DE102010018364A1 - Aqueous black-pigmented, UV-fluorescent inkjet ink comprises humectant, surfactant, wetting agent, pigment, optionally additives and remaining water - Google Patents

Aqueous black-pigmented, UV-fluorescent inkjet ink comprises humectant, surfactant, wetting agent, pigment, optionally additives and remaining water

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Publication number
DE102010018364A1
DE102010018364A1 DE201010018364 DE102010018364A DE102010018364A1 DE 102010018364 A1 DE102010018364 A1 DE 102010018364A1 DE 201010018364 DE201010018364 DE 201010018364 DE 102010018364 A DE102010018364 A DE 102010018364A DE 102010018364 A1 DE102010018364 A1 DE 102010018364A1
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DE
Germany
Prior art keywords
inkjet ink
characterized
ink according
anionic
particular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE201010018364
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German (de)
Inventor
Nicole Howald
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Hapa AG
Original Assignee
PELIKAN HARDCOPY PRODUCTION AG
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Priority to DE201010018364 priority Critical patent/DE102010018364A1/en
Publication of DE102010018364A1 publication Critical patent/DE102010018364A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/50Sympathetic, colour changing or similar inks
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/32Inkjet printing inks characterised by colouring agents
    • C09D11/324Inkjet printing inks characterised by colouring agents containing carbon black

Abstract

Aqueous black-pigmented, UV-fluorescent inkjet ink comprises (in wt.%): humectant (20-30) in the form of glycerol (6-17) and viscosity increasing co-humectant; surfactant (0.05-0.1); wetting agent (0.1-1.5); anionic self-dispersing black pigment (1-6); anionic blue-fluorescent optical brighteners (0.2-1.5); other additives; and remaining water.

Description

  • The invention relates to an aqueous black pigmented, UV-fluorescent ink jet ink containing a humectant, surfactant, wetting agent and pigment and optionally other additives
  • An inkjet ink of the above kind results for example from the WO 2006/009701 A2 , There, in all generality, an aqueous inkjet ink is disclosed, which fluoresces in the case of fluorescence-initiating radiation. It has a suitable viscosity and surface tension to be used in inkjet printing and contains a first colorant comprising a fluorescent dye and / or a fluorescent pigment which emit light when suitably irradiated. In addition to the first colorant is a second colorant, in particular in the form of carbon black and one or more dyes or pigments, said second colorant having an absorption band at a wavelength which is longer than that of the first colorant. An overlap should be possible. This patent does not address the problems of compatibility of the constituents of the inkjet ink, and more particularly does not address the possible foaming of the ink in the printhead or the formation of ink in the printing process.
  • The WO 2009/020998 A1 deals with an aqueous inkjet ink containing a color pigment, a UV-fluorescent material and an aqueous carrier. The fluorescent material constitutes about 0.01 to 2.0% of the aqueous inkjet ink, and is particularly present as a dye or pigment. It is preferred that the UV-fluorescent material is introduced in the form of a wax emulsion in the aqueous inkjet ink. The wax emulsion contains the UV-fluorescent material, a wax, a surfactant and a dispersant.
  • Please note the inkjet ink described below US 2009/0288580 A1 : It relates to a fluorescent inkjet ink containing a fluorescent colorant. This should preferably be a UV-fluorescent pigment. Preferably, the ink is to be incorporated with a dispersant which is in the form of a polymeric dispersant, alkaline salts, lignin and lignin derivatives.
  • Finally, on the EP 2 028 238 A to point. This discloses an aqueous ink composition containing water-insoluble colored particles (A) and water-insoluble particles (B). The water-insoluble particles (B) contain a carboxylate emulsifier and a water-insoluble polymer. The inclusion of a UV brightener in the described ink is mentioned, but only as an additive to yellowing. In the context of black pigmented inks, the effect of a UV brightener is not addressed.
  • The invention has the object to further develop the above-described prior art so that the problems of compatibility of the components of the inkjet ink and the foaming are addressed. It should be remembered that for security prints InkJet inks are needed, which look black under normal light and fluorescent under UV light. The proportion of black pigment should be optimized so that the fluorescence content is not covered too much. The InkJet ink should also exclude the formation of an ink lake on the printing plate and thus a streaky print image as much as possible during the printing process. Finally, the inkjet ink should show good water and lightfastness.
  • This object is achieved according to the invention in that it contains: about 20 to 30% by weight of humectant in the form of glycerol and a viscosity-increasing co-humectant, the content of glycerol in the ink-jet ink being from 6 to 17% by weight, about 0.01 to 0.1 wt.% surfactant, about 0.1 to 1.5 wt.% surfactant, about 1 to 6 wt.% anionic self-dispersing black pigment, about 0.2 to 1.5 wt. -% anionic, blue-fluorescent optical brightener, optionally further additives, and the remainder water.
  • Advantageous embodiments of this basic concept according to the invention also result from the subclaims as follows:
    It has been found in the practice of the invention that it preferably contains as humectant about 7 to 15 wt .-% glycerol and / or a total of about 22 to 28 wt .-% humectant, about 0.01 to 0.1 wt. % Surfactant, about 0.25 to 1.5 wt .-% wetting agent, about 2 to 4 wt .-% anionic self-dispersing black pigment and / or about 0.5 to 1 wt .-% anionic, blue-fluorescent optical brightener contains. In compliance with these conditions, the invention solves extensively the task.
  • It is particularly advantageous if the mentioned co-humectant is present in the form of diols or polyols. Particularly suitable are glycols, in particular in the form of ethylene glycol, diethylene glycol, triethylene glycol and / or 1,5-pentanediol, and / or 2-pyrrolidone. The co-humectants support the function of glycerol as humectants, liquid co-humectants, especially because they have a sufficiently high boiling point. In combination with glycerine, they result in an optimum adjustment of the desirable viscosity value useful for later inkjet printing. Further suitable co-humectants may also be mentioned: urea, urea derivatives, ethylene oxide adducts.
  • It is important for the technical success desired by the invention that the claimed inkjet ink contain a surfactant in an amount of about 0.01 to 0.1% by weight. Hereby, the surface tension should be optimally adjusted. The invention is not subject to any relevant limitation with regard to the choice of surfactant. It has been found that a surfactant is particularly advantageous when it is in the form of polyethoxylated 2,4,7,9-tetra-methyl-5-decyne-4,7-iols (Surfynol 440 / sold by the company Air Products ), 2,4,7,9-tetra-methyl-5-decyne-4,7-iols (Surfynol 104 / sold by Air Products), a silicone surfactant, especially a polyether-modified polydimethylsiloxane, of an N Alkylpyrrolidons, in particular in the form of 1-octyl-2-pyrrolidone or 1-dodecyl-2-pyrrolidone, an n-octylpyrrolidone (Surfadone LP 100) and / or an n-dodecylpyrrolidone (Surfadone LP 300) is present. Another advantage is the commercial product Sylwet copolymer L7607. Surfactants which correspond or approximate to the commercial products Surfynol and Silwet and are accordingly also suitable according to the invention are given by way of example in the formula EP 1 586 612 A1 (supra., [0014] and [0015]). Other particularly suitable surfactants can be determined expertly among the known surfactants.
  • As already mentioned, the inkjet ink according to the invention must contain about 0.25 to 1.5% by weight of wetting agent. In the context of the invention, in particular alcohols customarily used for this purpose are suitable, in particular in the form of propyl alcohol, isopropyl alcohol, diglycol, z. Butyl diglycol, propylene glycol n-propyl ether (commercial product Dowanol PnP) and propylene glycol n-butyl ether (Dowanol PnB). The wetting agents contemplated by the present invention act to control the penetration of the inkjet ink into, for example, paper. This function fulfills in particular the mentioned butyldiglycol.
  • To delineate, on the one hand, surfactants and, on the other hand, wetting agents in the practice of the present invention, the following should be noted: The surfactants reduce the surface tension of the ink, which, as already stated, helps the wetting agents penetrate the printed paper more quickly.
  • For the invention it is particularly important that a special anionic self-dispersing black pigment is used. As a result, it is precluded that only a black dye is contained in the ink. In any case, they are organic or inorganic black pigments which, which is essential to the invention, have anionic groups on their surface. The black pigment is present in particular in the form of an anionic self-dispersing carbon black. These are, in particular, those black pigments which on the surface have, in particular, one or more functional anionic groups, in particular in the form of a carbonyl, carboxy, hydroxyl and / or sulfonyl group, if appropriate also in the form of a salt, by means of a special surface treatment , Such anionic self-dispersing black pigments are described, for example, in US Pat EP 0 797 636 B1 disclosed. A particularly preferred example is sold by Cabot, USA under the trade name Cab-O-Jet 200, 300 and others. Other possible suitable self-dispersing pigments are SDP100, 1000, 2000 from Sensient.
  • Since the self-dispersing pigments are anionically stabilized, the optical brightener must also be anionic in order to promote the stability of the self-dispersing pigments. In the case of the anionic optical brightener, which is blue-fluorescent in the context of the invention, the invention is not subject to any significant restrictions. It also has the function of a fluorescent dye or is one and is preferably water-soluble. In particular, this is a stilbene and / or a pyrazole derivative. The optimal anionic, blue-fluorescent optical brightener has the CI index number Fluorescent Brightener 113.
  • In order to improve the shelf life of the inkjet ink according to the invention, it is generally advantageous to include a biocidal preservative in the form of a thiazole and / or isothiazole compound, in particular in the form of a 1,2-benzisothiazolin-3-one compound ,
  • For those skilled in the art readily apparent, the inkjet ink according to the invention, other additives can be incorporated, such as pH adjusting agent.
  • The particle size of the anionic self-dispersing black pigments used according to the invention corresponds to the commercial particle size. It is preferably below about 0.3 μm, in particular below about 0.2 μm. The range of 0.01 to 0.2 .mu.m, in particular from 0.03 to 0.180 microns, is considered particularly preferred.
  • It has been found that the invention undergoes a particularly advantageous embodiment, if by qualitative and quantitative optimization in the invention according to claim 1 and the dependent claims, the static surface tension, determined by the ring method according to Du Noüy using a digital Tensiometers K10T Krüss, DE, to about 30 to 45 mN / m, in particular to about 35 to 42 mN / m, is set.
  • The effect sought by the invention, referred to above, is optimally obtained when the dynamic viscosity to about 2 to 3 mPa · s, as measured by a cone plate rheometer from Brookfield, in particular about 2.2 to 2.7 mPa · s , This causes the printer to print the ink optimally.
  • It is not insignificant that within the scope of the invention the pH is between 5 and 10, in particular between 6 and 9. In general, this occurs immediately without any need for regulation. In individual cases, it may be useful to use a pH adjusting agent. For example, triethanolamine, caustic soda, any acids, buffers, such as ammonium acetate, and the like can be used for this purpose.
  • For further explanation of the invention: As presented above, this represents an optimized combination of individual parameters from a qualitative and quantitative point of view. It is essential that an anionic self-dispersing pigment, such as the commercially available self-dispersing carbon black with the trade name Cab-O-Jet ® , which has an anionic external charge on the surface particles, is combined with an anionic, blue-fluorescent component in the form of a water-soluble anionic optical brightener. Accordingly, the anionic self-dispersing pigment and the blue-fluorescent component must have the same anionic charge. A different charge would not achieve the effects of the invention. In addition, not only the designated humectants, surfactants and wetting agents must be included in the inkjet ink according to the invention, but this specific quantitative conditions are met. In this case, the special case of the term "humectant" is that it necessarily comprises glycerol on the one hand and other co-humectants on the other with specific specific conditions.
  • The precise coordination of the amount of surfactant to wetting agent largely avoids the mentioned foaming and also the puddling on the nozzle plate in the case of inkjet printing. Do not use too much surfactant or wetting agent. Finally, it has been shown that the pigment content must not be set too high, which optimally takes into account the present invention, since otherwise the fluorescence would be covered in an undesired manner. Here, the invention has yet to take into account, as has been found in their discovery: the higher the use of anionic optical brightener, the better the light fastness. However, the amount of anionic optical brightener should not be too high as the anionic self-dispersing pigment would otherwise precipitate and clog the nozzles with inkjet printing. Finally, the invention is expressly focused on a black pigmented inkjet ink, i. H. to an ink, which necessarily contains a self-dispersing black pigment. This does not exclude that in addition to the designated anionic self-dispersing pigment further pigments and optionally suitable dyes may be included. Examples which may be mentioned are: self-dispersing color pigment dispersions from Cabot or Sensient.
  • In summary, the main advantages of the invention can be stated as follows: The problem of foaming is excluded, as well as the puddling during inkjet printing on the nozzle plate. The ratio of pigment to blue fluorescent component is advantageously balanced. Fluorescence appears to be desirable upon UV irradiation. The pigmented ink meets the requirements for light and water fastness. The invention results in a readable print image, printing without offset, and largely avoids the phenomenon of "satellite" formation. Your life is very satisfying.
  • The invention will be explained in more detail with reference to examples and comparative examples.
  • Examples:
  • In the following, comparative examples and inventive examples of different formulations are given, from which the respective qualitative and quantitative composition is evident. It also reviews are made. The formulations identified in the Comparative Examples and Examples are prepared by mixing the specified ingredients together in the usual way. Special requirements are not to be considered here. Table 1 (comparative examples) A B C Demineralized water 68.5 68.2 69275 Proxel 0.1 0.1 0.1 ethylene glycol 15 12.5 10 glycerin 10 12.5 15 Surfynol 104PA 12:15 0.2 0125 diglycol 1.5 2 1 Blankophor BA267% 1.1 0.75 0.75 self-dispersing pigment 3.75 3.75 3.75 Total 100 100 100 Surface tension (mN / m) 34.3 31.6 35.0 PH value 8:44 8:39 8:40 Viscosity (mPa · s) 2:59 2.65 2:55 Viscosity 3Wo / 60 ° (mPa · s) 2.97 2.69 2.60
  • The surface tension was determined by the ring method according to du Noüy. In this case, a digital tensiometer K10T from. Krüss, DE, was used. The dynamic viscosity in mPa · s was determined using a cone plate rheometer from Brookfield.
  • Rating:
  • Recipe A caused instability after 3 weeks of storage at 60 ° C. Formulation B produced too much foam. The inkjet ink formed a lake on the nozzle plate and resulted in a streaky print image.
  • The latter also applies to Formulation C, which also left ink on the nozzle plate. Table 2 (Examples of the invention) D e Demineralized water 69.85 70.6 Proxel 0.1 0.1 ethylene glycol 10 10 glycerin 15 15 Surfynol 104PA 12:05 12:05 diglycol 0.5 0.5 Blankophor BA267% 0.75 0.75 self-dispersing pigment 3.75 3 Total 100 100 Surface tension (mN / m) 39.8 38.5 PH value 8:45 8:52 Viscosity (mPa · s) 2:48 2:39 Viscosity 3Wo / 60 ° (mPa · s) 2:54 2:42
  • The surface tension and viscosity information given in Table 1 apply equally to Table 2. Example D according to the invention shows a good tender. The disadvantages that occur in the comparative examples are eliminated. The formula E is characterized by a special stability, low foam and optimally visible fluorescence. Essentially no residual ink remained on the nozzle plate.
  • QUOTES INCLUDE IN THE DESCRIPTION
  • This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
  • Cited patent literature
    • WO 2006/009701 A2 [0002]
    • WO 2009/020998 A1 [0003]
    • US 2009/0288580 A1 [0004]
    • EP 2028238 A [0005]
    • EP 1586612 A1 [0010]
    • EP 0797636 B1 [0013]

Claims (13)

  1. Aqueous black-pigmented, UV-fluorescent inkjet ink containing a humectant, surfactant, wetting agent and pigment and optionally further additives, characterized in that it contains: about 20 to 30% by weight of humectant in the form of glycerine and a viscosity-increasing co-solvent Humectant, wherein the content of glycerin in the inkjet ink is 6 to 17 wt .-%, about 0.05 to 0.1 wt .-% of surfactant, about 0.1 to 1.5 wt .-% wetting agent, such as 1 to 6 wt .-% anionic self-dispersing black pigment, about 0.2 to 1.5 wt .-% anionic blue-fluorescent optical brightener, optionally further additives and the balance water.
  2. Inkjet ink according to claim 1, characterized in that it contains as humectant about 7 to 15 wt .-% glycerol and / or a total of about 22 to 28 wt .-% humectant, about 0.01 to 0.1 wt .-% surfactant , about 0.25 to 1.5% by weight of wetting agent, about 2 to 4% by weight of anionic self-dispersing black pigment and / or about 0.5 to 1% by weight of anionic, blue-fluorescent optical brightener.
  3. Inkjet ink according to claim 1 or 2, characterized in that the co-humectant in the form of di- and / or polydiols, in particular in the form of glycols as ethylene glycol, diethylene glycol, triethylene glycol and 1,5-pentanediol, and / or in the form of 2-pyrrolidone.
  4. Inkjet ink according to one of Claims 1 to 3, characterized in that the surfactant is in the form of the polyethoxylated 2,4,7,9-tetra-methyl-5-decyne-4,7-ol (Surfynol 440), 2,4 , 7,9-tetra-methyl-5-decyne-4,7-iols (Surfynol 104), a silicone surfactant, in particular a polyether-modified polydimethylsiloxane, an N-alkylpyrrolidone, in particular in the form of 1-octyl-2-ol pyrrolidone or 1-dodecyl-2-pyrrolidone, an n-octylpyrrolidone (Surfadone LP 100) and / or an n-dodecylpyrrolidone (Surfadone LP 300).
  5. Inkjet ink according to at least one of the preceding claims, characterized in that the wetting agent is in the form of an alcohol, in particular in the form of propyl alcohol, Isopropylalkohl, Butyldiglykol and / or a propylene glycol monopropyl ether.
  6. Inkjet ink according to at least one of the preceding claims, characterized in that the particles of the anionic self-dispersing black pigment have on their surface one or more functional anionic groups.
  7. Inkjet ink according to at least one of the preceding claims, characterized in that the anionic, blue-fluorescent optical brightener is a stilbene and / or a pyrazole derivative.
  8. Inkjet ink according to Claim 7, characterized in that the anionic, blue-fluorescent optical brightener has the CI index number Fluorescent Brightener 113.
  9. Inkjet ink according to at least one of the preceding claims, characterized in that it contains a biocidal preservative in the form of a thiazole and / or isothiazole compound, in particular as a 1,2-benzisothiazolin-3-one compound, and / or an isodiazole Contains derivative.
  10. Inkjet ink according to at least one of the preceding claims, characterized in that the average particle size of the anionic self-dispersing black pigment is below about 0.3 μm, in particular between 0.03 and 0.18 μm.
  11. Inkjet ink according to at least one of the preceding claims, characterized in that the static surface tension (determined by the ring method according to Du Noüy) is between about 30 to 45 mN / m, in particular between about 35 and 42 mN / m.
  12. Inkjet ink according to at least one of the preceding claims, characterized in that the dynamic viscosity about 2 to 3 mPa · s (measured with the cone plate rheometer), in particular about 2.2 to 2.7 mPa · s.
  13. Inkjet ink according to at least one of the preceding claims, characterized in that the pH is between 5 and 10, in particular between 6 and 9.
DE201010018364 2010-04-26 2010-04-26 Aqueous black-pigmented, UV-fluorescent inkjet ink comprises humectant, surfactant, wetting agent, pigment, optionally additives and remaining water Withdrawn DE102010018364A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3027606A1 (en) * 2015-03-02 2016-04-29 Commissariat Energie Atomique Process for producing a luminescent black ink and luminescent black ink thus obtained
EP3431558A4 (en) * 2016-03-14 2019-03-27 Toyo Ink SC Holdings Co., Ltd. Water-based ink-jet ink

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0797636B1 (en) 1994-12-15 2000-05-03 Cabot Corporation Ink jet ink formulations containing modified carbon products
EP1586612A1 (en) 2004-04-15 2005-10-19 Pelikan Hardcopy Production AG Aqueous ink for ink jets
WO2006009701A2 (en) 2004-06-22 2006-01-26 Pitney Bowes Inc. Ir absorbing photosensitive optically variable ink compositions and process
WO2009020998A1 (en) 2007-08-08 2009-02-12 Lexmark International, Inc. Fluorescent-wax emulsion for pigment ink detection
EP2028238A1 (en) 2007-08-09 2009-02-25 Fujifilm Corporation Water-based ink composition, ink set and image recording method
US20090288580A1 (en) 2008-05-23 2009-11-26 Xiaorong Cai Fluorescent Additives For Ink

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0797636B1 (en) 1994-12-15 2000-05-03 Cabot Corporation Ink jet ink formulations containing modified carbon products
EP1586612A1 (en) 2004-04-15 2005-10-19 Pelikan Hardcopy Production AG Aqueous ink for ink jets
WO2006009701A2 (en) 2004-06-22 2006-01-26 Pitney Bowes Inc. Ir absorbing photosensitive optically variable ink compositions and process
WO2009020998A1 (en) 2007-08-08 2009-02-12 Lexmark International, Inc. Fluorescent-wax emulsion for pigment ink detection
EP2028238A1 (en) 2007-08-09 2009-02-25 Fujifilm Corporation Water-based ink composition, ink set and image recording method
US20090288580A1 (en) 2008-05-23 2009-11-26 Xiaorong Cai Fluorescent Additives For Ink

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3027606A1 (en) * 2015-03-02 2016-04-29 Commissariat Energie Atomique Process for producing a luminescent black ink and luminescent black ink thus obtained
EP3431558A4 (en) * 2016-03-14 2019-03-27 Toyo Ink SC Holdings Co., Ltd. Water-based ink-jet ink

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