganic particles. Compared with those of the printed matter, the printed matter is remarkably inferior, and particularly the printed matter has remarkably poor long-term storage characteristics.
  • Oxygen permeability coefficient "instead of 20 (m 2 ⁇ S- 1 ⁇ Pa- polyvinyl alcohol (manufactured by Kuraray Co., Ltd. PVA) 5 parts, the oxygen permeability coefficient is 3 X 10- 23 (m 2 - S" 5 X 10 1 ⁇ Pa "1 polyvinyl alcohol) (except using Kuraray Co., Ltd. PVA) 5 parts, the same procedure as in example 3, ultraviolet excitation organic fluorescent dye is included as granules having a particle size of two hundred and ten to four hundred and ten nm A mold ink composition was prepared.
  • An ultraviolet-excited ink composition containing an organic fluorescent dye as a particulate having a particle size of 150 to 25 Onm was prepared in the same manner as in Example 3 except that the dispersion treatment time by a planetary ball mill was changed to 8 hours.
  • An ultraviolet-excited ink composition containing an organic fluorescent dye as granules having a particle size of 80 to 19 Onm was prepared in the same manner as in Example 3 except that the dispersion treatment time by a planetary ball mill was changed to 16 hours.
  • An ultraviolet-excited ink composition was prepared in the same manner as in Example 3, except that 0.1 part of "Fluorad FC430" manufactured by Sliem was added as a fluorinated surfactant.
  • 0.1 part of "Fluorad FC430" manufactured by Sliem was added as a fluorinated surfactant.
  • Example 3 In the same manner as in Example 3 except that the dispersion treatment time by a planetary ball mill was set to 1 hour, an ultraviolet-excited ink composition containing an organic fluorescent dye as particles having a particle size of 900 to 1,40 Onm was prepared. did.
  • Example 3 0.5 parts of the same organic fluorescent dye as in Example 3 was dissolved in 3 parts of methyl ethyl ketone.
  • the dye solution the average particle diameter 100 nm of silica force grain child 10 parts as inorganic particles 77 parts of water and oxygen permeability coefficient of 5 X 10- 2 ° of (m 2 ⁇ S- 1 ⁇ P a "1) Polyvinyl alcohol (PVA manufactured by Kuraray Co., Ltd.) was mixed in a slurry obtained by mixing 9.5 parts and mixed well by stirring to prepare an ultraviolet-excitation ink composition.
  • PVA Polyvinyl alcohol
  • each of the ink compositions of Examples 3 to 9 and Reference Examples 1 and 2 was characterized in that the organic fluorescent dye having a particle size of 10 to 80 nm was a particulate material in a bulk state.
  • the initial fluorescence emission intensity is high, and the decrease in the intensity after storage at high temperatures is small.
  • the printed matter printed using this has a fluorescence emission intensity after storage at room temperature at a practical level (30% or more), and can be read by a barcode reader.
  • the ink composition of Comparative Example 3 has a low initial fluorescence emission intensity because the organic fluorescent dye is completely dissolved in the solvent, and the intensity is further deteriorated after high-temperature storage. In the state of a printed material, the strength is further reduced, and the deterioration after long-term storage is remarkable.
  • the ink composition of Comparative Example 4 had a certain effect of improving the fluorescence emission intensity compared to Comparative Example 3 by adsorbing the organic fluorescent dye on the surface of the inorganic particles. Compared with those of the printed matter, the printed matter is remarkably inferior, and particularly the printed matter has remarkably poor long-term storage characteristics.
  • the fluorescence emission intensity of the printed matter after heat treatment was initially measured after storage for 6 months indoors and after storage for 3 months outdoors using a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation). It is shown as a relative value with the initial light emission intensity of Example 5 being 100%.
  • Example 5 the printed matter of Example 5 in which the crystallinity of the resin was 0.1 or more by the heat treatment was stored under severe storage conditions of 6 months at room temperature and 3 months at outdoor storage.
  • the decrease in the emission intensity was considerably suppressed, and it was found that the light resistance and weather resistance were further increased.
  • a dye that is substantially invisible or difficult to recognize in the visible light region and emits light when excited by ultraviolet rays (trade name “CD335” manufactured by Rieder de Haan, Inc., excitation wavelength: 365 nm, emission wavelength: 615 nm), and the mixture was dispersed for 4 hours using a planetary ball mill to prepare an ultraviolet-excited ink composition containing the above-mentioned dye as particles having a particle size of 210 to 410 nm.
  • An ultraviolet-excited ink composition containing a pigment as particulate matter having a particle size of 120 to 23 Onm was prepared in the same manner as in Example 10 except that the dispersion treatment time by a planetary ball mill was changed to 8 hours.
  • An ultraviolet-excited ink composition containing a pigment as particulate matter having a particle diameter of 1000 to 160 Onm was prepared in the same manner as in Example 10 except that the dispersion treatment time by a planetary ball mill was changed to 1 hour.
  • Example 10 In 90 parts of methyl ethyl ketone (boiling point 80 ° C), 1.0 part of the same pigment used in Example 10 was dissolved, and an acrylic resin (trade name “Dyana” manufactured by Mitsubishi Rayon) was further used as a binder. One part BR-106 ”) was added, and the mixture was dissolved with good stirring and mixing to prepare an ultraviolet-excitation ink composition.
  • an acrylic resin trade name “Dyana” manufactured by Mitsubishi Rayon
  • An ultraviolet-excited ink composition was prepared in the same manner as in Example 10, except that the dispersion treatment time by a planetary ball mill was 0.5 hour. Measured by dynamic light scattering method The particle size of the dye thus obtained was 2,200 to 2,900 nm.
  • the ink compositions of Examples 10 to 12 and Comparative Examples 5 to 7 were: No sedimentation of the organic fluorescent dye was observed, but sedimentation of the organic fluorescent dye was clearly observed in the ink composition of Comparative Example 6. Further, the ink compositions of Examples 10 to 12 and Comparative Examples 5 to 7 were filled in urethane sponges having continuous pores and used as a stamp ink. The ink of Comparative Example 6 was urea of the ink occluding body. Invaded the sponge in the evening, making printing impossible. In addition, in the ink of Comparative Example 6, a lot of print blurring was observed, which is considered to be caused by sedimentation of the pigment.
  • the fluorescence emission intensity in the ink state was measured by the same method as described above, and the fluorescence emission intensity when a printed material was obtained. was measured by the following method. In each case, the fluorescence emission intensity was shown as a relative value with the initial emission intensity of Example 10 being 100%.
  • Each ink composition was used as a stamping ink and used to form a print layer on white paper.
  • the fluorescence intensity of this printed matter initially and after storage in a room for three months was measured with a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation), and the initial light emission intensity of Example 10 was measured. The relative values are shown as 100%.
  • Table 5 The fluorescence intensity of this printed matter initially and after storage in a room for three months was measured with a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation), and the initial light emission intensity of Example 10 was measured. The relative values are shown as 100%. Table 5
  • the ink composition of Comparative Example 6 has a low initial fluorescence emission intensity because the organic fluorescent dye is completely dissolved in the solvent, and the intensity is more deteriorated after storage at a high temperature. Remarkable. Furthermore, although the ink composition of Comparative Example 8 caused the organic fluorescent dye to be adsorbed on the surface of the inorganic particles, the ink composition of Comparative Example 6 exhibited a certain effect of improving the fluorescence emission intensity as compared with Comparative Example 6, but the present invention Compared with those of the printed matter, the printed matter is remarkably inferior, and the printed matter has remarkably poor long-term storage characteristics.
  • an organic fluorescent dye that is substantially invisible or difficult to recognize in the visible light region and emits light in the visible light region when excited by ultraviolet light is used as bulk particles.
  • the presence of the mark allows the desired mark to be printed on the article without damaging its appearance, and allows the printed mark to be detected with high sensitivity over a long period of time, and is safe for the human body. It is possible to provide an ultraviolet-excitation type fluorescent composition, an ink composition, and a printed material thereof, which are not subject to any restrictions on the use environment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne une composition fluorescente qui présente une excellente résistance à la lumière, comprend une matière de base et un colorant organique particulaire fluorescent dont le diamètre des particules est compris entre 10 et 2.000 nm, et est excitée aux ultraviolets pour émettre une lumière dans le domaine du visible. L'invention concerne une composition d'encre contenant cette composition fluorescente et un solvant. La composition d'encre peut être utilisée pour imprimer une marque sur un article sans en altérer l'aspect. La marque imprimée peut être détectée avec une grande sensibilité et pendant une longue durée. En outre, cette composition d'encre n'est pas nocive pour le corps humain et n'impose aucune contrainte particulière par rapport à l'environnement dans lequel elle est employée.
PCT/JP2000/004790 1999-07-19 2000-07-17 Composition fluorescente, composition d'encre et matiere imprimee WO2001005907A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58539/00A AU5853900A (en) 1999-07-19 2000-07-17 Fluorescent composition, ink composition, and printed matter

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP11/205327 1999-07-19
JP20532799 1999-07-19
JP2000/70976 2000-03-09
JP2000070976 2000-03-09
JP2000/71622 2000-03-15
JP2000071622 2000-03-15

Publications (1)

Publication Number Publication Date
WO2001005907A1 true WO2001005907A1 (fr) 2001-01-25

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PCT/JP2000/004790 WO2001005907A1 (fr) 1999-07-19 2000-07-17 Composition fluorescente, composition d'encre et matiere imprimee

Country Status (2)

Country Link
AU (1) AU5853900A (fr)
WO (1) WO2001005907A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109517508A (zh) * 2018-10-31 2019-03-26 湖南航天三丰科工有限公司 一种水性光学隐身涂层材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08239610A (ja) * 1995-03-07 1996-09-17 Mikuni Shikiso Kk インクジェット用水性顔料インキ組成物
WO1997010307A1 (fr) * 1995-09-15 1997-03-20 Videojet Systems International, Inc. Composition d'encre par jet
JPH1017571A (ja) * 1996-07-01 1998-01-20 Toyo Ink Mfg Co Ltd 赤色蛍光材料及びそれを含有する組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08239610A (ja) * 1995-03-07 1996-09-17 Mikuni Shikiso Kk インクジェット用水性顔料インキ組成物
WO1997010307A1 (fr) * 1995-09-15 1997-03-20 Videojet Systems International, Inc. Composition d'encre par jet
JPH1017571A (ja) * 1996-07-01 1998-01-20 Toyo Ink Mfg Co Ltd 赤色蛍光材料及びそれを含有する組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109517508A (zh) * 2018-10-31 2019-03-26 湖南航天三丰科工有限公司 一种水性光学隐身涂层材料及其制备方法
CN109517508B (zh) * 2018-10-31 2021-01-26 湖南航天三丰科工有限公司 一种水性光学隐身涂层材料

Also Published As

Publication number Publication date
AU5853900A (en) 2001-02-05

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